Application of nano-LC - nano-ESI - Orbitrap-MS for trace determination of four priority PFAS in food products considering recently established tolerable weekly intake (TWI) limits.

An analytical method was developed and validated for the analysis of four priority perfluoroalkyl substances (PFAS), namely, perfluorooctanoic acid (PFOA), perfluorononanoic acid (PFNA), perfluorohexanesulfonic acid (PFHxS), and perfluorooctanesulfonate (PFOS) in food products using nanoscale liquid chromatography (nano-LC) coupled with nanoscale electrospray ionization (nano-ESI) and Orbitrap mass spectrometry (Orbitrap-MS) detection. The efficiency of two different nano-LC setups for chromatographic separation of selected PFAS was evaluated. The optimal LC separation of analytes was achieved using a reversed phase C18 (RP-C18) nano bore column with an integrated emitter. The effect of matrix concentration factor on signal suppression/enhancement was evaluated for different matrices. The method validation indicated analyte recoveries in the range 83-118% and within-laboratory reproducibility from 7 to 18%, while reanalysis of the materials from proficiency tests (PTs) showed that the accuracy of the obtained concentrations ranged from 85 to 124% of the provided consensus values. The method limits of quantification (m-LOQs) were set as first validation levels ranging from 0.001 to 0.3 ng g-1 sample depending on the type of the food group. The observed method performance characteristics met the criteria stated in Commission Regulation (EU) 2022/1428, Commission Recommendation (EU) 2022/1431, as well as Guidance Document on Analytical Parameters for the Determination of Per- and Polyfluoroalkyl Substances (PFAS) in Food and Feed with regards to the compliance testing of PFAS maximum levels (MLs) and monitoring purposes. The elaborated method was applied for the analysis of selected priority PFAS in different food groups collected from the Latvian retail market.

Data on occurrence of perfluoroalkyl substances in influents and effluents collected from different wastewater treatment plants in Latvia.

The data set provided in this paper contains occurrence data of 17 perfluoroalkyl substances (PFAS) (including 10 perfluorinated carboxylic acids and 7 perfluorinated sulfonic acids) in influent and effluent samples collected from 43 wastewater treatment plants (WWTPs) located in different cities in Latvia. Samples were collected in the period June-July 2021. In each WWTP one influent and one effluent sample were collected on the same day. Extraction and clean-up of the samples were performed using solid phase extraction (SPE) on a weak-anion SPE phase. Observed extracts were analysed using high performance liquid chromatography coupled with Orbitrap high resolution mass spectrometry (HPLC-Orbitrap-MS) on the content of selected PFAS representatives. The collected data are with fundamental scientific value and can be applied for local data analysis. The data set is useful for the estimation of overall background levels of PFAS and evaluation of local city WWTPs wastewater remediation efficiency towards the removal of PFAS contamination.

Occurrence of selected per- and polyfluorinated alkyl substances (PFASs) in food available on the European market - A review on levels and human exposure assessment.

Per- and polyfluorinated alkyl substances (PFASs) are considered emerging persistent organic pollutants, which are chemically, thermally, and biologically stable, or degrade to persistent end products. Dietary intake is considered as one of the main human exposure pathways of these chemicals and, having entered the human body, PFASs are not metabolised and accumulate in tissues, while their toxicological properties may cause various health problems. Several studies on the occurrence of PFASs in various food types have been conducted, including the assessment of dietary exposure. The most important sources were fish, meat, eggs, fruits, and vegetables. Fruits and vegetables recently showed relatively high levels of PFASs, and have become a more significant source of PFASs than meat. In 2020, the European Food Safety Authority (EFSA) published an opinion, setting the tolerable weekly intake (TWI) of 4.4 ng kg-1 b.w. for the sum of perfluorooctanoic acid (PFOA), perfluorononanoic acid (PFNA), perfluorohexanesulphonic acid (PFHxS), and perfluorooctanesulphonic acid (PFOS). The emphasis in this paper is on the systematization of available information on the distribution of PFASs and their levels in different food, with a special interest in data from the Europe. The current legislation and estimated dietary intakes by the general population are described. While the available information on tolerably daily intakes estimated in a number of European countries often exceeds the newly established EFSA TWI, a critical evaluation of performance characteristics of the reviewed analytical methodologies revealed the insufficient sensitivity of quantification procedures for accurate risk assessment according to the guidelines proposed by EFSA.

Legacy and alternative brominated, chlorinated, and organophosphorus flame retardants in indoor dust-levels, composition profiles, and human exposure in Latvia.

Flame retardants (FRs) are additives used in consumer products to reduce flammability, even though they can easily contaminate the indoor environment. Since it is common for people in modern cities to spend up to 85% of time indoors, the quality of the indoor environment is critical for human health. In this study, polybrominated diphenyl ethers (PBDEs), organophosphorus flame retardants (OPFRs), emerging brominated flame retardants (EBFRs), and dechlorane-related compounds (DRCs) were measured in household dust samples (n = 34) from Latvia, followed by human exposure assessment. Among all studied compounds, OPFRs showed the highest concentrations (1380-133,000 ng g-1). Despite the phase-out of PBDEs, they were the second most significant flame retardants in the studied dust samples (468-25,500 ng g-1) and the predominant compound was BDE-209. The concentrations of EBFRs were in the range of 120-7295 ng g-1, with the most abundant contaminant being DBDPE, which is widely used as a substitute for the deca-BDE formulation. DRCs were the least common flame retardants in the Latvian indoor environments, with concentrations ranging 22.4-192 ng g-1. Although the concentrations of specific FRs are known to vary between different countries, the levels and patterns observed in dust samples from Latvia were similar to those reported from Central Europe. Human exposure was evaluated as the estimated daily intake (EDI). The calculated exposure to most of the FRs was several orders of magnitude lower than the available reference dose (RfD) values.

The impact of baking on chlorinated paraffins: Characterization of C10-C17 chlorinated paraffins in oven-baked pastry products and unprocessed pastry dough by HPLC-ESI-Q-TOF-MS.

This study presents an HPLC-ESI-Q-TOF method for simultaneous quantification of short-chain chlorinated paraffins (SCCPs, C10-13) and an additional characterization of medium-chain chlorinated paraffins (MCCPs, C14-17) in oven-baked pastry products (n = 38) and unprocessed pastry dough material (n = 15). Almost 2 times higher SCCP levels were found in the dough material. ΣSCCP concentrations in products ranged from 0.3 ng g-1 to 23.0 ng g-1 (mean: 6.3 ng g-1), while the results for dough ranged from 5.8 ng g-1 to 22.8 ng g-1 (mean: 12.9 ng g-1). Regardless of the sample matrix, the most abundant CP homologue groups were hepta- and octa-chlorinated undecanes and dodecanes. The average chlorination degree found in dough samples fell within a range of 55-60% (w/w). Meanwhile, a slight decrease of CP chlorination degree was observed for oven-baked products, in particular for C10-C12 SCCPs, thus indicating that thermal decomposition of CPs occurs even under relatively mild conditions.