ASTM D7599-16
(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 US 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.
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. 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
...
General Information
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Designation:D7599 −16
Standard Test Method for
Determination of Diethanolamine, Triethanolamine,
N-Methyldiethanolamine and N-Ethyldiethanolamine in Water
by Single Reaction Monitoring Liquid Chromatography/
1
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 recoveryfor N-methyldiethanolamineatthislevelwas88%as
shown in Table 3. If your instrument’s sensitivity can meet the
1.1 This procedure covers the determination of
requirementsinthistestmethod, N-methyldiethanolaminemay
diethanolamine, triethanolamine, N-methyldiethanolamine and
have a 25 µg/L reporting limit.
N-ethyldiethanolamine (referred to collectively as ethano-
1.5 This standard does not purport to address all of the
laminesinthistestmethod)insurfacewaterbydirectinjection
safety concerns, if any, associated with its use. It is the
using liquid chromatography (LC) and detected with tandem
responsibility of the user of this standard to establish appro-
mass spectrometry (MS/MS). These analytes are qualitatively
priate safety and health practices and determine the applica-
and quantitatively determined by this test method. This test
bility of regulatory limitations prior to use.
method adheres to single reaction monitoring (SRM) mass
spectrometry.
2. Referenced Documents
1.2 ThistestmethodhasbeendevelopedbyUSEPARegion
2
2.1 ASTM Standards:
5 Chicago Regional Laboratory (CRL).
D1129Terminology Relating to Water
1.3 The values stated in SI units are to be regarded as
D1193Specification for Reagent Water
standard. No other units of measurement are included in this
D2777Practice for Determination of Precision and Bias of
standard.
Applicable Test Methods of Committee D19 on Water
1.4 The Detection Verification Level (DVL) and Reporting
D3856Guide for Management Systems in Laboratories
Range for the ethanolamines are listed in Table 1.
Engaged in Analysis of Water
1.4.1 The DVL is required to be at a concentration at least
D3694Practices for Preparation of Sample Containers and
3 times below the Reporting Limit (RL) and have a signal/
for Preservation of Organic Constituents
noise ratio greater than 3:1. Fig. 1 displays the signal/noise
D5847Practice for Writing Quality Control Specifications
ratios at the DVLs and at higher concentrations for
for Standard Test Methods for Water Analysis
N-methyldiethanolamine.
E2554Practice for Estimating and Monitoring the Uncer-
1.4.2 The reporting limit is the concentration of the Level 1
tainty of Test Results of a Test Method Using Control
calibration standard as shown in Table 2 for diethanolamine,
Chart Techniques
triethanolamine, and N-ethyldiethanolamine and Level 2 for
2.2 Other Documents:
N-methyldiethanolamine. The reporting limit for
EPApublication SW-846Test Methods for Evaluating Solid
N-methyldiethanolamine is set at 50 µg/L due to poor sensi-
3
Waste, Physical/Chemical Methods
tivity at a 5 µg/L concentration which did not meet the DVL
criteria. The DVL for N-methyldiethanolamine is at 10 µg/L,
3. Terminology
which forces a raised reporting limit (chromatograms are
3.1 Definitions:
shown in Fig. 1). However, the multi-laboratory validation
required a spike of all target analytes at 25 µg/L. The mean
2
For referenced ASTM standards, visit the ASTM website, www.astm.org, or
1
This test method is under the jurisdiction ofASTM Committee D19 on Water contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM
andisthedirectresponsibilityofSubcommitteeD19.06onMethodsforAnalysisfor Standards volume information, refer to the standard’s Document Summary page on
Organic Substances in Water. the ASTM website.
3
Current edition approved Feb. 1, 2016. Published May 2016. Originally Available from National Technical Information Service (NTIS), U.S. Depart-
ɛ2
approved in 2009. Last previous edition approved in 2009 as D7599 – 09 . DOI: ment of Commerce, 5285 Port Royal Road, Springfield, VA, 22161 or at http://
10.1520/D7599-16. www.epa.gov/epawaste/hazard/testmethods/index.htm.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
1
---------------------- Page: 1 ----------------------
D7599−16
TABLE 1 Detection Verification Level and Reporting Range
4. Summary of Test Methods
Analyte DVL (µg/L) Reporting Range
4.1 This is a performance-based method and modifications
(µg/L)
are allowed to improve performance.
Diethanolamine 5 25-500
Triethanolamine 5 25-500
4.2 For ethanolamines analysis, samples are shipped to the
N-Ethyldiethanolamin
...
This document is not an ASTM standard and is intended only to provide the user of an ASTM standard an indication of what changes have been made to the previous version. Because
it may not be technically possible to adequately depict all changes accurately, ASTM recommends that users consult prior editions as appropriate. In all cases only the current version
of the standard as published by ASTM is to be considered the official document.
´2
Designation: D7599 − 09 D7599 − 16
Standard Test Method for
Determination of Diethanolamine, Triethanolamine,
N-Methyldiethanolamine and N-Ethyldiethanolamine in Water
by Single Reaction Monitoring Liquid Chromatography/
1
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. A number in parentheses indicates the year of last reapproval. A
superscript epsilon (´) indicates an editorial change since the last revision or reapproval.
1
ε NOTE—This test method was changed editorially in February 2012.
2
ε NOTE—Added research report footnote to Section 16 editorially in June 2013.
1. 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 US 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.
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.
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.
1.5 This standard does not purport to address all of the safety concerns, if any, associated with its use. It is the responsibility
of the user of this standard to establish appropriate safety and health practices and determine the applicability of regulatory
limitations prior to use.
2. Referenced Documents
2
2.1 ASTM Standards:
D1129 Terminology Relating to Water
D1193 Specification for Reagent Water
D2777 Practice for Determination of Precision and Bias of Applicable Test Methods of Committee D19 on Water
D3856 Guide for Management Systems in Laboratories Engaged in Analysis of Water
D3694 Practices for Preparation of Sample Containers and for Preservation of Organic Constituents
D5847 Practice for Writing Quality Control Specifications for Standard Test Methods for Water Analysis
E2554 Practice for Estimating and Monitoring the Uncertainty of Test Results of a Test Method Using Control Chart Techniques
1
This test method is under the jurisdiction of ASTM Committee D19 on Water and is the direct responsibility of Subcommittee D19.06 on Methods for Analysis for
Organic Substances in Water.
Current edition approved Dec. 1, 2009Feb. 1, 2016. Published January 2010May 2016. Originally approved in 2009. Last previous edition approved in 2009 as D7599
ɛ2
– 09 . DOI: 10.1520/D7599-09E02.10.1520/D7599-16.
2
For referenced ASTM standards, visit the ASTM website, www.astm.org, or contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM Standards
volume information, refer to the standard’s Document Summary page on the ASTM website.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
1
---------------------- Page: 1 ----------------------
D7599 − 16
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-Ethyldiet
...
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