ASTM D7597 - 16(2017)

    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

    Active Standard ASTM D7597 | Developed by Subcommittee: D19.06

    Book of Standards Volume: 11.02


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    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 test method has been investigated for use with reagent and surface water.

    1. 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 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 organophosphonates are listed in Table 1.

    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

    Positive

    10

    50–1500

    Pinacolyl methylphosphonic acid

    Negative

    5

    50–1500

    Pinacolyl methylphosphonic acid

    Positive

    5

    50–1500

    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.

    FIG. 1 Example ESI Positive Mode SRM Chromatograms Signal/Noise Ratios

    Example ESI Positive Mode SRM Chromatograms Signal/Noise
 RatiosExample ESI Positive Mode SRM Chromatograms Signal/Noise
 Ratios

    FIG. 2 Example ESI Negative Mode SRM Chromatograms Signal/Noise Ratios

    Example ESI Negative Mode SRM Chromatograms Signal/Noise
 RatiosExample ESI Negative Mode 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 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.

    TABLE 2 Concentrations of Calibration Standards (PPB)

    Analyte/Surrogate

    LV 1

    LV 2

    LV 3

    LV 4

    LV 5

    LV 6

    LV 7

    Diisopropyl methylphosphonate

    5

    10

    20

    35

    50

    100

    150

    Ethyl hydrogen dimethylamidophosphate

    5

    10

    20

    35

    50

    100

    150

    Ethyl methylphosphonic acid

    50

    100

    200

    350

    500

    1000

    1500

    Isopropyl methylphosphonic acid

    50

    100

    200

    350

    500

    1000

    1500

    Methylphosphonic acid

    50

    100

    200

    350

    500

    1000

    1500

    Pinacolyl methylphosphonic acid

    50

    100

    200

    350

    500

    1000

    1500

    DIMP-D14 (Surrogate)

    5

    10

    20

    35

    50

    100

    150

    PMPA-13C4 (Surrogate)

    25

    50

    100

    175

    250

    500

    750

    MPA-D3 (Surrogate)

    25

    50

    100

    175

    250

    500

    750

    TABLE 3 Multi-Laboratory Recovery Data in Reagent Water

    Analyte

    ESI
    Mode

    Spike Conc.
    (ppb)

    # Results

    # Labs

    Bias

    Precision

    Mean
    Recovery
    (%)

    Min
    Recovery
    (%)

    Max
    Recovery
    (%)

    Overall SD
    (%)

    Pooled
    within-lab
    SD (%)

    Overall
    RSD (%)

    Pooled
    within-lab
    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

    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

    D3694 Practices for Preparation of Sample Containers and for Preservation of Organic Constituents

    D3856 Guide for Management Systems in Laboratories Engaged in Analysis of Water

    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

    Other Documents

    EPA Publication SW-846 Test Methods for Evaluating Solid Waste, Physical/Chemical Methods


    ICS Code

    ICS Number Code 13.060.50 (Examination of water for chemical substances)

    UNSPSC Code

    UNSPSC Code 41115705(Liquid chromatographs); 12352103(Organo metallic compounds)


    Referencing This Standard
    Link Here
    Link to Active (This link will always route to the current Active version of the standard.)

    DOI: 10.1520/D7597-16R17

    Citation Format

    ASTM D7597-16(2017), 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, ASTM International, West Conshohocken, PA, 2017, www.astm.org

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