The three methods at a glance
- EPA Method 533 — 25 short-chain and modern PFAS in finished drinking water. Isotope-dilution direct injection LC-MS/MS. Required for the 2024 NPDWR PFAS rule.
- EPA Method 537.1 — 18 longer-chain legacy PFAS in finished drinking water. Solid-phase extraction LC-MS/MS. Reference method for UCMR3 and many state programs.
- EPA Method 1633 — 40 PFAS in wastewater, surface water, groundwater, soil, sediment, biosolids, and fish tissue. Isotope-dilution LC-MS/MS with matrix-specific extraction. Required for NPDES industrial discharge characterization.
EPA 533: the modern drinking-water method
EPA 533 was published in 2019 specifically to cover the short-chain PFAS replacement chemistries (HFPO-DA / GenX, ADONA, 9Cl-PF3ONS) that the older 537.1 method couldn't capture. The 25-analyte list includes:
- PFAA carboxylates: PFBA, PFPeA, PFHxA, PFHpA, PFOA, PFNA, PFDA, PFUnA, PFDoA
- PFAA sulfonates: PFBS, PFPeS, PFHxS, PFHpS, PFOS, PFNS, PFDS
- FT sulfonates: 4:2 FTS, 6:2 FTS, 8:2 FTS
- Replacement chemistries: HFPO-DA (GenX), ADONA, 9Cl-PF3ONS, 11Cl-PF3OUdS, NFDHA
The method uses isotope-dilution direct injection — no solid-phase extraction step — which simplifies the workflow and reduces blank contamination risk. Sub-ppt sensitivity (typically 1-2 ng/L MDL per analyte).
Use EPA 533 when: testing finished drinking water for NPDWR compliance, UCMR5 monitoring, or any modern PFAS exposure assessment that needs the short-chain replacement chemistries.
EPA 537.1: the legacy drinking-water method
EPA 537.1 (published 2018, with 537 originally from 2009) is the longer-chain legacy method:
- 18 analytes, mostly C4 and longer perfluoroalkyl carboxylates and sulfonates.
- Solid-phase extraction with styrene-divinylbenzene SPE cartridges.
- Used for UCMR3 PFAS monitoring (2013-2015) and many state drinking-water programs that pre-date the 533 publication.
- LOQ typically 1.4 ng/L per analyte.
Use EPA 537.1 when: required for state-program comparability (some state agencies still specify 537.1 by name), for a particular analyte not in the 533 list, or when the source water has historical 537.1 data that needs to be tracked over time.
EPA 1633: multi-matrix for non-potable
Finalized in 2024 as part of EPA's PFAS Strategic Roadmap, Method 1633 extends PFAS quantitation to non-drinking-water matrices:
- 40 analytes — includes the 533 and 537.1 lists plus additional fluorotelomers, sulfonamides, and perfluorohexane-1-sulfonate variants.
- Matrices: wastewater, surface water, groundwater, soil, sediment, biosolids, leachate, and fish/biota tissue.
- Sample prep: matrix-specific extraction (SPE for waters, solvent extraction with cleanup for solids, basic digestion for biosolids).
- Isotope-dilution quantitation: every analyte paired with a 13C or 18O labeled internal standard, with extracted-internal-standards for matrix-correction.
Use EPA 1633 when: testing wastewater (NPDES permit characterization), soil or sediment (Superfund site assessment, AFFF firefighting-foam impact zones), biosolids (Class A / B sewage sludge land-application permits), or fish tissue (state advisory programs).
The 2024 NPDWR PFAS rule
EPA finalized the National Primary Drinking Water Regulation for PFAS in April 2024. The rule sets federal MCLs for six PFAS:
- PFOA — 4 ng/L (4 ppt)
- PFOS — 4 ng/L
- PFNA — 10 ng/L
- PFHxS — 10 ng/L
- HFPO-DA (GenX) — 10 ng/L
- Mixture of PFNA / PFHxS / HFPO-DA / PFBS — Hazard Index ≤ 1
Public water systems must complete initial monitoring by 2027 and reduce concentrations to compliance by 2029. The required reference method is EPA 533 or EPA 537.1; either is acceptable.
What an EPA-method PFAS COA should show
A defensible PFAS COA from any of the three methods includes:
- Method name and date (e.g. "EPA 533, March 2019 revision").
- Observed concentration per analyte in ng/L (or µg/L), with the method's MDL noted.
- Pass / fail per analyte against the cited regulatory MCL.
- For the mixture rule, the calculated Hazard Index and the individual analyte contributions.
- Isotope-labeled internal-standard recovery for each analyte (typically 70-130 %).
- Method-blank result (should be at or below MDL).
- Field-blank result if shipped with the sample (catches transit contamination).
- Hold-time documentation (PFAS samples should be analyzed within 28 days of collection).
The contamination footprint
PFAS analytical chemistry has a particularly hostile blank problem. PFAS are everywhere: in the analytical workflow itself (Teflon-coated tubing, sample bottles, lab equipment), in the analyst's clothing (water-repellent jacket coatings, Gore-Tex), and in the water supply of the lab building. A credible lab takes all-PFAS-free containment seriously — HDPE bottles only, no fluoropolymer tubing, separate analytical bench from other chromatography work, dedicated solvent supplies.
When evaluating a PFAS COA from any lab, the method-blank result and the field-blank result are the first things to check. If those aren't reported, the lab probably isn't running them — and PFAS results without blank documentation aren't defensible.
Summary
EPA 533 is the modern drinking-water method covering short-chain PFAS including the 2024 NPDWR-regulated analytes. EPA 537.1 is the legacy long-chain drinking-water method. EPA 1633 extends to wastewater, soil, biosolids, and tissue for non-potable matrices. All three use isotope-dilution LC-MS/MS quantitation at ppt sensitivity. A credible COA reports method-blank, field-blank, and isotope-labeled internal-standard recovery per analyte.
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