ASTM D7599-2009e2 0625 Standard Test Method for Determination of Diethanolamine Triethanolamine N-Methyldiethanolamine and N-Ethyldiethanolamine in Water by Single Reaction Monitor.pdf

1、Designation: D7599 092Standard 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; t

2、he 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.1N

3、OTEThis test method was changed editorially in February 2012.2NOTEAdded research report footnote to Section 16 editorially in June 2013.1. Scope1.1 This procedure covers the determination ofdiethanolamine, triethanolamine, N-methyldiethanolamine andN-ethyldiethanolamine (referred to collectively as

4、ethano-lamines in this test method) in surface water by direct injectionusing liquid chromatography (LC) and detected with tandemmass spectrometry (MS/MS). These analytes are qualitativelyand quantitatively determined by this method. This methodadheres to single reaction monitoring (SRM) mass spectr

5、om-etry.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 thisstandard.1.4 The Detection Verification Level (DVL) and ReportingRange for the ethanol

6、amines 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/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

7、 limit is the concentration of the Level 1calibration standard as shown in Table 2 for diethanolamine,triethanolamine, 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 whi

8、ch did not meet the DVLcriteria. The DVL for N-methyldiethanolamine is at 10 g/L,which forces a raised reporting 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 le

9、vel was 88 % asshown in Table 3. If your instruments sensitivity can meet therequirements in this test method, 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

10、the user of this standard to establish appro-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

11、of Precision and Bias ofApplicable Test 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 Specificat

12、ionsfor Standard Test Methods for Water 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 Methods31This test method i

13、s 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 Dec. 1, 2009. Published January 2010. DOI: 10.1520/D7599-09E02.2For referenced ASTM standards, visit the ASTM

14、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 onthe ASTM website.3Available from National Technical Information Service (NTIS), U.S. Depart-ment of Commerce, 5285 Port Royal

15、 Road, Springfield, VA, 22161 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. Terminology3.1 Definitions:3.1.1 detection verification level (DVL), na concentrationthat h

16、as 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.3.1.3 ethanolamines, nin this test method,diethanolamine, triethanolamine, N-methyldiethanolam

17、ine andN-ethyldiethanolamine collectively.3.2 Abbreviations:3.2.1 NDnon-detect4. Summary of Test Methods4.1 This is a performance-based method and modificationsare allowed to improve performance.4.2 For ethanolamines analysis, samples are shipped to thelab between 0C and 6C and analyzed within 7 day

18、s ofcollection. In the lab, the samples are spiked with surrogate,filtered using a syringe-driven Millex HV PVDF filter unit andanalyzed directly by LC/MS/MS.4.3 Diethanolamine, triethanolamine,N-methyldiethanolamine and N-ethyldiethanolamine and di-ethanolamine-D8(surrogate) are identified by reten

19、tion timeand one SRM transition. The target analytes and surrogate arequantitated using the SRM transitions utilizing an externalcalibration. The final report issued for each sample lists theconcentration of diethanolamine, triethanolamine,N-methyldiethanolamine and N-ethyldiethanolamine and thediet

20、hanolamine-D8surrogate recovery.5. Significance and Use5.1 N-Ethyldiethanolamine, N-methyldiethanolamine andtriethanolamine are Schedule 3 compounds under the ChemicalWeapons Convention (CWC). Schedule 3 chemicals includethose that have been produced, stockpiled or used as achemical weapon, poses ot

21、herwise a risk to the object andpurpose of the CWC because they possess such lethal orincapacitating toxicity as well as other properties that mightenable it to be used as a chemical weapon, poses otherwise arisk to the object and purpose of the CWC by virtue of itsimportance in the production of on

22、e or more chemicals listed inSchedules 1 or 2, or it may be produced in large commercialquantities for purposes not prohibited under the CWC.4Etha-nolamines have a broad spectrum of applications. They areused to produce adhesives, agricultural products, cement grind-ing aids, concrete additives, det

23、ergents, specialty cleaners,personal care products, gas treatments, metalwork, oil wellchemicals, packaging and printing inks, photographicchemicals, rubber, textile finishing, urethane coatings, textilelubricants, polishes, pesticides, and pharmaceuticals. Ethano-lamines are readily dissolved in wa

24、ter, biodegradable and thebio-concentration potential is low.55.2 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

25、 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. Detergentscontaining ethanolamines mus

26、t not be used to clean glassware.The glassware is then dried and heated in an oven at 250C for15 to 30 minutes. All glassware is subsequently cleaned withacetone, then methanol.6.3 All reagents and solvents should be pesticide residuepurity or higher to minimize interference problems.6.4 Matrix inte

27、rferences 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 System7.1.1 Liquid Chromatography (LC) SystemAcomplete LCsystem is needed in

28、 order to analyze samples.6Asystem that iscapable of performing at the flows, pressures, controlledtemperatures, sample volumes and requirements of the stan-dard may be used.7.1.2 Analytical Column-WatersAtlantis HILIC Silica,100 mm 2.1 mm, 3 m particle size, or equivalent.7.1.3 Tandem Mass Spectrom

29、eter (MS/MS) SystemAMS/MS system capable of MRM analysis.7A system that iscapable of performing at the requirements 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 Corporat

30、ion, Catalog # SLHV033NS) or similarmay be used.4Additional information about CWC and ethanolamines are available on theInternet at http:/www.opcw.org (2009).5Additional information can be found on the Dow Chemical Company websiteat http:/ (2009).6A Waters Alliance High Performance Liquid Chromatogr

31、aphy (HPLC) Systemwas used to develop this test method. The multi-laboratory study included Agilentand Waters LC systems.7A Waters Quattro micro API mass spectrometer was used to develop this testmethod. The multi-laboratory study included Applied Biosystems, Varian andWaters mass spectrometers.TABL

32、E 1 Detection Verification Level and Reporting RangeAnalyte DVL (g/L) Reporting Range(g/L)Diethanolamine 5 25-500Triethanolamine 5 25-500N-Ethyldiethanolamine 5 25-500N-Methyldiethanolamine 10 50-500D7599 09227.2.1.1 A25-mL lock tip glass syringe size is recommendedsince a 25-mL sample size is used

33、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 spectropho-tometry grade che

34、micals 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.8Other reagent grades may beused provided they are first determined to be of sufficientlyhigh purity to permit their use

35、 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

36、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 acetate (CAS # 631-61-8).8.8 Diethanolamine (CAS # 111-42-2).8.9 Triethanolamine (CAS # 102-71-6).8.10 N-Ethyldiethanolamine (CA

37、S # 139-87-7).8.11 N-Methyldiethanolamine (CAS # 105-59-9).8.12 Bis(2-hydroxyethyl)-D8-amine; (Diethanolamine-D8),where the ethylene moieties contain all2H (CAS # 103691-51-6).8.12.1 Diethanolamine-D8is used as a surrogate in thisstandard.8Reagent Chemicals, American Chemical Society Specifications,

38、 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. Pharmacopeial Convention, Inc.

39、 (USPC), Rockville,MD.FIG. 1 Example SRM Chromatograms Signal/Noise RatiosTABLE 2 Concentrations of Calibration Standards (PPB)Analyte/Surrogate LV 1 LV 2 LV 3 LV 4 LV 5 LV 6 LV 7Diethanolamine 25 50 75 150 250 350 500Triethanolamine 25 50 75 150 250 350 500N-Ethyldiethanolamine 25 50 75 150 250 350

40、 500N-Methyldiethanolamine 25 50 75 150 250 350 500Diethanolamine-D8(Surrogate) 25 50 75 150 250 350 500D7599 09239. 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 Saf

41、etyData Sheets (MSDS) for all reagents 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 samplin

42、g prac-tices should be followed. Refer to Guide D3856 and PracticesD3694.10.2 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 Conditions6:11.1.1 Injection v

43、olumes 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.Thegradient conditions for the liquid chromatograph are shown inTable 4.11.1.2 TemperaturesColumn, 30C; Samplecompartment, 15C.11.1.3 Seal WashSol

44、vent: 50 % Acetonitrile/50 % Water;Time: 5 minutes.11.1.4 Needle WashSolvent: 50 % Acetonitrile/50 % Wa-ter; Normal wash, approximately 13 second wash time.11.1.5 Autosampler PurgeThree loop volumes.11.1.6 Specific instrument manufacturer wash/purge speci-fications should be followed in order to eli

45、minate samplecarry-over in the analysis of ethanolamines.11.2 Mass Spectrometer Parameters7:11.2.1 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

46、 10 scans per peakfor adequate quantitation. This standard contains only onesurrogate and four target compounds which are located in theTABLE 3 Multi-Laboratory Recovery Data in Reagent WaterAnalyte SpikeConc.(ppb)# Results # Labs Bias PrecisionMeanRecovery(%)MinRecovery(%)MaxRecovery(%)Overall SD(%

47、)Pooledwithin-labSD (%)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 1

48、7.98 5.90 17.61 5.70Triethanolamine 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-Ethyldiethanola

49、mine 25 24 6 90.61 31.00 132.00 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 25.24 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-Methyldiethanol