ASTM D7599-16(2017)
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 (Surrogate) | 25 | 50 | 75 | 150 | 250 | 350 | 500 |
TABLE 3 Multi-Laboratory Recovery Data in Reagent Water
| Analyte | Spike Conc. | # Results | # Labs | Bias | Precision | |||||
| Mean | Min | Max | Overall SD | Pooled | Overall | Pooled | ||||
| 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 |
| N-Methyldiethanolamine | 425 | 24 | 6 | 94.75 | 63.00 | 115.76 | 15.02 | 3.34 | 15.85 | 3.72 |
| Diethanolamine-D8 (Surrogate) | 200 | 96 | 6 | 103.02 | 60.00 | 151.95 | 21.13 | 9.40 | 20.51 | 9.25 |
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.
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.
