【国外标准】 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 Liqu

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.4,55.2 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.1.1 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 RangeAnalyte ESI Mode DVL (μg/L) Reporting Range (μg/L)Diisopropyl methylphosphonate Positive 1 5–150Ethyl hydrogen dimethylamidophosphate Negative 0.25 5–150Ethyl hydrogen dimethylamidophosphate Positive 0.25 5–150Ethyl methylphosphonic acid Negative 5 50–1500Ethyl methylphosphonic acid Positive 5 50–1500Isopropyl methylphosphonic acid Negative 10 50–1500Isopropyl Methylphosphonic acid Positive 5 50–1500Methylphosphonic acid Negative 20 100–1500Methylphosphonic acid Positive 10 50–1500Pinacolyl methylphosphonic acid Negative 5 50–1500Pinacolyl methylphosphonic acid Positive 5 50–15001.4.1 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 RatiosFIG. 2 Example ESI Negative Mode SRM Chromatograms Signal/Noise Ratios1.4.2 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 7Diisopropyl methylphosphonate 5 10 20 35 50 100 150Ethyl hydrogen dimethylamidophosphate 5 10 20 35 50 100 150Ethyl methylphosphonic acid 50 100 200 350 500 1000 1500Isopropyl methylphosphonic acid 50 100 200 350 500 1000 1500Methylphosphonic acid 50 100 200 350 500 1000 1500Pinacolyl methylphosphonic acid 50 100 200 350 500 1000 1500DIMP-D14 (Surrogate) 5 10 20 35 50 100 150PMPA-13C4 (Surrogate) 25 50 100 175 250 500 750MPA-D3 (Surrogate) 25 50 100 175 250 500 750TABLE 3 Multi-Laboratory Recovery Data in Reagent WaterAnalyte ESIMode Spike Conc.(ppb) # Results # Labs Bias PrecisionMeanRecovery(%) MinRecovery(%) MaxRecovery(%) Overall SD(%) Pooledwithin-labSD (%) OverallRSD (%) Pooledwithin-labRSD (%)DIMP Pos 5 16 4 95.1 65.8 136.0 17.6 19.4 21.3 22.4DIMP Pos 10 19 5 98.2 80.0 121.0 6.1 5.5 13.6 13.8DIMP Pos 25 26 6 102.9 74.4 128.0 5.6 5.7 14.5 14.1DIMP Pos 125 22 5 96.6 80.4 120.0 4.4 4.5 11.0 11.4DIMP-D14 Pos 25 86 6 102.6 54.8 127.6 9.8 9.5 11.2 10.9EHDMAP Neg 5 12 3 57.5 0.0 220.0 31.4 22.3 71.1 123.6EHDMAP Neg 10 16 4 47.1 0.0 178.0 13.3 10.8 66.8 142.0EHDMAP Neg 25 22 5 84.1 54.0 141.2 6.9 6.6 22.9 27.3EHDMAP Neg 125 18 4 87.4 64.2 141.6 5.0 5.1 25.4 29.1EHDMAP Pos 5 16 4 77.0 0.0 134.2 7.4 8.0 51.4 66.8EHDMAP Pos 10 20 5 70.0 0.0 143.0 7.7 10.0 53.6 76.5EHDMAP Pos 25 26 6 89.6 60.0 128.8 5.2 6.2 23.5 26.2EHDMAP Pos 125 22 5 87.5 59.0 123.2 5.2 6.0 23.9 27.3EMPA Neg 50 16 4 110.1 74.8 170.6 22.4 17.2 25.6 23.3EMPA Neg 100 20 5 108.3 87.7 175.0 11.1 8.7 24.8 22.9EMPA Neg 250 26 6 104.8 82.0 122.6 6.1 5.5 11.8 11.3EMPA Neg 1250 22 5 101.5 87.2 126.4 8.4 8.1 11.2 11.0EMPA Pos 50 16 4 95.4 77.6 122.8 12.9 13.3 13.1 13.7EMPA Pos 100 20 5 96.0 61.4 132.5 9.5 9.5 15.9 16.6EMPA Pos 250 26 6 99.7 70.0 133.2 5.9 5.4 18.2 18.2EMPA Pos 1250 21 5 93.9 84.0 108.4 2.7 3.0 7.7 8.2IMPA Neg 50 16 4 88.0 56.6 140.4 23.7 26.0 23.5 26.7IMPA Neg 100 20 5 88.0 68.5 118.0 12.9 14.3 13.4 15.2IMPA Neg 250 26 6 98.1 72.8 144.0 13.1 11.9 19.2 19.6IMPA Neg 1250 21 5 90.7 73.1 103.0 5.5 6.1 8.7 9.6IMPA Pos 50 16 4 98.3 47.8 139.6 19.2 20.5 27.2 27.7IMPA Pos 100 19 5 95.4 72.3 120.5 9.8 10.3 12.4 13.0IMPA Pos 250 26 6 97.0 79.2 188.4 7.4 7.6 10.9 11.2IMPA Pos 1250 21 5 91.3 70.4 115.5 5.1 5.2 11.4 12.5MPA Neg 50 16 4 98.7 3.3 175.0 14.2 25.3 60.5 61.3MPA Neg 100 20 5 100.0 41.9 142.0 8.9 9.2 30.8 30.8MPA Neg 250 26 6 99.5 66.0 124.5 7.6 7.6 14.5 14.5MPA Neg 1250 22 5 102.7 81.8 130.5 10.5 9.9 12.4 12.1MPA Pos 50 16 4 68.3 9.8 139.6 13.4 20.3 36.6 53.6MPA Pos 100 20 5 80.5 48.4 149.7 14.0 12.6 26.8 33.3MPA Pos 250 26 6 91.7 33.9 153.7 8.0 7.8 31.8 34.7MPA Pos 1250 22 5 95.8 31.8 208.2 12.6 8.3 43.4 45.3MPA-D3 Neg 250 84 6 111.2 57.2 190.8 16.2 12.5 30.0 26.9MPA-D3 Pos 250 68 5 104.4 58.4 151.8 14.3 14.0 18.0 17.3PMPA Neg 50 15 4 87.8 77.6 124.4 8.4 8.2 13.8 15.7PMPA Neg 100 19 5 91.6 83.6 98.2 2.8 3.0 4.4 4.8PMPA Neg 250 26 6 101.0 77.2 123.8 5.0 4.8 12.1 12.0PMPA Neg 1250 22 5 99.2 84.8 126.5 4.9 4.8 12.3 12.4PMPA Pos 50 16 4 90.8 60.8 148.8 15.8 16.1 25.6 28.2PMPA Pos 100 15 4 95.2 86.8 114.0 3.8 4.0 7.9 8.3PMPA Pos 250 20 5 103.8 85.2 136.1 4.5 3.8 15.3 14.7PMPA Pos 1250 12 3 99.8 88.8 117.5 5.2 5.0 7.5 7.5PMPA-13C6 Neg 250 83 6 99.5 74.8 128.3 9.4 9.2 11.1 11.11.5 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.1.6 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.