Significance and Use
5.1 This test method has been developed by the U.S. EPA Region 5 Chicago Regional Laboratory (CRL).
5.2 PFCs are widely used in various industrial and commercial products; they are persistent, bio-accumulative, and ubiquitous in the environment. PFCs have been reported to exhibit developmental toxicity, hepatotoxicity, immunotoxicity, and hormone disturbance. A draft Toxicological Profile for Perfluoroalkyls from the U.S. Department of Health and Human Services is available.7 PFCs have been detected in soils, sludges, and surface and drinking waters. Hence, there is a need for a quick, easy, and robust method to determine these compounds at trace levels in various soil matrices for understanding of the sources and pathways of exposure.
5.3 This method has been used to determine selected polyfluorinated compounds in sand (Table 4) and four ASTM reference soils (Table 5).
TABLE 4 Single-Laboratory Recovery Data in Ottawa Sand
| Sample | Measured ng/kg from Ottawa Sand P&A Data (400 ng/kg spike for all PFCs except 2000 ng/kg for PFBA and PFPeA and 8000 ng/kg spike for FHEA, FDEA, and FOEA) | ||||||||||
| PFTreA | PFTriA | PFDoA | PFUnA | PFDA | PFNA | PFOA | PFHpA | PFHxA | PFPeA | PFBA | |
| Unspiked 1 | | | | | | | | | | | |
| Unspiked 2 | | | | | | | | | | | |
| P&A 1 | 389.6 | 394.3 | 384.7 | 376.7 | 362.1 | 347.6 | 345.8 | 232.9 | 222.2 | 1614.9 | 1344.5 |
| P&A 2 | 462.1 | 424.6 | 397.2 | 379.1 | 378.4 | 376.9 | 365.9 | 247.9 | 229.8 | 1710.1 | 1388 |
| P&A 3 | 402.7 | 387.7 | 383.1 | 365.9 | 374.7 | 363.3 | 347.1 | 242.4 | 222.9 | 1658.9 | 1376 |
| P&A 4 | 403.9 | 397.1 | 395.4 | 381.5 | 379 | 359.4 | 342.7 | 246.8 | 225.8 | 1693.6 | 1401.9 |
| P&A 5 | 467.2 | 445.8 | 412.6 | 388.5 | 376.8 | 370.3 | 369.7 | 249.3 | 231.4 | 1716.5 | 1433.4 |
| P&A 6 | 392.1 | 385.3 | 374.2 | 370.9 | 353.2 | 351.7 | 340.3 | 236.7 | 220.5 | 1659 | 1366.4 |
| Mean Recovery (ng/kg) | 419.6 | 405.8 | 391.2 | 377.1 | 370.7 | 361.5 | 351.9 | 242.7 | 225.4 | 1675.5 | 1385 |
| % Mean Recovery | 104.9 | 101.4 | 97.8 | 94.3 | 92.7 | 90.4 | 88 | 60.7 | 56.4 | 83.8 | 69.3 |
| Standard Deviation | 35.4 | 24.1 | 13.5 | 8 | 10.6 | 11.1 | 12.6 | 6.6 | 4.4 | 38.5 | 30.7 |
| RSD (%) | 8.4 | 5.9 | 3.5 | 2.1 | 2.9 | 3.1 | 3.6 | 11 | 1.9 | 2.3 | 2.2 |
|
|
|
|
|
|
|
|
|
|
|
|
|
| Sample | PFBS | PFHxS | PFOS | PFechS | FOUEA | FHpPA | FHUEA | FHEA | FOEA | FDEA |
|
| Unspiked 1 | | | | | | | | | | |
|
| Unspiked 2 | | | | | | | | | | |
|
| P&A 1 | 337.4 | 349.1 | 340.3 | 342.8 | 389.5 | 371.3 | 372.5 | 7023.5 | 8202.6 | 8564.9 |
|
| P&A 2 | 347.3 | 358.3 | 345.9 | 347.2 | 408.7 | 377.2 | 387.1 | 7346.1 | 8542.6 | 9308 |
|
| P&A 3 | 366.3 | 330.1 | 331.7 | 345.4 | 401.5 | 361.4 | 379 | 6844.3 | 7402.4 | 8989.2 |
|
| P&A 4 | 348.2 | 343.6 | 338.3 | 347.6 | 404.9 | 377.5 | 388.1 | 7258.2 | 7551.9 | 9173.4 |
|
| P&A 5 | 351.8 | 361.7 | 365.6 | 362.6 | 417.5 | 395.1 | 391.8 | 7461.3 | 7821.2 | 9287.4 |
|
| P&A 6 | 336.7 | 343.4 | 363.7 | 342.5 | 394.5 | 356.9 | 374.5 | 7559.3 | 8002.2 | 8367.1 |
|
| Mean Recovery (ng/kg) | 347.9 | 347.7 | 347.7 | 348 | 402.7 | 373.2 | 382.1 | 7248.8 | 7920.5 | 8948.3 |
|
| % Mean Recovery | 87 | 86.9 | 86.9 | 87 | 100.7 | 93.3 | 95.5 | 90.6 | 99 | 111.9 |
|
| Standard Deviation | 10.9 | 11.5 | 13.9 | 7.4 | 10 | 13.6 | 7.9 | 270.4 | 421.3 | 395.3 |
|
| RSD (%) | 3.1 | 3.3 | 4 | 2.1 | 2.5 | 3.6 | 2.1 | 3.7 | 5.3 | 4.4 |
|
TABLE 5 Single-Laboratory Surrogate Recovery Data in Ottawa Sand
| Sample | Measured ng/kg from Ottawa Sand – 400 ng/kg spike | ||||||||
| MPFBA | MPFHxA | MPFHxS | MPFOA | MPFNA | MPFOS | MPFDA | MPFUnA | MPFDoA | |
| Unspiked 1 | 420.0 | 433.5 | 431.8 | 428.0 | 439.4 | 429.2 | 442.6 | 443.3 | 447.7 |
| Unspiked 2 | 366.5 | 396.8 | 378.5 | 384.9 | 389.8 | 373.6 | 404.9 | 400.8 | 425.8 |
| P&A 1 | 361.1 | 364.3 | 356.3 | 377.0 | 376.6 | 354.4 | 384.9 | 391.3 | 409.3 |
| P&A 2 | 383.6 | 378.4 | 357.3 | 389.4 | 379.7 | 375.7 | 395.7 | 399.2 | 412.2 |
| P&A 3 | 374.5 | 378.5 | 375.4 | 390.5 | 378.6 | 372.4 | 382.5 | 386.9 | 402.2 |
| P&A 4 | 370.1 | 384.4 | 366.1 | 396.3 | 384.4 | 374.2 | 397.8 | 406.2 | 420.5 |
| P&A 5 | 370.1 | 386.8 | 372.0 | 395.7 | 381.1 | 372.8 | 394.4 | 399.9 | 421.5 |
| P&A 6 | 363.6 | 384.8 | 356.1 | 397.9 | 384.9 | 368.6 | 389.5 | 392.3 | 402.9 |
| Mean Recovery (ng/kg dry weight) | 376.2 | 388.4 | 374.2 | 394.9 | 389.3 | 377.6 | 399.0 | 402.5 | 417.7 |
| % Mean Recovery | 94.0 | 97.1 | 93.5 | 98.7 | 97.3 | 94.4 | 99.8 | 100.6 | 104.4 |
| Standard Deviation | 19.0 | 20.4 | 24.9 | 15.0 | 20.7 | 21.9 | 19.0 | 17.6 | 14.9 |
| RSD (%) | 5.1 | 5.3 | 6.7 | 3.8 | 5.3 | 5.8 | 4.8 | 4.4 | 3.6 |
Scope
1.1 This procedure covers the determination of selected polyfluorinated compounds (PFCs) in a soil matrix using solvent extraction, filtration, followed by liquid chromatography (LC) and detection with tandem mass spectrometry (MS/MS). These analytes are qualitatively and quantitatively determined by this method. This method adheres to multiple reaction monitoring (MRM) mass spectrometry. This procedure utilizes a quick extraction and is not intended to generate an exhaustive accounting of the content of PFCs in difficult soil matrices. An exhaustive extraction procedure for polyfluoralkyl substances, such as published by Washington et al.,2 for difficult matrices should be considered when analyzing PFCs.
1.2 Units—The values stated in SI units are to be regarded as standard. No other units of measurement are included in this standard.
1.3 The Method of Detection Limit3 and Reporting Range4 for the target analytes are listed in Table 1.
TABLE 1 Method Detection Limit and Reporting RangeA
| Analyte | MDL | Reporting Limit |
| PFTreA | 6.76 | 25–1000 |
| PFTriA | 5.26 | 25–1000 |
| PFDoA | 3.56 | 25–1000 |
| PFUnA | 2.45 | 25–1000 |
| PFDA | 5.54 | 25–1000 |
| PFOS | 18.83 | 50–1000 |
| PFNA | 2.82 | 25–1000 |
| PFecHS | 2.41 | 25–1000 |
| PFOA | 6.24 | 25–1000 |
| PFHxS | 7.75 | 25–1000 |
| PFHpA | 5.80 | 25–1000 |
| PFHxA | 15.44 | 50–1000 |
| PFBS | 6.49 | 25–1000 |
| PFPeA | 20.93 | 125–5000 |
| PFBA | 22.01 | 125–5000 |
| FHEA | 199.04 | 600–20 000 |
| FOEA | 258.37 | 750–20 000 |
| FDEA | 137.46 | 500–20 000 |
| FOUEA | 4.85 | 25–1000 |
| FhpPa | 5.09 | 25–1000 |
| FHUEA | 3.50 | 25–1000 |
TABLE 2 Concentrations of Calibration Standards (ng/L)
| Analyte/Surrogate | LV1 | LV2 | LV3 | LV4 | LV5 | LV6 | LV7 | LV8 | LV9 |
| PFPeA, PFBA | 25 | 50 | 100 | 200 | 300 | 400 | 500 | 750 | 1000 |
| PFTreA, PFTriA, PFDoA, PFUnA, PFDA, PFOS, PFNA, PFHxA, PFHpA, PFBS, PFechS, PFOA, PFHxS, FOUEA, FHUEA, FHpPA, MPFBS, MPFHxA, MPFUnA, MPFOA, MPFDA, MPFOS, MPFNA, MPFHxS, MPFBA | 5 | 10 | 20 | 40 | 60 | 80 | 100 | 150 | 200 |
| FHEA, FOEA, FDEA | 100 | 200 | 400 | 800 | 1200 | 1600 | 2000 | 3000 | 4000 |
1.3.1 The reporting limit in this test method is the minimum value below which data are documented as non-detects. Analyte detections between the method detection limit and the reporting limit are estimated concentrations and are not reported following this test method. In most cases, the reporting limit is calculated from the concentration of the Level 1 calibration standard as shown in Table 2 for the polyfluorinated compounds after taking into account a 2-g sample weight and a final extract volume of 10 mL, 50 % water/50 % MeOH with 0.1 % acetic acid. The final extract volume is assumed to be 10 mL because 10 mL of 50 % water/50 % MeOH with 0.1 % acetic acid was added to each soil sample and only the liquid layer after extraction is filtered, leaving the solid and any residual solvent behind. It is raised above the Level 1 calibration concentration for PFOS, PFHxA, FHEA, and FOEA; these compounds can be identified at the Level 1 concentration but the standard deviation among replicates at this lower spike level resulted in a higher reporting limit.
1.4 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, health and environmental practices and determine the applicability of regulatory limitations prior to use.
1.5 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.
