EPA-OW/OST: 1633 (Solids and Biosolids): Per- and Polyfluoroalkyl Substances (PFAS) in Solids and Biosolids Samples by LC-MS/MS

Summary
Analytes
Revisions
Data and Sites

Official Method Name

Draft Method 1633 Analysis of Per- and Polyfluoroalkyl Substances (PFAS) in Aqueous, Solid, Biosolids, and Tissue Samples by LC-MS/MS

Current Revision

Final version

Media

SOILS/SEDIMENT

Instrumentation

Liquid Chromatography with Tandem Mass Spectrometry

Method Subcategory

Organic

Method Source

EPA-OW/OST

Citation

Draft Method 1633: Analysis of Per- and Polyfluoroalkyl Substances (PFAS) in Aqueous, Solid, Biosolids, and Tissue Samples by LC-MS/MS

Brief Method Summary

Solid samples are spiked with isotopically labeled standards, extracted into basic methanol, and cleaned up by carbon and SPE cartridges before analysis. Analyses of the sample extracts are conducted by LC-MS/MS in the multiple reaction monitoring (MRM) mode. Sample concentrations are determined by isotope dilution or extracted internal standard quantification using isotopically labeled compounds added to the samples before extraction. Note revised errata sheet dated February 8, 2022.

Scope and Application

The method covers the determination of Per- and Polyfluoroalkyl Substances (PFAS) in Aqueous, Solid, Biosolids, and Tissue Samples

Applicable Concentration Range

As analyzed and uncorrected for original sample mass (5 grams of sediment or 0.5 grams of biosolids), ML ranges from 1.6 - 1,560 ng/L but most compounds range 1.6 - 62.5 ng/L.

Interferences

(A) Glass equipment: Cleaned by washing with detergent and baking in a kiln or furnace. After detergent washing, glassware should be rinsed immediately with reagent water. Prior to use, baked glassware must be solvent rinsed and then air dried. A solvent rinse procedure using methanolic ammonium hydroxide (1%), toluene, and methanol is recommended. (B) SPE manifold contamination: Cleaned by sonicating in methanolic ammonium hydroxide (1%) and air drying prior to use. Smaller parts, like the needles, adapters, reservoirs, and stopcocks associated with the manifold require rinsing with tap water prior to sonicating in methanolic ammonium hydroxide (1%) and air drying. When in use, after loading the samples but prior to elution procedures, the chamber must be rinsed with methanolic ammonium hydroxide (1%). (C) Fluoropolymer interferences: SPE and carbon cleanup are required to remove these compounds.

Quality Control Requirements

Extracted Internal Standard (EIS), Non-Extracted Internal Standard (NIS), Native Standards Solution, Calibration standard solutions, Qualitative Standards, Instrument Blank, Sodium iodide/cesium iodide mass calibration solution.

Sample Handling

Collect samples as grab samples using wide-mouth, HDPE, 500-mL jars with linerless HDPE or polypropylene caps and fill no more than ¾ full.

Maximum Holding Time

90 days at either 0 - 6 ºC or ≤ -20 ºC, no light, with caveat. Extracts - 90 days (0 - 4 ºC, no light, caveat)

Relative Cost

Sample Preparation Methods

This method has 38 analytes associated with it.

Analyte	Detection Level	Bias	Precision	Spiking Level
11-Chloroeicosafluoro-3-oxaundecane-1-sulfonic acid(763051-92-9) 11-Chloroeicosafluoro-3-oxaundecane-1-sulfonic acid 11Cl-PF3OUdS Ethanesulfonic acid, 2-[(8-chloro-1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8-hexadecafluorooctyl)oxy]-1,1,2,2-tetrafluoro-	0.071 ng/g	102% Rec	3.30 % RSD	10.00 ng/g
1H,1H, 2H, 2H-Perfluorodecane sulfonic acid(39108-34-4) 1H,1H, 2H, 2H-Perfluorodecane sulfonic acid 8:2FTS	0.225 ng/g	116% Rec	3.80 % RSD	10.00 ng/g
1H,1H, 2H, 2H-Perfluorohexane sulfonic acid(757124-72-4) 1H,1H, 2H, 2H-Perfluorohexane sulfonic acid 4:2FTS	0.282 ng/g	100% Rec	0.50 % RSD	10.00 ng/g
1H,1H, 2H, 2H-Perfluorooctane sulfonic acid(27619-97-2) 1H,1H, 2H, 2H-Perfluorooctane sulfonic acid 6:2FTS	0.116 ng/g	113% Rec	6.50 % RSD	10.00 ng/g
2H,2H,3H,3H-Perfluorooctanoic acid(914637-49-3) 2H,2H,3H,3H-Perfluorooctanoic acid 5:3FTCA	0.363 ng/g	91% Rec	3.10 % RSD	62.50 ng/g
3-Perfluoroheptyl propanoic acid(812-70-4) 3-Perfluoroheptyl propanoic acid 7:3FTCA	0.308 ng/g	90% Rec	4.10 % RSD	62.50 ng/g
3-Perfluoropropyl propanoic acid(356-02-5) 3-Perfluoropropyl propanoic acid 3:3FTCA	0.060 ng/g	96% Rec	3.30 % RSD	12.50 ng/g
4,8-Dioxa-3H-perfluorononanoic acid(919005-14-4) 4,8-Dioxa-3H-perfluorononanoic acid ADONA	0.057 ng/g	100% Rec	3.20 % RSD	10.00 ng/g
9-Chlorohexadecafluoro-3-oxanonane-1-sulfonic acd(756426-58-1) 9-Chlorohexadecafluoro-3-oxanonane-1-sulfonic acd 9Cl-PF3ONS	0.038 ng/g	105% Rec	4.40 % RSD	10.00 ng/g
Hexafluoropropylene oxide dimer acid(13252-13-6) HFPO-DA Hexafluoropropylene oxide dimer acid Propanoic acid, 2,3,3,3-tetrafluoro-2-(1,1,2,2,3,3,3-heptafluoropropoxy)-	0.136 ng/g	100% Rec	5.90 % RSD	10.00 ng/g
N-ethyl perfluorooctanesulfonamidoacetic acid(2991-50-6) Glycine, N-ethyl-N-[(1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-heptadecafluorooctyl)sulfonyl]- N-ethyl perfluorooctanesulfonamidoacetic acid N-ethyl perfluorooctanesulfonamidoacetic acid NEtFOSAA NEtFOSAA	0.044 ng/g	102% Rec	1.60 % RSD	2.50 ng/g
N-methyl perfluorooctanesulfonamide(31506-32-8) N-methyl perfluorooctanesulfonamide NMeFOSA	0.049 ng/g	104% Rec	4.40 % RSD	2.50 ng/g
N-methyl perfluorooctanesulfonamidoacetic acid(2355-31-9) Glycine, N-[(1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-heptadecafluorooctyl)sulfonyl]-N-methyl- N-methyl perfluorooctanesulfonamidoacetic acid N-methyl perfluorooctanesulfonamidoacetic acid NMeFOSAA NMeFOSAA	0.030 ng/g	102% Rec	4.00 % RSD	2.50 ng/g
N-methyl perfluorooctanesulfonamidoethanol(24448-09-7) N-methyl perfluorooctanesulfonamidoethanol NMeFOSE	0.203 ng/g	103% Rec	1.30 % RSD	25.00 ng/g
Nonafluoro-3,6-dioxaheptanoic acid(151772-58-6) NFDHA Nonafluoro-3,6-dioxaheptanoic acid	0.084 ng/g	97% Rec	16.20 % RSD	5.00 ng/g
Perfluoro(2-ethoxyethane)sulfonic acid(113507-82-7) PFEESA Perfluoro(2-ethoxyethane)sulfonic acid	0.018 ng/g	99% Rec	3.80 % RSD	5.00 ng/g
Perfluoro-1-decanesulfonic acid(335-77-3) 1-Decanesulfonic acid, 1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heneicosafluoro- PFDS Perfluoro-1-decanesulfonic acid	0.040 ng/g	96% Rec	5.20 % RSD	2.50 ng/g
Perfluoro-1-nonanesulfonic acid(68259-12-1) 1-Nonanesulfonic acid, 1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,9-nonadecafluoro- PFNS Perfluoro-1-nonanesulfonic acid	0.046 ng/g	97% Rec	3.00 % RSD	2.50 ng/g
Perfluoro-1-octanesulfonamide(754-91-6) 1-Octanesulfonamide, 1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-heptadecafluoro- PFOSA Perfluoro-1-octanesulfonamide	0.068 ng/g	104% Rec	3.40 % RSD	2.50 ng/g
Perfluoro-3-methoxypropanoic acid(377-73-1) PFMPA Perfluoro-3-methoxypropanoic acid	0.033 ng/g	101% Rec	1.80 % RSD	5.00 ng/g
Perfluoro-4-methoxybutanoic acid(863090-89-5) PFMBA Perfluoro-4-methoxybutanoic acid	0.029 ng/g	103% Rec	2.60 % RSD	5.00 ng/g
Perfluorobutanesulfonic acid(375-73-5) 1,1,2,2,3,3,4,4,4-Nonafluoro-1-butanesulfonic acid PFBS Perfluorobutanesulfonic acid	0.014 ng/g	101% Rec	3.20 % RSD	2.50 ng/g
Perfluorobutanoic acid(375-22-4) PFBA Perfluorobutanoic acid	0.401 ng/g	100% Rec	1.00 % RSD	10.00 ng/g
Perfluorodecanoic acid(335-76-2) PFDA Perfluorodecanoic acid	0.031 ng/g	104% Rec	1.50 % RSD	2.50 ng/g
Perfluorododecanesulfonic acid(79780-39-5) PFDoS Perfluorododecanesulfonic acid	0.038 ng/g	89% Rec	6.50 % RSD	2.50 ng/g
Perfluorododecanoic acid(307-55-1) PFDoA Perfluorododecanoic acid Perfluorolauric acid	0.059 ng/g	104% Rec	12.10 % RSD	2.50 ng/g
Perfluoroheptanesulfonic acid(375-92-8) PFHpS Perfluoroheptanesulfonic acid	0.057 ng/g	96% Rec	4.40 % RSD	2.50 ng/g
Perfluoroheptanoic acid(375-85-9) PFHpA Perfluoroheptanoic acid	0.029 ng/g	98% Rec	2.20 % RSD	2.50 ng/g
Perfluorohexanesulfonic acid(355-46-4) 1,1,2,2,3,3,4,4,5,5,6,6,6-Tridecafluorohexane-1-sulfonic acid PFHxS Perfluorohexanesulfonic acid	0.018 ng/g	105% Rec	2.00 % RSD	2.50 ng/g
Perfluorohexanoic acid(307-24-4) PFHxA Perfluorohexanoic acid Undecafluoro-1-hexanoic acid	0.020 ng/g	98% Rec	2.20 % RSD	2.50 ng/g
Perfluorononanoic acid(375-95-1) PFNA Perfluorononanoic acid	0.086 ng/g	100% Rec	2.70 % RSD	2.50 ng/g
Perfluorooctanesulfonic acid(1763-23-1) 1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-Heptadecafluoro-1-octanesulfonic acid PFOS Perfluorooctane sulfonate Perfluorooctanesulfonic acid	0.067 ng/g	105% Rec	3.40 % RSD	2.50 ng/g
Perfluorooctanoic acid(335-67-1) Hexanoyl fluoride, 3,3,4,4,5,5,6,6,6-nonafluoro-2-oxo- PFOA Perfluoroheptanecarboxylic acid Perfluorooctanoic acid	0.037 ng/g	98% Rec	2.00 % RSD	2.50 ng/g
Perfluoropentanesulfonic acid(2706-91-4) PFPeS Perfluoropentanesulfonic acid	0.015 ng/g	101% Rec	4.30 % RSD	2.50 ng/g
Perfluoropentanoic acid(2706-90-3) PFPeA Perfluoropentanoic acid	0.021 ng/g	105% Rec	3.40 % RSD	5.00 ng/g
Perfluorotetradecanoic acid(376-06-7) PFTA Perfluoromyristic acid Perfluorotetradecanoic acid	0.032 ng/g	101% Rec	2.50 % RSD	2.50 ng/g
Perfluorotridecanoic acid(72629-94-8) PFTrDA Perfluorotridecanoic acid	0.038 ng/g	107% Rec	5.20 % RSD	2.50 ng/g
Perfluoroundecanoic acid(2058-94-8) PFUnA Perfluoroundecanoic acid	0.033 ng/g	102% Rec	4.00 % RSD	2.50 ng/g

Precision Descriptor Notes:	Extract, concentrate, and analyze four aliquots of the matrix type to be tested, spiked with 200 µL of the native standard solution, 50 µL of the EIS solution, and 50 µL of NIS solution. At least one method blank, matching the matrix being analyzed, must be prepared with the Initial Precision and Recovery (IPR) batch. All sample processing steps that are to be used for processing samples including preparation and extraction, cleanup and concentration, must be included in this test. Using results of the set of four analyses, compute the average percent recovery (R) of the extracts and the relative standard deviation (RSD) of the concentration for each target and EIS compound. For each native and isotopically labeled compound, compare RSD and % recovery with the corresponding limits for initial precision and recovery in Table 5. If RSD and R for all compounds meet the acceptance criteria, system performance is acceptable, and analysis of blanks and samples may begin. If, however, any individual RSD exceeds the precision limit or any individual R falls outside the range for recovery, system performance is unacceptable for that compound. Correct the problem and repeat the test.
Detection Level Note:	Minimum detection levels (MDLs) for all the analytes are determined using the MDL procedure at 40 CFR Part 136, Appendix B. An MDL determination must be performed for all compounds. The minimum level of quantification (ML) is then calculated by multiplying the MDL by 3.18 and rounding the result to the nearest 1, 2 or 5 x 10n, where n is zero or an integer.

Precision Descriptor Notes:

Extract, concentrate, and analyze four aliquots of the matrix type to be tested, spiked with 200 µL of the native standard solution, 50 µL of the EIS solution, and 50 µL of NIS solution. At least one method blank, matching the matrix being analyzed, must be prepared with the Initial Precision and Recovery (IPR) batch. All sample processing steps that are to be used for processing samples including preparation and extraction, cleanup and concentration, must be included in this test. Using results of the set of four analyses, compute the average percent recovery (R) of the extracts and the relative standard deviation (RSD) of the concentration for each target and EIS compound. For each native and isotopically labeled compound, compare RSD and % recovery with the corresponding limits for initial precision and recovery in Table 5. If RSD and R for all compounds meet the acceptance criteria, system performance is acceptable, and analysis of blanks and samples may begin. If, however, any individual RSD exceeds the precision limit or any individual R falls outside the range for recovery, system performance is unacceptable for that compound. Correct the problem and repeat the test.

Detection Level Note:

Minimum detection levels (MDLs) for all the analytes are determined using the MDL procedure at 40 CFR Part 136, Appendix B. An MDL determination must be performed for all compounds. The minimum level of quantification (ML) is then calculated by multiplying the MDL by 3.18 and rounding the result to the nearest 1, 2 or 5 x 10n, where n is zero or an integer.

Revision	PDF/Link
Final version
3rd Draft EPA 1633
2nd Draft EPA 1633
Revised errata sheet
Draft EPA 1633

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EPA-OW/OST: 1633 (Solids and Biosolids): Per- and Polyfluoroalkyl Substances (PFAS) in Solids and Biosolids Samples by LC-MS/MS

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