ASTM D7597-16
(Test Method)Standard Test Method for Determination of Diisopropyl Methylphosphonate, Ethyl Hydrogen Dimethylamidophosphate, Ethyl Methylphosphonic Acid, Isopropyl Methylphosphonic Acid, Methylphosphonic Acid and Pinacolyl Methylphosphonic Acid in Water by Liquid Chromatography/Tandem Mass Spectrometry
Standard Test Method for Determination of Diisopropyl Methylphosphonate, Ethyl Hydrogen Dimethylamidophosphate, Ethyl Methylphosphonic Acid, Isopropyl Methylphosphonic Acid, Methylphosphonic Acid and Pinacolyl Methylphosphonic Acid in Water by Liquid Chromatography/Tandem Mass Spectrometry
SIGNIFICANCE AND USE
5.1 Organophosphate pesticides affect the nervous system by disrupting the enzyme that regulates acetylcholine, a neurotransmitter. They were developed during the early 19th century, but their effects on insects, which are similar to their effects on humans, were discovered in 1932. Some are poisonous and were used as chemical weapon agents. Organophosphate pesticides are usually not persistent in the environment.4, 5
5.2 This test method is for the analysis of selected organophosphorous-based chemical weapon agent degradation products from Sarin (GB), Soman (GD), Tabun (GA) and VX. This method has been investigated for use with reagent and surface water.
SCOPE
1.1 This procedure covers the determination of diisopropyl methylphosphonate (DIMP), ethyl hydrogen dimethylamidophosphate (EHDMAP), ethyl methylphosphonic acid (EMPA), isopropyl methylphosphonic acid (IMPA), methylphosphonic acid (MPA) and pinacolyl methylphosphonic acid (PMPA) (referred to collectively as organophosphonates in this test method) in surface water by direct injection using liquid chromatography (LC) and detected with tandem mass spectrometry (MS/MS) using electrospray ionization (ESI). These analytes are qualitatively and quantitatively determined by this method. This 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 organophosphonates are listed in Table 1.
1.4.1 The DVL is required to be at a concentration at least three 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 for the organophosphonates in the ESI positive mode and Fig. 2 in the ESI negative mode.RSD (%)
DIMP
Pos
5
16
4
95.1
65.8
136.0
17.6
19.4
21.3
22.4
DIMP
Pos
10
19
5
98.2
80.0
121.0
6.1
5.5
13.6
13.8
DIMP
Pos
25
26
6
102.9
74.4
128.0
5.6
5.7
14.5
14.1
DIMP
Pos
125
22
5
96.6
80.4
120.0
4.4
4.5
11.0
11.4
DIMP-D14
Pos
25
86
6
102.6
54.8
127.6
9.8
9.5
11.2
10.9
EHDMAP
Neg
5
12
3
57.5
0.0
220.0
31.4
22.3
71.1
123.6
EHDMAP
Neg
10
16
4
47.1
0.0
178.0
13.3
10.8
66.8
142.0
EHDMAP
Neg
25
22
5
84.1
54.0
141.2
6.9
6.6
22.9
27.3
EHDMAP
Neg
125
18
4
87.4
64.2
141.6
5.0
5.1
25.4
29.1
EHDMAP
Pos
5
16
4
77.0
0.0
134.2
7.4
8.0
51.4
66.8
EHDMAP
Pos
10
20
5
70.0
0.0
143.0
7.7
10.0
53.6
76.5
EHDMAP
Pos
25
26
6
89.6
60.0
128.8
5.2
6.2
23.5
26.2
EHDMAP
Pos
125
22
5
87.5
59.0
123.2
5.2
6.0
23.9
27.3
EMPA
Neg
50
16
4
110.1
74.8
170.6
22.4
17.2
25.6
23.3
EMPA
Neg
100
20
5
108.3
87.7
175.0
11.1
8.7
24.8
22.9
EMPA
Neg
250
26
6
104.8
82.0
122.6
6.1
5.5
11.8
11.3
EMPA
Neg
1250
22
5
101.5
87.2
126.4
8.4
8.1
11.2
11.0
EMPA
Pos
50
16
4
95.4
77.6
122.8
12.9
13.3
13.1
13.7
EMPA
Pos
100
20
5
96.0
61.4
132.5
9.5
9.5
15.9
16.6
EMPA
Pos
250
26
6
99.7
70.0
133.2
5.9
5.4
18.2
18.2
EMPA
Pos
1250
21
5
93.9
84.0
108.4
2.7
3.0
7.7
8.2
IMPA
Neg
50
16
4
88.0
56.6
140.4
23.7
26.0
23.5
26.7
...
General Information
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Designation:D7597 −16
Standard Test Method for
Determination of Diisopropyl Methylphosphonate, Ethyl
Hydrogen Dimethylamidophosphate, Ethyl
Methylphosphonic Acid, Isopropyl Methylphosphonic Acid,
Methylphosphonic Acid and Pinacolyl Methylphosphonic
Acid in Water by Liquid Chromatography/Tandem Mass
1
Spectrometry
This standard is issued under the fixed designation D7597; 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 Level 2 due to not meeting the DVL criteria at the lower
concentration level. The DVL for MPA in the ESI negative
1.1 This procedure covers the determination of diisopropyl
mode is at 20 µg/L, which forces a raised reporting limit.
methylphosphonate (DIMP), ethyl hydrogen dimethylami-
However,themulti-laboratoryvalidationrequiredaspikeofall
dophosphate (EHDMAP), ethyl methylphosphonic acid
target analytes at Level 1 concentrations. The mean recovery
(EMPA), isopropyl methylphosphonic acid (IMPA), methyl-
for MPAin the ESI negative mode at this level was 98.7% as
phosphonic acid (MPA) and pinacolyl methylphosphonic acid
shown in Table 3. If your instrument’s sensitivity can meet the
(PMPA)(referredtocollectivelyasorganophosphonatesinthis
requirements in this test method, MPA may have a 50 µg/L
test method) in surface water by direct injection using liquid
reporting limit.
chromatography (LC) and detected with tandem mass spec-
1.5 This standard does not purport to address all of the
trometry (MS/MS) using electrospray ionization (ESI). These
safety concerns, if any, associated with its use. It is the
analytesarequalitativelyandquantitativelydeterminedbythis
responsibility of the user of this standard to establish appro-
method. This method adheres to single reaction monitoring
priate safety and health practices and determine the applica-
(SRM) mass spectrometry.
bility of regulatory limitations prior to use.
1.2 ThistestmethodhasbeendevelopedbyUSEPARegion
5 Chicago Regional Laboratory (CRL).
2. Referenced Documents
1.3 The values stated in SI units are to be regarded as 2
2.1 ASTM Standards:
standard. No other units of measurement are included in this
D1129Terminology Relating to Water
standard.
D1193Specification for Reagent Water
1.4 The detection verification level (DVL) and reporting
D2777Practice for Determination of Precision and Bias of
range for the organophosphonates are listed in Table 1.
Applicable Test Methods of Committee D19 on Water
1.4.1 The DVL is required to be at a concentration at least
D3856Guide for Management Systems in Laboratories
three times below the reporting limit (RL) and have a signal/
Engaged in Analysis of Water
noise ratio greater than 3:1. Fig. 1 displays the signal/noise
D3694Practices for Preparation of Sample Containers and
ratios at the DVLs for the organophosphonates in the ESI for Preservation of Organic Constituents
positive mode and Fig. 2 in the ESI negative mode.
D5847Practice for Writing Quality Control Specifications
1.4.2 The reporting limit is the concentration of the Level 1 for Standard Test Methods for Water Analysis
calibration standard as shown in Table 2 for the organophos-
E2554Practice for Estimating and Monitoring the Uncer-
phonatesexceptforMPAintheESInegativemodewhichisat 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 Feb. 1, 2016. Published May 2016. Originally contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM
ɛ1
approved in 2009. Last previous edition approved in 2009 as D7597 – 09 . DOI: Standards volume information, refer to the standard’s Document Summary page on
10.1520/D7597-16. the ASTM website.
Copyright ©ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA19428-2959. United States
1
---------------------- Page: 1 ----------------------
D7597−16
TABLE 1 Detection Verification Level and Reporting Range
Analyte ESI Mode DVL (µg/L) Reporting Range (µg/L)
Diisopropyl methylphosphonate Positive 1 5–150
Ethyl hydrogen dimethylamidophosphate Negative 0.25 5–150
Ethyl hydrogen dimethylamidophosphate Positive 0.25 5–150
Ethyl methylphosphonic acid Negative 5 50–1500
Ethyl methylphosphonic acid Positive 5 50–1500
Isopropyl methylphosphonic acid Negative 10 50–1500
Isopropyl Methylphosphonic acid Positive 5 50–1500
Methylphosphonic acid Negative 20 100–1500
Methylphosphonic acid P
...
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: D7597 − 09 D7597 − 16
Standard Test Method for
Determination of Diisopropyl Methylphosphonate, Ethyl
Hydrogen Dimethylamidophosphate, Ethyl
Methylphosphonic Acid, Isopropyl Methylphosphonic Acid,
Methylphosphonic Acid and Pinacolyl Methylphosphonic
Acid in Water by Liquid Chromatography/Tandem Mass
1
Spectrometry
This standard is issued under the fixed designation D7597; 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 diisopropyl methylphosphonate (DIMP), ethyl hydrogen dimethylamidophos-
phate (EHDMAP), ethyl methylphosphonic acid (EMPA), isopropyl methylphosphonic acid (IMPA), methylphosphonic acid
(MPA) and pinacolyl methylphosphonic acid (PMPA) (referred to collectively as organophosphonates in this test method) in
surface water by direct injection using liquid chromatography (LC) and detected with tandem mass spectrometry (MS/MS) using
electrospray ionization (ESI). These analytes are qualitatively and quantitatively determined by this method. This 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 organophosphonates are listed in Table 1.
1.4.1 The DVL is required to be at a concentration at least three 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 for the organophosphonates in the ESI positive mode and
Fig. 2 in the ESI negative mode.
1.4.2 The reporting limit is the concentration of the Level 1 calibration standard as shown in Table 2 for the organophosphonates
except for MPA in the ESI negative mode which is at Level 2 due to not meeting the DVL criteria at the lower concentration level.
The DVL for MPA in the ESI negative mode is at 20 μg/L, which forces a raised reporting limit. However, the multi-laboratory
validation required a spike of all target analytes at Level 1 concentrations. The mean recovery for MPA in the ESI negative mode
at this level was 98.7 % as shown in Table 3. If your instrument’s sensitivity can meet the requirements in this test method, MPA
may have a 50 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
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 D7597
ɛ1
– 09 . DOI: 10.1520/D7597-09E02.10.1520/D7597-16.
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 ----------------------
D7597 − 16
TABLE 1 Detection Verification Level and Reporting Range
Analyte ESI Mode DVL (μg/L) Reporting Range (μg/L)
Diisopropyl methylphosphonate Positive 1 5–150
Ethyl hydrogen dimethylamidophosphate Negative 0.25 5–150
Ethyl hydrogen dimethylamidophosphate Positive 0.25 5–150
Ethyl methylphosphonic acid Negative 5 50–1500
Ethyl methylphosphonic acid Positive 5 50–1500
Isopropyl methylphosphonic ac
...
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