1、Designation: D7599 091Standard 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 2012.1. Scope1.1 This procedure covers the determination of dietha-nolamine, triethanolamine, N-methyldiethanolamine andN-ethyldiethanolamine (referred to collectively as ethano-lamines in this test method) in surface water by direct injectionusing liqu
4、id 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 spectrom-etry.1.2 This test method has been developed by US EPARegion5 Chicago Regional
5、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 ethanolamines are listed in Table 1.1.4.1 The DVL is required to be at a concentration at
6、 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 limit is the concentration of the Level 1calibration standard as shown in Table 2
7、 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 which did not meet the DVLcriteria. The DVL for N-methyldiethanolamine is at 10 g/L,w
8、hich 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 level was 88 % asshown in Table 3. If your instruments sensitivity can meet therequi
9、rements 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 the user of this standard to establish appro-priate safety and health practices an
10、d 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 Methods of Committee D19 on WaterD3856 Gui
11、de 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 AnalysisE2554 Practice for Estimating and
12、Monitoring the Uncer-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:1This test method is under the jurisdiction of AS
13、TM 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 February 2012. DOI: 10.1520/D7599-09E01.2For referenced ASTM standards, visit the ASTM website, www.astm.org, orcont
14、act 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, 22161
15、 or at http:/www.epa.gov/epawaste/hazard/testmethods/index.htm.1Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.3.1.1 detection verification level (DVL), na concentrationthat has a signal/noise ratio greater than 3:1 and is at least 3
16、times 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, dietha-nolamine, triethanolamine, N-methyldiethanolamine andN-ethyldiethanolamine collectively.3.2 Abbreviati
17、ons: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 days ofcollection. In the lab, the samples are spiked with
18、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 retention timeand one SRM transition. The target analytes and
19、 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 thediethanolamine-D8surrogate recovery.5. Significance and Use5
20、.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 otherwise a risk to the object andpurpose of the CWC becau
21、se 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 one or more chemicals listed inSchedules 1 or 2, or it may
22、 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, detergents, specialty cleaners,personal care products, gas
23、treatments, metalwork, oil wellchemicals, packaging and printing inks, photographic chemi-cals, rubber, textile finishing, urethane coatings, textile lubri-cants, polishes, pesticides, and pharmaceuticals. Ethano-lamines are readily dissolved in water, biodegradable and thebio-concentration potentia
24、l 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 baselines. All of these materialsare demonstrated t
25、o 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 must not be used to clean glassware.The glassware is th
26、en 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 interferences may be caused by contaminantsthat are co-e
27、xtracted 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) SystemA completeLC system is needed in order to analyze samples.6A systemthat is capable
28、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 3 2.1 mm, 3 m particle size, or equivalent.7.1.3 Tandem Mass Spectrometer (MS/MS) SystemAMS/MS system capable of MRM
29、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 Corporation, Catalog # SLHV033NS) or similarmay be used.
30、7.2.1.1 A 25-mL lock tip glass syringe size is recommendedsince 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.4Additional information about CWC and ethanolamines are avail
31、able 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 Chromatography (HPLC) Systemwas used to develop this test method. The multi-laboratory study included Agilentand Waters
32、 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.TABLE 1 Detection Verification Level and Reporting RangeAnalyte DVL (g/L) Reporting Range (g/L)Diethanolamine 5 2
33、5-500Triethanolamine 5 25-500N-Ethyldiethanolamine 5 25-500N-Methyldiethanolamine 10 50-500D7599 09128. Reagents and Materials8.1 Purity of ReagentsHigh-performance liquid chroma-tography (HPLC) pesticide residue analysis and spectropho-tometry grade chemicals shall be used in all tests. Unlessindic
34、ated 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 without affecting the accuracy ofthe measurem
35、ents.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 to interfere with the analysis.8.3 GasesUltrap
36、ure 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 (CAS # 139-87-7).8.11 N-Methyldiethanolamine (CAS
37、 # 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.9. Hazards9.1 Normal laboratory safety applies to this method. Ana-lysts should wear safety glasses, gloves
38、, 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 SamplingGrab samples must be collected in$25-mL pre-cleaned amber glass bottles with Teflon-linedcaps demonstrated to be free of interferences. T
39、his test method8Reagent 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 St
40、ates Pharmacopeiaand National Formulary, U.S. Pharmacopeial Convention, Inc. (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 500Trieth
41、anolamine 25 50 75 150 250 350 500N-Ethyldiethanolamine 25 50 75 150 250 350 500N-Methyldiethanolamine 25 50 75 150 250 350 500Diethanolamine-D8(Surrogate) 25 50 75 150 250 350 500D7599 0913requires a 25-mL sample size per analysis. Conventionalsampling practices should be followed. Refer to Guide D
42、3856and Practices D3694.10.2 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 volumes of all calibration standards andsamples ar
43、e 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; Sample compart-ment, 15C.11.1.3 Seal WashSolvent: 50 % Acetonitrile/50 % Water;Time: 5 min
44、utes.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 eliminate samplecarry-over in the analysis of eth
45、anolamines.11.2 Mass Spectrometer Parameters7:11.2.1 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.
46、 This standard contains only one surro-gate and four target compounds which are located in the samemultiple reaction monitoring (MRM) experiment window.Variable parameters regarding retention times, SRM Transi-tions and cone and collision energies are shown in Table 5.The instrument is set in the El
47、ectrospray (+) positive setting.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: 14.5Io
48、n Energy 1: 0.5Entrance Energy: 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 3 103TorrInter-Channel Delay: 0.02 secondsInter-Scan Delay: 0.1 secondsRepeats: 1Span:
49、 0 DaltonsDwell: 0.1 Seconds12. 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 followed when performing the test method.12.2 Calibration and StandardizationTo calibrate the in-strument, analyze seven calibration standards containing theseven concentration lev
