Water Industry Journal talks to PFAS scientific expert Marcus Chadha about the tough challenges that lie ahead for UK water measurement companies.
How many PFAS have been identified globally? Which ones present the most serious risk to health / the environment?
There are over 4000 known or suspected PFAS compounds globally in commerce. Their thermal and chemical stability as well as their surface-tension lowering properties, has led to their prominent use in many products for more than 50 years. For example, as coatings in grease proof food packaging, stain repellents, surfactants, and firefighting foam. PFAS cause environmental concern as many types do not naturally degrade and often bioaccumulate.
As a result, PFAS are almost ubiquitous in the environment, and assessments are being increasingly applied by governing bodies to gain a comprehensive understanding of the risks they pose.
In terms of their detection, each PFAS compound falls into two categories: volatile and non-volatile. We can measure volatile PFAS using Gas Chromatography Mass Spectrometry (GCMS) and non-volatile using Liquid Chromatography Mass Spectrometry (LCMS). That being said, we must not forget neutral PFAS, while we know they are present; it is much harder to detect chemically neutral PFAS compounds because of their lower functional properties used to aid their detection.
What specific types are recognised in the UK?
Every country is at a different stage in their regulated PFAS monitoring. Until recently, the UK routinely monitored for two types of PFAS compounds: PFOS and PFOA. These were the most commonly used by manufacturing in UK1, with PFOS being banned completely in June 20082. They are extremely toxic and are known to bioaccumulate in the food chain, having entered the environment from manufacturing effluent and consumer products.
The collaborative research between Agilent and the Environment Agency has led to the development of a method which can test for the presence of 47 PFAS compounds in water.3
How are PFAS currently regulated in the UK compared to the rest of the world?
Implementing this new method will take the number of PFAS compounds regulated in the UK from two to 47 in 2022. However, other countries have seen a quicker acceleration. For example, in Sweden, testing has been extended to 26 PFAS compounds since 2013. The European Union drinking water directive has recently increased their regulated list to 20 PFAS compounds as of December 2020. Federal regulation in the US by USEPA is expected imminently for PFOS and PFOA, but several states already have regulations in drinking water for many PFAS and national monitoring studies for PFAS have been ongoing for the last decade.
In the UK, the extended list of 47 PFAS compounds has been tested in groundwater and will soon be tested in other waters such as surface water. The Drinking Water Inspectorate (DWI) is using the data from the research to inform fellow environmental monitoring companies on the PFAS compounds they will need to investigate in the UK.
Testing multiple sub-classes of PFAS in one method with the presence of short-chain and long-chain compounds with differing solubility can present challenges, however advances in mass spectrometry and method development are helping to navigate these challenges. We have developed a new method using direct injection into an LCMS and utilizing Agilent’s proprietary dynamic multiple reaction monitoring (MRM) to achieve sensitivity of less than 1ng/L.
Why are more stringent regulations needed?
Greater regulations are needed because we simply do not know enough about the extent of the effect that PFAS have on health and the environment. As we investigate further, newer and different PFAS have been detected in waters around the world.
There have been discussions 4 that all the 4000 plus PFAS will need some form of methodology capable of detecting them within the next three years. We may not necessarily measure them all but need to better understand which sub-groups or certain compounds are more prevalent and pose a greater risk.
In terms of detection levels, they have initially been set quite conservatively at 100 nanograms per litre. The industry expects these to drop significantly to one nanogram per litre and even lower than one nanogram per litre for some compounds for certain water types in the future.
Analytically there are two main ways to monitor for PFAS compounds: targeted, where we look at a set list of compounds using quantitative analysis, and untargeted, where we screen for suspect PFAS compounds or unknowns PFAS compounds in the environment. This enables us to have a holistic understanding of the presence of different types of PFAS in the UK’s waters and an idea of the extent of the problem.
Do the UK water industry and decision-makers appreciate the scale of the problem?
Yes, they are becoming increasingly aware, but water companies and commercial contact laboratories have risen to the challenge and are moving quickly to adapt to meet the new requirements to protect customers.
Something we’ve seen in the US that will soon be introduced in the UK is requiring manufacturers to authenticate the PFAS they create; they must measure how much PFAS their products contain and monitor PFAS in influent and effluent to reduce their environmental impact. This accountability is becoming of paramount importance. In fact, studies using our chemometric software for environmental profiling have detected PFAS in waters and been able to track them back to their original source of contamination. 5
There are calls to increase number of PFAS measured in UK waters from two to 47. If enforced, what is the scale of the challenge ahead for our water measurement companies in terms of cost and logistics.
There is a big challenge ahead for water measurement companies, and it will help to collaborate with analytical companies to bolster PFAS measurement procedures. For example, companies will need to first understand the regulations for measuring the 47 different compounds. They will then need to develop existing applications for PFAS testing with new instruments, as some of the new PFAS compounds are trickier than others to detect and require more sensitive equipment. This may mean staff will require extra training to become familiar with the new test requirements. This will have some cost implications for water companies.
What innovations could help solve the problem?
The work on this new targeted workflow for detection and identification of 47 PFAS compounds in drinking water, can be made more efficient with several innovations.
There are a few tips and hardware modifications to make the testing of PFAS as efficient and accurate as possible. We recommend that as well as using the most sensitive mass spectrometers to achieve the best results, using direct injection will make workflows as time efficient as possible, preventing the need for additional sample preparation. Investing in a PFC Free Kit helps to avoid contamination of these ubiquitous compounds by removing ‘background noise’ from the instrument and achieve true blank injections to ensure subsequent samples give accurate readings. Valve switching can also help reduce background levels and carry over of the long-chained PFAS compounds.
What is the importance of LCMS analytical instruments for environmental analysis?
The advantage that LCMS brings for environmental analysis is the ability to detect compounds at lower levels. Using traditional HPLC and GC, we can detect low milligrams per litre which are parts per million. Using the latest and most innovative instruments, we are now able to detect sub-nanograms per litre which are parts per trillion and streamline analysis even further.
This new PFAS method uses an UHPLC coupled to a triple quadrupole mass spectrometer – the Agilent 6495C Triple Quadrupole LC/MS – for targeted analysis at lower levels.
About Marcus’s work
Marcus Chadha, an EMEA LCMS Field Application Specialist Manager at Agilent Technologies, is working closely with the Environment Agency on a new method for monitoring an increased number of PFAS. The new method, developed on Agilent instrumentation, has now been adopted by the Drinking Water Inspectorate (DWI).
References
1 https://consult.environment-agency.gov.uk/environment-and-business/challenges-and-choices/user_uploads/perfluorooctane-sulfonate-and-related-substances-pressure-rbmp-2021.pdf
2 Microsoft Word – PFOS & PFOA General Information phe v1 (publishing.service.gov.uk)
3 Information-Letter-PFAS-Monitoring.pdf (dwi.gov.uk)
4 https://www.oecd.org/officialdocuments/publicdisplaydocumentpdf/?cote=ENV-JM-MONO(2018)7&doclanguage=en
5 https://link.springer.com/article/10.1007/s00216-021-03463-9
