ASTM D7599-16(2017)
(Test Method)Standard Test Method for Determination of Diethanolamine, Triethanolamine, N-Methyldiethanolamine and N-Ethyldiethanolamine in Water by Single Reaction Monitoring Liquid Chromatography/Tandem Mass Spectrometry (LC/MS/MS)
Standard Test Method for Determination of Diethanolamine, Triethanolamine, <emph type="ital">N</emph>-Methyldiethanolamine and <emph type="ital">N</emph >-Ethyldiethanolamine in Water by Single Reaction Monitoring Liquid Chromatography/Tandem Mass Spectrometry (LC/MS/MS)
SIGNIFICANCE AND USE
5.1 N-Ethyldiethanolamine, N-methyldiethanolamine and triethanolamine are Schedule 3 compounds under the Chemical Weapons Convention (CWC). Schedule 3 chemicals include those that have been produced, stockpiled or used as a chemical weapon, poses otherwise a risk to the object and purpose of the CWC because they possess such lethal or incapacitating toxicity as well as other properties that might enable it to be used as a chemical weapon, poses otherwise a risk to the object and purpose of the CWC by virtue of it’s importance in the production of one or more chemicals listed in Schedules 1 or 2, or it may be produced in large commercial quantities for purposes not prohibited under the CWC.4 Ethanolamines have a broad spectrum of applications. They are used to produce adhesives, agricultural products, cement grinding aids, concrete additives, detergents, specialty cleaners, personal care products, gas treatments, metalwork, oil well chemicals, packaging and printing inks, photographic chemicals, rubber, textile finishing, urethane coatings, textile lubricants, polishes, pesticides, and pharmaceuticals. Ethanolamines are readily dissolved in water, biodegradable and the bio-concentration potential is low.5
5.2 This test method has been investigated for use with reagent and surface water.
SCOPE
1.1 This procedure covers the determination of diethanolamine, triethanolamine, N-methyldiethanolamine and N-ethyldiethanolamine (referred to collectively as ethanolamines in this test method) in surface water by direct injection using liquid chromatography (LC) and detected with tandem mass spectrometry (MS/MS). These analytes are qualitatively and quantitatively determined by this test method. This test method adheres to single reaction monitoring (SRM) mass spectrometry.
1.2 This test method has been developed by U.S. EPA Region 5 Chicago Regional Laboratory (CRL).
1.3 The values stated in SI units are to be regarded as standard. No other units of measurement are included in this standard.
1.4 The Detection Verification Level (DVL) and Reporting Range for the ethanolamines are listed in Table 1.
TABLE 1 Detection Verification Level and Reporting Range
Analyte
DVL (μg/L)
Reporting Range (μg/L)
Diethanolamine
5
25–500
Triethanolamine
5
25–500
N-Ethyldiethanolamine
5
25–500
N-Methyldiethanolamine
10
50–500
1.4.1 The DVL is required to be at a concentration at least 3 times below the Reporting Limit (RL) and have a signal/noise ratio greater than 3:1. Fig. 1 displays the signal/noise ratios at the DVLs and at higher concentrations for N-methyldiethanolamine.
FIG. 1 Example SRM Chromatograms Signal/Noise Ratios
1.4.2 The reporting limit is the concentration of the Level 1 calibration standard as shown in Table 2 for diethanolamine, triethanolamine, and N-ethyldiethanolamine and Level 2 for N-methyldiethanolamine. The reporting limit for N-methyldiethanolamine is set at 50 μg/L due to poor sensitivity at a 5 μg/L concentration which did not meet the DVL criteria. The DVL for N-methyldiethanolamine is at 10 μg/L, which forces a raised reporting limit (chromatograms are shown in Fig. 1). However, the multi-laboratory validation required a spike of all target analytes at 25 μg/L. The mean recovery for N-methyldiethanolamine at this level was 88 % as shown in Table 3. If your instrument’s sensitivity can meet the requirements in this test method, N-methyldiethanolamine may have a 25 μg/L reporting limit.
TABLE 2 Concentrations of Calibration Standards (PPB)
Analyte/Surrogate
LV 1
LV 2
LV 3
LV 4
LV 5
LV 6
LV 7
Diethanolamine
25
50
75
150
250
350
500
Triethanolamine
25
50
75
150
250
350
500
N-Ethyldiethanolamine
25
50
75
150
250
350
500
N-Methyldiethanolamine
25
50
75
150
250
350
500
Diethanolamine-D8 (Su...
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This international standard was developed in accordance with internationally recognized principles on standardization established in the Decision on Principles for the
Development of International Standards, Guides and Recommendations issued by the World Trade Organization Technical Barriers to Trade (TBT) Committee.
Designation:D7599 −16 (Reapproved 2017)
Standard Test Method for
Determination of Diethanolamine, Triethanolamine,
N-Methyldiethanolamine and N-Ethyldiethanolamine in Water
by Single Reaction Monitoring Liquid Chromatography/
Tandem Mass Spectrometry (LC/MS/MS)
This standard is issued under the fixed designation D7599; the number immediately following the designation indicates the year of
original adoption or, in the case of revision, the year of last revision.Anumber in parentheses indicates the year of last reapproval.A
superscript epsilon (´) indicates an editorial change since the last revision or reapproval.
1. Scope shown in Fig. 1). However, the multi-laboratory validation
required a spike of all target analytes at 25 µg/L. The mean
1.1 This procedure covers the determination of
recoveryfor N-methyldiethanolamineatthislevelwas88%as
diethanolamine, triethanolamine, N-methyldiethanolamine and
shown in Table 3. If your instrument’s sensitivity can meet the
N-ethyldiethanolamine (referred to collectively as ethano-
requirementsinthistestmethod, N-methyldiethanolaminemay
laminesinthistestmethod)insurfacewaterbydirectinjection
have a 25 µg/L reporting limit.
using liquid chromatography (LC) and detected with tandem
1.5 This standard does not purport to address all of the
mass spectrometry (MS/MS). These analytes are qualitatively
safety concerns, if any, associated with its use. It is the
and quantitatively determined by this test method. This test
responsibility of the user of this standard to establish appro-
method adheres to single reaction monitoring (SRM) mass
priate safety and health practices and determine the applica-
spectrometry.
bility of regulatory limitations prior to use.
1.2 This test method has been developed by U.S. EPA
1.6 This international standard was developed in accor-
Region 5 Chicago Regional Laboratory (CRL).
dance with internationally recognized principles on standard-
1.3 The values stated in SI units are to be regarded as
ization established in the Decision on Principles for the
standard. No other units of measurement are included in this
Development of International Standards, Guides and Recom-
standard.
mendations issued by the World Trade Organization Technical
Barriers to Trade (TBT) Committee.
1.4 The Detection Verification Level (DVL) and Reporting
Range for the ethanolamines are listed in Table 1.
2. Referenced Documents
1.4.1 The DVL is required to be at a concentration at least
2.1 ASTM Standards:
3 times below the Reporting Limit (RL) and have a signal/
D1129Terminology Relating to Water
noise ratio greater than 3:1. Fig. 1 displays the signal/noise
D1193Specification for Reagent Water
ratios at the DVLs and at higher concentrations for
D2777Practice for Determination of Precision and Bias of
N-methyldiethanolamine.
Applicable Test Methods of Committee D19 on Water
1.4.2 The reporting limit is the concentration of the Level 1
D3856Guide for Management Systems in Laboratories
calibration standard as shown in Table 2 for diethanolamine,
Engaged in Analysis of Water
triethanolamine, and N-ethyldiethanolamine and Level 2 for
D3694Practices for Preparation of Sample Containers and
N-methyldiethanolamine. The reporting limit for
for Preservation of Organic Constituents
N-methyldiethanolamine is set at 50 µg/L due to poor sensi-
D5847Practice for Writing Quality Control Specifications
tivity at a 5 µg/L concentration which did not meet the DVL
for Standard Test Methods for Water Analysis
criteria. The DVL for N-methyldiethanolamine is at 10 µg/L,
E2554Practice for Estimating and Monitoring the Uncer-
which forces a raised reporting limit (chromatograms are
tainty of Test Results of a Test Method Using Control
Chart Techniques
This test method is under the jurisdiction ofASTM Committee D19 on Water
andisthedirectresponsibilityofSubcommitteeD19.06onMethodsforAnalysisfor
Organic Substances in Water. For referenced ASTM standards, visit the ASTM website, www.astm.org, or
Current edition approved June 15, 2017. Published July 2017. Originally contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM
approved in 2009. Last previous edition approved in 2016 as D7599 – 16. DOI: Standards volume information, refer to the standard’s Document Summary page on
10.1520/D7599-16R17. the ASTM website.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
D7599−16 (2017)
TABLE 1 Detection Verification Level and Reporting Range
3.3.20 SDS, n—Safety Data Sheets
Reporting Range
Analyte DVL (µg/L) 3.3.21 SRM, n—Single Reaction Monitoring
(µg/L)
3.3.22 SS, n—Surrogate Standard
Diethanolamine 5 25–500
Triethanolamine 5 25–500
3.3.23 TC, n—Target Compound
N-Ethyldiethanolamine 5 25–500
N-Methyldiethanolamine 10 50–500 –6
3.3.24 µM, n—micromolar,1×10 moles/L
3.3.25 VOA, n—Volatile Organic Analysis
2.2 Other Documents:
4. Summary of Test Methods
EPApublication SW-846Test Methods for Evaluating Solid
Waste, Physical/Chemical Methods
4.1 This is a performance-based method and modifications
are allowed to improve performance.
3. Terminology
4.2 For ethanolamines analysis, samples are shipped to the
3.1 Definitions:
lab between 0°C and 6°C and analyzed within 7 days of
3.1.1 For definitions of terms used in this standard, refer to
collection. In the lab, the samples are spiked with surrogate,
Terminology D1129.
filtered using a syringe-driven filter unit and analyzed directly
3.2 Definitions of Terms Specific to This Standard:
by LC/MS/MS.
3.2.1 detection verification level, DVL, n—a concentration
4.3 Diethanolamine, triethanolamine,
that has a signal/noise ratio greater than 3:1 and is at least 3
N-methyldiethanolamine and N-ethyldiethanolamine and di-
times below the reporting limit (RL).
ethanolamine-D (surrogate) are identified by retention time
3.2.2 ethanolamines, n—in this test method,
and one SRM transition. The target analytes and surrogate are
diethanolamine, triethanolamine, N-methyldiethanolamine and
quantitated using the SRM transitions utilizing an external
N-ethyldiethanolamine collectively.
calibration. The final report issued for each sample lists the
3.2.3 independent reference material, IRM, n—amaterialof
concentration of diethanolamine, triethanolamine,
known purity and concentration obtained either from the
N-methyldiethanolamine and N-ethyldiethanolamine and the
NationalInstituteofStandardsandTechnology(NIST)orother
diethanolamine-D surrogate recovery.
reputable supplier. The IRM shall be obtained from a different
lot of material than is used for calibration.
5. Significance and Use
3.3 Acronyms:
5.1 N-Ethyldiethanolamine, N-methyldiethanolamine and
3.3.1 CCC, n—Continuing Calibration Check
triethanolamineareSchedule3compoundsundertheChemical
3.3.2 IC, n—Initial Calibration
Weapons Convention (CWC). Schedule 3 chemicals include
3.3.3 LC, n—Liquid Chromatography those that have been produced, stockpiled or used as a
chemical weapon, poses otherwise a risk to the object and
3.3.4 LCS/LCSD, n—Laboratory Control Sample/
purpose of the CWC because they possess such lethal or
Laboratory Control Sample Duplicate
incapacitating toxicity as well as other properties that might
3.3.5 MDL, n—Method Detection Limit
enable it to be used as a chemical weapon, poses otherwise a
3.3.6 MeOH, n—Methanol
risk to the object and purpose of the CWC by virtue of it’s
–3
3.3.7 mM, n—millimolar,1×10 moles/L importanceintheproductionofoneormorechemicalslistedin
Schedules 1 or 2, or it may be produced in large commercial
3.3.8 MRM, n—Multiple Reaction Monitoring
quantities for purposes not prohibited under the CWC. Etha-
3.3.9 MS/MSD, n—Matrix Spike/Matrix Spike Duplicate
nolamines have a broad spectrum of applications. They are
3.3.10 NA, adj—Not Available
usedtoproduceadhesives,agriculturalproducts,cementgrind-
ing aids, concrete additives, detergents, specialty cleaners,
3.3.11 ND, n—non-detect
personal care products, gas treatments, metalwork, oil well
3.3.12 P&A, n—Precision and Accuracy
chemicals, packaging and printing inks, photographic
3.3.13 PPB, n—parts per billion
chemicals, rubber, textile finishing, urethane coatings, textile
3.3.14 PPT, n—parts per trillion
lubricants, polishes, pesticides, and pharmaceuticals. Ethano-
lamines are readily dissolved in water, biodegradable and the
3.3.15 QA, adj—Quality Assurance
bio-concentration potential is low.
3.3.16 QC, adj—Quality Control
5.2 This test method has been investigated for use with
3.3.17 RL, n—Reporting Limit
reagent and surface water.
3.3.18 RSD, n—Relative Standard Deviation
3.3.19 RT, n—Retention Time
Additional information about CWC and ethanolamines are available from the
Available from National Technical Information Service (NTIS), U.S. Depart- Organisation for the Prohibition of Chemical Weapons, https://www.opcw.org.
ment of Commerce, 5285 Port Royal Road, Springfield, VA, 22161 or at http:// Additional information can be found on the Dow Chemical Company website
www.epa.gov/epawaste/hazard/testmethods/index.htm. at http://www.dow.com/amines/prod/index.htm.
D7599−16 (2017)
FIG. 1Example SRM Chromatograms Signal/Noise Ratios
TABLE 2 Concentrations of Calibration Standards (PPB)
6.4 Matrix interferences may be caused by contaminants
Analyte/Surrogate LV 1 LV 2 LV 3 LV 4 LV 5 LV 6 LV 7 that are co-extracted from the sample. The extent of matrix
Diethanolamine 25 50 75 150 250 350 500 interferences can vary considerably from sample source de-
Triethanolamine 25 50 75 150 250 350 500
pending on variations of the sample matrix.
N-Ethyldiethanolamine 25 50 75 150 250 350 500
N-Methyldiethanolamine 25 50 75 150 250 350 500
7. Apparatus
Diethanolamine-D (Surrogate) 25 50 75 150 250 350 500
7.1 LC/MS/MS System:
7.1.1 LiquidChromatography(LC)System—AcompleteLC
6. Interferences system is needed in order to analyze samples. This should
include a sample injection system, a solvent pumping system
6.1 Methodinterferencesmaybecausedbycontaminantsin
capable of mixing solvents, a sample compartment capable of
solvents, reagents, glassware and other apparatus producing
maintaining required temperature and a temperature controlled
discrete artifacts or elevated baselines. All of these materials
columncompartment.Asystemthatiscapableofperformingat
are demonstrated to be free from interferences by analyzing
the flows, pressures, controlled temperatures, sample volumes
laboratory reagent blanks under the same conditions as
and requirements of the standard may be used.
samples.
7.1.2 Analytical Column-Waters —A HILIC column was
6.2 All glassware is washed in hot water with a detergent,
used to develop this test method. Any column that achieves
rinsed in hot water followed by distilled water. Detergents
containing ethanolamines must not be used to clean glassware.
AWatersAlliance High Performance Liquid Chromatography (HPLC) System
Theglasswareisthendriedandheatedinanovenat250°Cfor
(a trademark of the Waters Corporation, Milford, MA), or equivalent, was found
15 to 30 minutes. All glassware is subsequently cleaned with
suitable for use. The multi-laboratory study included Agilent and Waters LC
acetone, then methanol. systems.
AWatersAtlantis(atrademarkoftheWatersCorporation,Milford,MA)HILIC
6.3 All reagents and solvents should be pesticide residue
Silica,100mm×2.1mm,3µmparticlesize,orequivalent,hasbeenfoundsuitable
purity or higher to minimize interference problems. for use.
D7599−16 (2017)
TABLE 3 Multi-Laboratory Recovery Data in Reagent Water
Bias Precision
Spike Conc.
Mean Min Max Pooled Pooled
Analyte # Results # Labs
Overall SD Overall
(ppb)
Recovery Recovery Recovery within-lab within-lab
(%) RSD (%)
(%) (%) (%) SD (%) RSD (%)
Diethanolamine 25 24 6 96.34 51.00 156.96 31.31 10.96 32.50 9.49
Diethanolamine 50 24 6 101.41 54.00 154.80 29.54 7.97 29.13 7.91
Diethanolamine 200 24 6 101.57 61.00 138.00 20.98 10.50 20.66 10.85
Diethanolamine 425 24 6 102.06 70.00 138.82 17.98 5.90 17.61 5.70
Triethanolamine 25 24 6 87.70 35.96 157.20 27.00 25.18 30.79 27.48
Triethanolamine 50 24 6 94.95 67.00 121.66 16.39 9.57 17.26 9.66
Triethanolamine 200 22 6 105.00 79.50 132.00 14.06 11.81 13.39 11.52
Triethanolamine 425 24 6 96.94 40.00 144.94 27.56 4.41 28.43 5.76
N-Ethyldiethanolamine 25 24 6 90.61 31.00 132.00 39.42 7.47 43.51 10.42
N-Ethyldiethanolamine 50 23 6 111.88 49.00 146.00 28.71 7.19 25.66 7.56
N-Ethyldiethanolamine 200 24 6 106.20 60.00 134.00 23.09 11.96 21.74 12.23
N-Ethyldiethanolamine 425 24 6 99.67 51.00 130.00 23.07 4.68 23.15 6.01
N-Methyldiethanolamine 25 24 6 88.43 41.72 133.60 25.24 13.29 28.55 16.70
N-Methyldiethanolamine 50 24 6 102.28 56.00 153.80 25.85 8.73 25.27 8.22
N-Methyldiethanolamine 200 24 6 101.02 59.00 136.50 20.07 9.51 19.87 9.54
N-Methyldiethanolamine 425 24 6 94.75 63.00 115.76 15.02 3.34 15.85 3.72
Diethanolamine- 200 96 6 103.02 60.00 151.95 21.13 9.40 20.51 9.25
D (Surrogate)
adequateresolutionmaybeused.Theretentiontimesandorder 8.2 Purity of Water—Unless otherwise indicated, references
of elution may change depending on the column that is used towatershallbeunderstoodtomeanreagentwaterconforming
and need to be monitored. toType1ofSpecificationD1193.Itmustbedemonstratedthat
7.1.3 Tandem Mass Spectrometer (MS/MS) System—A this water does not contain contaminants at concentrations
MS/MS system capable of MRM analysis. A system that is sufficient to interfere with the analysis.
capableofperformingattherequirementsinthisstandardmay
8.3 Gases—Ultrapure nitrogen and argon.
be used.
8.4 Acetonitrile (CAS # 75-05-8).
7.2 Filtration Device:
8.5 Methanol (CAS # 67-56-1).
7.2.1 Hypodermic syringe—A luer-lock tip glass syringe
capable of holding a syringe-driven filter unit.
8.6 Acetone (CAS # 67-64-1).
7.2.1.1 A25-mLlocktipglasssyringesizeisrecommended
8.7 Ammonium acetate (CAS # 631-61-8).
since a 25-mL sample size is used in this test method.
7.2.2 Filter unit —PVDF filter units were used to filter the
8.8 Diethanolamine (CAS # 111-42-2).
samples.
8.9 Triethanolamine (CAS # 102-71-6).
8. Reagents and Materials
8.10 N-Ethyldiethanolamine (CAS # 139-87-7).
8.1 Purity of Reagents—High-performance liquid chroma-
8.11 N-Methyldiethanolamine (CAS # 105-59-9).
tography (HPLC) pesticide residue analysis and spectropho-
8.12 Bis(2-hydroxyethyl)-D -amine; (Diethanolamine-D ),
8 8
tometry grade chemicals shall be used in all tests. Unless
wheretheethylenemoietiescontainall H(CAS#103691-51-
indicated otherwise, it is intended that all reagents shall
6).
conform to th
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