PFAS, Total Organic Precursors (TOPS) and Total Organic Fluorine (TOF)

“What’s the difference and when to use one over the other?”

Over the past ten years, there has been an extraordinary amount of attention focused on perfluorooctane sulfonic acid (PFOS), perfluorooctanoic acid (PFOA) and related per- and polyfluorinated alkyl substances (PFAS), particularly with respect to their characterization, delineation, management and regulation in the environment. Environmental stakeholders are continually developing a better understanding of: occurrence, exposure and toxicity; proper sampling and analysis protocols; and remedial options.

From an analytical standpoint, testing for PFAS has been primarily through liquid chromatography coupled with tandem mass spectrometry (LC/MS/MS). As a “targeted” analytical technique, the results are limited to a fixed set of parameters. In other words, the results do not necessarily provide a comprehensive measure of the potential magnitude of the total pool of PFAS that may exist in contaminated soils and water, nor does it measure the potential for PFAS formation due to natural transformation of precursor compounds over time to the regulated end products.

In an attempt to identify the presence of other, non-target PFAS present in a contaminated sample, the total oxidizable precursors (TOPs) assay was developed [1]. More recently, there has been a focus by laboratories to develop and validate lower cost alternatives that also provide a more comprehensive measure of total PFAS impact. This has resulted in several methods for measuring total organic fluorine (TOF) as a proxy for total PFAS contamination.

Each of these analytical approaches offers distinct advantages for environmental practitioners. At the same time, the limitations of each need to be considered when assessing their utility in different situations.

“What’s the Difference?”

PFAS by LC/MS/MS

The determination of individual, target PFAS is performed using isotope dilution and liquid chromatography coupled with tandem mass spectrometry (LC/MS/MS). These analytical protocols represent industry accepted best practices and are typically based on United States Environmental Protection Agency (US EPA) methods.

Samples are spiked with isotopically labelled analogues of the native compounds being measured. Solid samples undergo an aqueous (methanol/water) extraction. Liquid samples or extracts from solid samples are submitted for solid phase extraction (SPE), clean-up and concentration. The resultant extracts are then analysed by LC/MS/MS.

Total Oxidizable Precursors (TOPs) Assay

PFAS analyses using LC/MS/MS typically identify, quantify and report 20-50 PFAS. However, it is well understood that there are potentially thousands of PFAS (5000+) present in the environment, most of which are unknown or uncharacterized. These are often referred to as ”dark matter”

It has been shown [2] that through biological processes precursor compounds within this PFAS dark matter can break down or transform into PFAS end products that are measured. By doing so, this dark matter can contribute toxicity risk beyond that identified by PFAS by LC/MS/MS.

Based on a published method [1], the TOPs assay is an analytical approach developed to provide an indication of non-target PFAS by modelling the in situ behavior of the dark matter in the laboratory. In short, the TOPs assay provides an approach to accelerating and predicting in situ precursor behavior.

To summarize the method:

• Samples are collected in duplicate
• The first aliquot is analyzed for target PFAS using LC/MS/MS to establish current or baseline concentrations
• The second aliquot is oxidized, transforming PFAS precursors to PFAS end products, and analyzed by LC/MS/MS
• The change in target PFAS concentration is representative of higher molecular weight PFAS (“precursors”) that may, over time, convert to the lower molecular weight PFAS end products

Total Organic Fluorine (TOF) by Combustion Ion Chromatography (CIC)

The measurement of TOF in environmental matrices, among others (e.g. AFFF, consumer products, etc.) provides the user with single result that is representative of the total PFAS concentration in the sample. Considering organic fluorine as a proxy for PFAS, the concentration measured in a sample will be representative of total PFAS.

Sample extracts are prepared in a manner that removes inorganic fluorine compounds, leaving only organofluorine compounds, the majority of which will be PFAS. The extracts are then incinerated at high temperature (>1000° C), and the mineralized fluorine measured by ion chromatography.

The advantages and limitations of the various PFAS test methods are presented in Table 1.

Table 1: Advantages and Limitations of PFAS Test Methods

TEST NAME	PROJECT OBJECTIVE	ADVANTAGES	LIMITATIONS
PFAS by LC/MS/MS	Characterization of individual PFAS Target PFAS delineation Risk Assessment Regulatory Compliance	Provides accurate concentrations for individual PFAS Typical parameter lists include 30-40 compounds 1-2 ng/L reporting limits meets all current regulatory standards	Higher cost test “Targeted analysis”, i.e., reports 30-40 individual compounds…out of a potential 5000+ PFAS
Total Oxidizable Precursors (TOPs) Assay	Indication of total PFAS contamination PFAS (target and non-target) delineation Risk Assessment Regulatory Compliance Future Liability	Provides accurate concentrations for individual PFAS Indicates the presence of compounds not measured by PFAS by LC/MS/MS Indicates potential for future liability due to transformation of precursor compounds	Labor intensive assay, leads to longer turnaround times High cost Not fully quantitative High sample variability Does not necessarily provide a “total” PFAS result
Total Organic Fluorine (TOF)	Measure of total PFAS contamination “Is my sample “PFAS-free?”	Provides concentration of organic fluorine, which is representative of the presence or absence of PFAS Less labour intensive Lower priced analysis	Reporting limits 1-2 ug/L (total F) in water

“When do I use PFAS by LC/MS/MS, TOPs Assay and/or TOF by CIC?”

ANALYTICAL NEED	PFAS BY LC/MS/MS	TOPS ASSAY	TOF BY CIC
Regulatory Compliance
Site Characterization
Contaminant Delineation
Complete Remediation
Site Risk (Future Liability)
PFAS-Free Product (e.g. AFFF)

The Bureau Veritas PFAS Analytical “Toolkit”

PFAS by LC-MS/MS

• Target PFAS determined at trace levels
• Compliant with modified EPA Method 537 and Method 533
• Accredited by Standards Council of Canada (SCC), US Department of Defense (QSM 5.3) and the US National Environmental Laboratory Accreditation Program (NELAP)

TOPs Assay

• Target PFAS determined at trace levels, before and after oxidizing the sample to simulate natural processes
• The measurement of PFAS is compliant with modified EPA Method 537 and Method 533
• Accredited by Standards Council of Canada (SCC) and the US National Environmental Laboratory Accreditation Program (NELAP)

TOF by CIC

• Measure of total PFAS based on the organofluorine content in a sample
• No current EPA method
• Accredited through Standards Council of Canada (SCC)

References

[1] Houtz, E.F. and Sedlak, D.L. (2012), Environ. Sci. Technol., 46, 9342-9349

[2] Wang, et. al. (2005) Environ. Sci. Technol., 39, 7516-7528