Perfluorinated Compounds (PFCs) in Soil of the Pearl River Delta, China: Spatial Distribution, Sources, and Ecological Risk Assessment.

This study investigated the levels, spatial distribution, sources, and ecological risks of 16 perfluorinated compounds (PFCs) in 68 surface soil samples (0-20 cm) from 7 cities in the Pearl River Delta (PRD), China. Sixteen target PFCs, including perfluoroalkyl carboxylic acids (PFCAs, C5-C14, C16, and C18) and perfluoroalkyl sulfonic acids (PFSAs, C4, C6, C8, and C10), were analyzed by high-performance liquid chromatography-negative electrospray ionization-tandem mass spectrometry (HPLC/ESI-MS/MS). Concentrations of total PFCs (∑PFCs) ranged from 2.19 to 98.5 µg kg-1 (dry weight, dw), with an average of 5.97 µg kg-1 dw. Perfluorooctane sulfonate (PFOS) was the dominant PFC, accounting for 23.9% of ∑PFCs. The highest ∑PFCs was found in the soil sample collected from Dongguan with a large number of manufacturing industries. There were no significant differences of ∑PFCs among unban, industrial, and agricultural soils, indicating similar pollution sources in soil of the PRD. More than 70% of ∑PFCs in soil of the PRD could be attributed to the four principal components, represented by PFOS and perfluorooctanoic acid (PFOA), perfluoropentanoic acid (PFPeA) and perfluorohexanoic acid (PFHxA), perfluorodecanoic acid (PFDA), and perfluoroundecanoic acid (PFUdA). Ecological risk assessment indicated that PFOA had low risk to soil plants and animals. However, the risk of PFOS to soil plants was relatively high in some studied regions.

Assessment of perfluoroalkyl substances levels in tap and bottled water samples from Turkey.

Perfluoroalkyl and polyfluoroalkyl substances (PFASs) draw considerable attention for their potential toxic effects in humans and environment. Drinking water is accepted as one of the major exposure pathways for PFASs. In this study, we measured concentrations of 10 perfluoroalkyl substances in 94 tap water samples collected in two different sampling periods (August 2017 and February 2018) from 33 provinces of Turkey, as well as in 26 different brands of plastic and glass-bottled water samples sold in supermarkets in Turkey. Perfluorohexanoic acid (PFHxA), perfluorobutane sulfonate (PFBS) and perfluoropentanoic acid (PFPeA) were the most frequently detected PFASs in the samples of tap waters. The maximum concentrations in tap waters were measured as 2.90, 2.37, 2.18, 2.04, and 1.93 ng/L, for PFHxA, perfluorooctanoic acid (PFOA), perfluorohexane sulfonate (PFHxS), perfluorooctane sulfonate (PFOS), and perfluorobutanoic acid (PFBA), respectively. The most abundant perfluorinated chemical in tap water samples was PFBA with 17%, followed by PFOS (13%), PFBS (12%), perfluoroheptanoic acid (PFHpA) (11%), PFHxA (11%), and PFOA (11%). The total PFASs concentration in tap water ranged from 0.08 to 11.27 ng/L. As regards bottled waters, the concentrations of PFASs were generally lower than those in tap water samples. These results revealed that tap water samples in Turkey might be considered generally safe based on the established guidelines around the world. However, due to their persistence and potential to accumulate and reach higher concentrations in the environment, careful monitoring of PFASs in all types of water is critical.

Exposure assessment to parabens, bisphenol A and perfluoroalkyl compounds in children, women and men by hair analysis.

Population is continuously exposed to endocrine disrupting compounds present in everyday products such as parabens, bisphenol A (BPA), and perfluoroalkyl compounds (PFCs). The aims of this study were, first, to evaluate human exposure to three parabens (methylparaben (MeP), ethylparaben (EtP) and propylparaben (PrP)), BPA and six PFCs (perfluorobutanoic acid, perfluoropentanoic acid, perfluorohexanoic acid, perfluoroheptanoic acid (PFHpA), perfluorooctanoic acid (PFOA) and perfluorooctanesulfonic acid (PFOS)) through the analysis of hair samples from children, women and men and, then, to evaluate possible relationships between pollutant concentration in hair and age, gender, smoking and dyeing habits or hair colour. Hair samples were collected from 42 volunteers from Seville (Spain) (10 children, 16 women and 16 men). Six of the monitored pollutants (MeP, EtP, PrP, BPA, PFHpA and PFOS) were detected in at least 76% of the samples analysed. The highest concentrations and frequency of detection (100% of the samples) corresponded to MeP and PrP (up to 14,187 and 9009 ng/g, respectively). BPA was found in 83% of the samples at concentrations in the range from 24 to 1427 ng/g whereas PFCs were detected at concentrations in the range from 0.6 to 15.5 ng/g, being PFHpA and PFOS the ones most frequently detected (86% and 76%, respectively). Concentrations of BPA and parabens in adults were statistically higher than those in children. The results of this study reveal the suitability of hair for biomonitoring endocrine disrupting compounds of high concern (PFCs, parabens and BPA) to which population is internally or/and externally but continuously exposed.

Perfluorohexanoic acid toxicity, part II: Application of human health toxicity value for risk characterization.

Perfluorohexanoic acid (PFHxA) is a short-chain, six-carbon PFAA and is a primary impurity, degradant, and metabolite associated with the short-chain fluorotelomer-based chemistry used in the United States, Europe and Japan today. With the shift towards short-chain PFAA chemistry, uncertainties remain regarding human health risks associated with current exposure levels. Here, we present a critical review and assessment of data relevant to human health risk assessment to today's short-chain PFAA chemistry. Human biomonitoring surveys indicate that PFHxA is infrequently detected in the environment as well as in human serum and urine; however, human health concerns may persist in locations where PFHxA is detected. In a companion paper (Luz et al., 2019) we comprehensively evaluate the available toxicity data for PFHxA, and derive a chronic human health-based reference dose (RfD) for PFHxA of 0.25 mg/kg-day based on benchmark dose modeling of renal papillary necrosis in chronically exposed female rats. In this paper, we apply this RfD in human health-based screening levels calculations, and derive a drinking water lifetime health advisory of 1400 µg/L and a residential groundwater screening level for children of 4000 µg/L. Compared to environmental concentration data, even sites with more elevated concentrations of PFHxA in the environment are at least an order of magnitude lower than these screening levels. Available PFHxA human serum and urine biomonitoring data, used as a biomarker for general population exposure, demonstrates that the general human population exposures to PFHxA are low. Previous estimates of daily intake rates for infants exposed to PFHxA through breast milk, formula, and baby foods (Lorenzo et al., 2016) combined with the most conservative PFHxA peer-reviewed toxicity value (Luz et al., 2019) demonstrate that the margin of safety for PFHxA is high. Therefore, PFHxA and related fluorotelomer precursors currently appear to present negligible human health risk to the general population and are not likely to drive or substantially contribute to risk at sites contaminated with PFAS mixtures. PFHxA may also represent a suitable marker for the safety of fluorotelomer replacement chemistry used today.

Risk exposure assessment of per- and polyfluoroalkyl substances (PFASs) in drinking water and atmosphere in central eastern China.

We examined per- and polyfluoroalkyl substances (PFASs) in air from eight cities, and in water from six drinking-water treatment plants (DWTPs), in central eastern China. We analyzed raw and treated water samples from the DWTPs for 17 ionic PFASs with high-performance liquid chromatography/negative-electrospray-ionization tandem mass spectrometry (HPLC/(-)ESI-MS/MS), and analyzed the gas and particle phases of atmospheric samples for 12 neutral PFASs by gas chromatography-mass spectrometry (GC-MS). Perfluorooctanoic acid (PFOA) and perfluorohexanoic acid (PFHxA) were the dominant compounds in drinking water, and fluorotelomer alcohols (FTOHs) dominated in atmospheric samples. Of all the compounds in the treated water samples, the concentration of PFOA, at 51.0 ng L-1, was the highest. Conventional treatments such as coagulation (COA), flocculation (FOC), sedimentation (SED), and sand filtration (SAF) did not remove PFASs. Advanced treatments, however, including ultrafiltration (UF) and activated carbon (AC), removed the majority of PFASs except for shorter-chain PFASs such as perfluorobutanoic acid (PFBA) and perfluoropentanoic acid (PFPA). We also investigated human exposure to PFASs via drinking water and the atmosphere and found that the mean daily intake of PFASs was 0.43 ng kg-1 day-1.

Quantification of allyl hexanoate in pineapple beverages and yogurts as a case study to characterise a source of uncertainty in dietary exposure assessment to flavouring substances.

One source of uncertainty in the estimation of dietary exposure to flavouring substances is the uncertainty in the occurrence and concentration levels of these substances naturally present or added to foodstuffs. The aim of this study was to assess the variability of concentration levels of allyl hexanoate, considered as a case study, in two main food categories to which it is often added: pineapple juice-based beverages and yogurts containing pineapple. Thirty-four beverages and 29 yogurts, with pineapple fruit or juice and added flavourings declared as ingredients on the package, were purchased from the local market (in Rome) and analysed. Analytical methods based on the stir bar sorptive extraction (SBSE) technique for the isolation of the target analyte, and on GC-MS analysis for final determination, were developed for the two food categories. In beverages, allyl hexanoate concentrations ranged from less than 0.01 to 16.71 mg l(-1), whereas in yogurts they ranged from 0.02 to 89.41 mg kg(-1). Average concentrations in beverages and yogurts with pineapple as the main fruit ingredient (1.91 mg l(-1) for beverages, 9.61 mg kg(-1) for yogurts) were in fair agreement with average use level data reported from industry surveys for the relevant food categories (4.5 and 6.0 mg kg(-1), respectively). Within the group of yogurts a single product was found to contain a level of allyl hexanoate more than 10-fold higher than the average reported use level. The screening techniques developed by the European Food Safety Authority (EFSA) using use level data provided by industry gave estimates of exposure that were of the same order of magnitude as the estimates obtained for regular consumers who would be loyal to the pineapple yogurt and beverage products containing the highest observed concentration of the substance of interest. In this specific case the uncertainty in the results obtained with the use of standard screening techniques for exposure assessment based on industry reported use levels is low.

Assessment of strawberry aroma through SPME/GC and ANN methods. Classification and discrimination of varieties.

To provide an efficient and running analytical tool to strawberry plant breeders who have to characterize and compare the aromatic properties of new cultivars to those already known, a HS-SPME/GC-MS analysis method has been coupled with a statistical treatment method issued from the current development of artificial neuron networks (ANN), and more specifically, the unsupervised learning systems called Kohonen self-organizing maps (SOMs). So, 70 strawberry samples harvested at CIREF from 17 known varieties have been extracted by using a DVB/Carboxen/PDMS SPME fiber according to the headspace procedure, and then chromatographed. A panel of 23 characteristic aromatic constituents has been selected according to published results relative to strawberry aroma. The complex resulting matrix, collecting the relative abundance of the 23 selected constituents for each sample, has been input into the SOM software adapted and optimized from the Kohonen approach described by one of the authors. After a period of training, the self-organized system affords a map of virtual strawberries to which real samples are compared and plotted in the best matching unit (BMU) of the map. The efficiency for discriminating the real samples according to their variety is dependent on the number of units selected to define the map. In this case, a 24-unit map allowed the complete discrimination of the 17 selected varieties. Moreover, to test the validity of this approach, two additional samples were blind-analyzed and the results were computed according to the same procedure. At the end of this treatment, both samples were plotted into the same unit as those of the same variety used for training the map.