Analysis of perfluoroalkyl substances in waters from Germany and Spain
Abstract
Water has been identified as one of the main routes of human exposure to perfluoroalkyl substances (PFASs). This work assessed the presence of 21 PFASs along the whole water cycle using a new fast and cost effective analytical method based on an online sample enrichment followed by liquid chromatography coupled to tandem mass spectrometry (LC-MS/MS). The method was validated for different types of matrices (ultrapure water, tap water and treated wastewater). The quality parameters for the 21 selected compounds presented good limits of detection (LOD) and quantification (LOQ) ranging, in general, from 0.83-10 ng/L to 2.8-50 ng/L, respectively. The method was applied to assess the occurrence of PFASs in 148 water samples of different steps along the whole water cycle, including: mineral bottled water, tap water, river water and treated effluent wastewater, from Germany to Spain. In addition, in order to prove the good performance of the online analytical method, the analysis of PFASs was carried out in parallel using a method based on offline anionic solid phase extraction (SPE) followed by LC-MS/MS. Consistent results were obtained using both approaches. The more frequently found compounds were perfluoroalkyl acids, such as the perfluorobutanoic acid which was in the 54% of the tap water samples investigated with concentrations in the range between 2.4 and 27 ng/L, the perfluoroheptanoic acid (0.23-53 ng/L) and perfluorooctanoic acid (0.16-35 ng/L), and the sulphonate perfluor…
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The high PFOS/PFHxS levels indicate strong localized contamination likely linked to historical industrial emissions and legacy uses of PFOS-containing products, including firefighting foams.
“indicating strong localized contamination likely linked to historical industrial emissions and legacy uses of PFOS-containing products, including firefighting foams [32,33,34,35].”
From Integrated Targeted and Suspect Screening Workflow for Identifying PFAS of Concern in Urban-Impacted Serbian Rivers (2026) · cites this paper as [32]
Elevated concentrations of long-chain PFCAs, such as PFDA (213 ng/L) and PFNA (52 ng/L), underline the influence of persistent legacy sources in Spain surface waters.
“Elevated concentrations of long-chain PFCAs, such as PFDA (213 ng/L) and PFNA (52 ng/L), further underline the influence of persistent legacy sources in Spain surface waters [32].”
From Integrated Targeted and Suspect Screening Workflow for Identifying PFAS of Concern in Urban-Impacted Serbian Rivers (2026) · cites this paper as [32]
The comparative overview of maximum concentrations of targeted PFAS in European surface waters reveals pronounced spatial differences among freshwater systems across Europe.
“The comparative overview of maximum concentrations of targeted PFAS in European surface waters (Table S7) reveals pronounced spatial differences among freshwater systems across Europe”
From Integrated Targeted and Suspect Screening Workflow for Identifying PFAS of Concern in Urban-Impacted Serbian Rivers (2026) · cites this paper as [32]
Exceptionally high PFOS concentrations were reported in Spain (2709 ng/L) and France (197 ng/L branched-PFOS and 173 ng/L linear-PFOS), with elevated PFHxS levels (217 ng/L) in France.
“Exceptionally high PFOS concentrations were reported in Spain (2709 ng/L) [32] and France (197 ng/L of branched-PFOS and 173 ng/L of linear-PFOS) [33], with the latter accompanied by elevated PFHxS levels (217 ng/L) [33]”
From Integrated Targeted and Suspect Screening Workflow for Identifying PFAS of Concern in Urban-Impacted Serbian Rivers (2026) · cites this paper as [32]
Llorca et al. reported an exceptionally high PFOS concentration (2709 ng/L) at a single Spanish surface water site.
“In the study by Llorca et al., [32] an exceptionally high PFOS concentration (2709 ng/L) was reported at a single Spanish surface water site.”
From Integrated Targeted and Suspect Screening Workflow for Identifying PFAS of Concern in Urban-Impacted Serbian Rivers (2026) · cites this paper as [32]
54% of all tap water samples were contaminated with PFBA at concentrations ranging from 2.4-27 ng/L.
“Overall, 54% of all tap water samples were contaminated with PFBA at concentrations ranging from 2.4–27 ng L−1 (Llorca et al., 2012).”
From Per- and polyfluoroalkyl substances in water and wastewater: A critical review of their global occurrence and distribution (2022) · cites this paper as Llorca et al., 2012
Between 2010 and 2012, a large-scale study spanning 32 cities in Germany and Spain analyzed 148 water samples for 21 PFAS, and 88% contained at least one quantifiable amount of PFAS.
“Between 2010 and 2012, a large-scale study spanning 32 cities in Germany and Spain analyzed samples of ultrapure water, tap water, and treated wastewater. There were 148 water samples analyzed for the presence of 21 PFAS, and 88% contained at least one quantifiable amount of PFAS.”
From Per- and polyfluoroalkyl substances in water and wastewater: A critical review of their global occurrence and distribution (2022) · cites this paper as Llorca et al., 2012
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“Maximum Σ PFAS N values range from 35.02 ng/L in Malta ( N = 7) [37] and 42 ng/L in Finland ( N = 23) [36] to substantially higher maxima in France ( Σ PFAS N = 725 ng/L; N = 22) [33] and Spain ( Σ PFAS N = 2878 ng/L; N = 21) [32].”
InfluentialSelf-citation
- Authors
- Llorca, M., Farré, M., Picó, Y., Müller, J., Knepper, T. P., & Barceló, D.
- Affiliations
- Consejo Superior de Investigaciones Científicas (ES)
- Universitat de València (ES)
- Hochschule Fresenius (DE)
- Corresponding author
- Farré, Marinella
- Venue
- Science of The Total Environment
- Publisher
- Elsevier BV
- Published
- 2012-08
- Volume
- 431
- Pages
- 139-150
- ISSN
- 0048-9697 (ISSN-L)
- OpenAlex
- W1977892371
- Cited by
- 170
- References
- 42
- Citations by year
- 2026: 10 · 2025: 14 · 2024: 14 · 2023: 21 · 2022: 12 · 2021: 11 · 2020: 12 · 2019: 10 · 2018: 9 · 2017: 17 · 2016: 8 · 2015: 12 · 2014: 12 · 2013: 6 · 2012: 2
- FWCI
- 8.19
- Type
- journal article
- Language
- en
- Open access
- closed
- Locations
- The Science of The Total Environment (publishedVersion)
- PubMed (publishedVersion)
- Funders
- “Assessing and predicting effects on water quantity and quality in Iberian rivers caused by global change” (SCARCE) (CSD-2009-00065)
- “Environmental ChemOinformatic - Marie Curie Initial Training Network” (ECO-ITN) (PITN-GA-2009-238701)
- Topics
- Physical Sciences › Environmental Science › Environmental Chemistry › Per- and polyfluoroalkyl substances research
- Life Sciences › Pharmacology, Toxicology and Pharmaceutics › Pharmaceutical Science › Fluorine in Organic Chemistry
- Physical Sciences › Chemistry › Analytical Chemistry › Analytical chemistry methods development
- Keywords
- perfluorinated compounds, PFAS, drinking water contamination, tap water, bottled water, treated wastewater, river water, perfluorooctanoic acid, perfluorobutanoic acid, PFOS, short-chain PFAS, human exposure, health risks, Germany, Spain
- MeSH terms
- Caprylates, Chromatography, Liquid, Environmental Exposure, Environmental Monitoring, Fluorocarbons, Germany, Humans, Spain, Waste Disposal, Fluid, Water Pollutants, Chemical, Tandem Mass Spectrometry, Limit of Detection, Drinking Water
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