ASTM D7599-16(2017)

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...

General Information

• Status: Published
• Publication Date: 14-Jun-2017
• ICS: 13.060.50 - Examination of water for chemical substances
• Technical Committee: D19 - Water
• Drafting Committee: D19.06 - Methods for Analysis for Organic Substances in Water

Relations

• Replaces: ASTM D7599-16 - 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)
• Effective Date: 15-Jun-2017
• Refers: ASTM E2554-18 - Standard Practice for Estimating and Monitoring the Uncertainty of Test Results of a Test Method Using Control Chart Techniques
• Effective Date: 01-Apr-2018
• Refers: ASTM E2554-18e1 - Standard Practice for Estimating and Monitoring the Uncertainty of Test Results of a Test Method Using Control Chart Techniques
• Effective Date: 01-Apr-2018

Standards Content (Sample)

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/
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 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
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
1
This test method is under the jurisdiction ofASTM Committee D19 on Water
andisthedirectresponsibilityofSubcommitteeD19.06onMethodsforAnalysisfor
2
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 [e-mail]. 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
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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
...