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Food contact materials (FCMs) from three countries were analysed for all extractable organofluorines (EOFs) from the materials and subsequently by target and non-target analysis for per- and polyfluoroalkyl substances (PFAS). The EOF varied by two orders of magnitude for FCM from UK and Saudi Arabia ranging between 2.14 and 483 ng cm-2 (0.2-48 ng g-1) showing that one quarter of all samples were above the Danish regulation for PFAS in FCM. Target PFAS showed high variability in composition and accounted for less than 1% of the EOF. Non-target PFAS screening using HPLC-ICP-MS and coupled simultaneously to HRMS showed the occurrence of organofluorines which were identified by neither LC-MS/MS nor LC-HRMS. This illustrates that the current target PFAS approaches fail to identify EOFs from FCM, which would be a problem with the new EU proposal to ban all PFAS.

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Wild boars have been reported as bioindicators for per- and polyfluoroalkyl substances (PFAS) in a variety of studies. However, data about PFAS levels in wild boars from sites with limited industrial and general human activity is scarce. In this study, wild boar (Sus scrofa) organs from the Bohemian Forest National Park (Czech Republic) were used as bioindicators for PFAS pollution. In this work, 29 livers and 24 kidneys from 30 wild boars (0.5-5 years) were investigated using a fluorine mass balance approach. For this, the samples were measured using high performance liquid chromatography with electrospray ionisation tandem mass spectrometry (HPLC-ESI-MS/MS), targeting 30 PFAS, including legacy and replacement PFAS, direct total oxidisable precursor assay (dTOPA) and combustion ion chromatography (CIC). Perfluorocarboxylic acids (PFCAs) from C7 to C14 and perfluorooctanesulfonic acid (PFOS) were detected in >50 % of samples. In the livers, PFCAs dominated the profile with median concentrations of 230 µg/kg for perfluorononanoic acid (PFNA) and 75 µg/kg perfluorooctanoic acid (PFOA). PFOA and PFNA concentrations in the livers were one order of magnitude higher than in livers from wild boars caught in rural NE Germany considered as background concentration. PFOS in liver contributed only 30 % to the Σc(PFASTarget) with a median concentration of 170 µg/kg. Kidneys and livers contain an average of 2460 µg F/kg and 6800 µg F/kg extractable organic fluorine (EOF) respectively. Σc(PFASTarget) add up to a maximum of 10 % of the extractable organic fluorine. After oxidisation of the samples, PFOA, PFNA and Σc(PFASdTOPA) increased in livers, but could not explain the EOF. The elevated concentration of PFOA and PFNA may indicate differences in biomagnification for different habitats or an unidentified PFAS source in proximity to the national park.

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GenX (hexafluoropropylene oxide dimer acid) belongs to the group of per- and poly-fluoroalkyl substance (PFAS) compounds introduced to replace perfluorooctanoic acid (PFOA), which has been phased out in industrial and consumer product formulations. While GenX has been investigated in lab animals, there is limited information available regarding its uptake and translocation in wheat and rice. This study reports on a greenhouse experiment in which wheat and rice grown under flooded and non-flooded conditions were exposed to two GenX concentrations in the soil (0.4 mg kg-1 and 2 mg kg-1). GenX was analysed in the soil, porewater and shoots using targeted liquid chromatography-tandem mass spectroscopy (LC-MS/MS) analysis. Extractable organic fluorine (EOF) was determined using high-resolution continuum source graphite furnace molecular absorption spectrometry (HR-GFMAS) instrument. Results showed that different species took up different amounts of GenX. The GenX concentration in rice shoots was found to be 2.34 (± 0.45) and 4.11 (± 0.87) µg g-1 under flooded and non-flooded conditions, respectively, at a low exposure level. At high exposure, the GenX concentrations in flooded and non-flooded rice shoots increased threefold to 10.4 (± 0.41) and 13.4 (± 0.72) µg g-1, respectively. Wheat shoots showed similar concentrations and increases between low- and high-level exposure. The translocation factor was significantly higher (P = 0.013) in non-flooded rice compared to flooded rice. The GenX bioaccumulation behaviours under the same culture conditions (e.g. temperature, humidity, light, same GenX concentration in the soil) were significantly different in non-flooded and flooded rice (P < 0.001). Non-flooded rice plants displayed a higher level of GenX bioaccumulation than flooded ones. Following exposure to GenX, flooded rice plants showed a reduction in biomass (25%) compared to the control plants (P < 0.014). Our findings indicate that GenX is a bioaccumulative compound, the presence of which likely inhibits the growth of plants.

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Per and polyfluoroalkylated substances (PFAS) are common additives in ski waxes for their water repellent characteristic. Abrasion of ski wax leaves PFAS on the snow surface, however, little is known about the distribution and concentration of PFAS in snow and soil due to skiing. In this study we analysed different ski waxes, snowmelts and soil from family skiing areas from Alpine locations using targeted high performance liquid chromatography tandem mass spectrometry (HPLC-MS/MS) to understand more about PFAS distribution in the environment. In general, we found a very diverse PFAS pattern in the analysed media. PFAS level was higher in skiing areas compared to the non-skiing ones that were used as control. ∑target PFAS ranged between <1.7 ng L-1 and 143 ng L-1 in snowmelt, <0.62 ng g-1 and 5.35 ng g-1 in soil and <1.89 and 874 ± 240 ng g-1 in ski wax samples. Snowmelt was dominated by short-chained PFAS, while soil and wax contained both short and long-chained PFAS. Extractable organic fluorine (EOF) was several orders of magnitude higher for waxes (0.5-2 mg g-1) than for soils (up to 0.3 µg g-1), while total fluorine (TF) content of the waxes was even higher, up to 31 210 ± 420 µg g-1. We also showed that the ∑ target PFAS accounts for up to 1.5% in EOF content, showing that targeted LC-MS/MS gives a limited measure of the pollution originated from ski waxes and non-targeted analysis and EOF is necessary for a better overview on PFAS distribution.

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Wastewater treatment plants are a major source of per and polyfluoroalkyl substances (PFAS) in the environment; moreover, long chain PFAS are known to accumulate in sewage sludge. Although publications on PFAS in wastewater are available from around the globe, little information is available from Central Europe. In this study influent, effluent, and sludge from two wastewater treatment plants from Austria were analysed for target PFAS compounds with HPLC MS/MS and extractable organic fluorine (EOF) content with combustion ion chromatography (CIC). The sum of 31 target PFAS increased from 22 to 47 ng L-1 in influent to 140 - 213 ng L-1 in effluent and around 10 ng g-1 in sludge, while EOF were found to be consistent (2.3 - 3.5 µg F L-1) in influent/effluent and 280 ng F g-1 in sludge. Mass balance analysis showed an increase in the identified PFAS compounds in the effluent compared to the influent (from 0.9% - 1.3% to 3.6% - 6.1%), suggesting biotransformation of non-targeted PFAS precursor compounds. In conclusion, wastewater treatment plants transform some PFAS, and wastewater effluent is a source of PFAS contamination in surface water.

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Per- and polyfluoroalkyl substances (PFAS) are emerging organic pollutants and can occur in surface and groundwater. To identify the degree of pollution in surface water with PFAS, often targeted HPLC-ESI-MS/MS has been employed in which commonly 30-40 compounds are analyzed. However, other PFAS and organofluorines remain undetected. We sampled surface water of the river Spree and the Teltow Canal in Berlin, Germany, which are affected by the effluent discharge of wastewater treatment plants. Here, we employed high-resolution continuum source graphite furnace molecular absorption spectrometry (HR-CS-GFMAS) for measuring extractable organofluorines (EOF) and compared in a mass balance approach the total fluorine to the identified and quantified PFAS from the targeted analysis. The analysis highlights that the EOF are in the range expected for an urban river system (Winchell et al. in Sci Total Environ 774, 2021). However, downstream of an effluent discharge, the EOF increased by one order of magnitude, e.g., 40.3 to 574 ng F L-1, along the Teltow Canal. From our target analytes, mostly short-chained perfluorinated carboxylic acids and sulfonates occur in the water, which however makes up less than 10% of the EOF. The increase in EOF in the Teltow Canal correlates well with the increase of perfluorohexanoic acid (PFHxA), indicating that PFHxA is characteristic for the discharged EOF but not responsible for the increase. Hence, it points to PFHxA precursor discharge. The study highlights that EOF screening using HR-CS-GFMAS is necessary to identify the full scale of pollution with regard to PFAS and other organofluorines such as pharmaceutical compounds from the effluent of WWTPs.

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In this study the elemental distribution of selected essential (Ca, Mg, Al, Mn, Cu, Fe, Co, Cr, Zn, Ni and Se) and the non-essential (Pb, Hg and As) elements were determined in the bulb and peel of Amadumbe (Colocasia esculenta) samples from eight different sites in KwaZulu-Natal, South Africa. The concentration of Se and As in the soil and in the Amadumbe bulbs were below the detection limit of 0.09 µg g⁻¹. The total and bioavailable concentrations of the elements in conjunction with pH, soil organic matter (SOM) and cation exchange capacity (CEC) were determined in the soil samples from the eight sites. Statistical analysis was done to evaluate the impact of soil quality parameters on the chemical composition of the Amadumbe root. The results show accumulation or exclusion of certain elements by the bulb as evidenced by the noticeable increase or decrease of the concentrations of elements, respectively. Ca and Mg were found to be major elements in the range (2000-12000 µg g⁻¹), whilst Mn, Zn, Fe and Al were found to be minor elements in the range (20-400 µg g⁻¹). A general trend observed was that the plant favours the absorption of Zn over Cu. A positive correlation between Mg & Ca, Cu & Fe and Co & Ni was also observed. Statistical analysis revealed that the plant tended to accumulate Mg, Ca, Co, Cr and Pb whilst it excluded Hg and Fe, to a lesser extent.

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The distribution of eight selected elements (As, Ca, Cr, Cu, Fe, Mg, Mn and Zn) in edible Macadamia (Macadamia integrifolia) nuts from eight sampling sites in the south east coast region of South Africa is investigated. The levels of the elements in all the Macadamia nuts are found to be in the decreasing order of Mg > Ca > Fe > Zn > Cu > Cr > As. The exception is Mn, which exhibited large variability with concentrations in nuts ranging from 10.21 +/- 0.47 microg g(-1) to 216.4 +/- 0.4 microg g(-1). The impact of soil quality parameters: soil pH, cation exchange capacity, soil organic matter and elemental concentrations, as well as interactions in the soil on the elemental composition in the nuts are also studied. At the Ifafa site, south of Durban, typical elemental concentrations (in microg g(-1) dry weight) in the (nuts and soil) are Mg (4920 and 4656), Ca (2169 and 6173), Fe (92 and 20200), Zn (52 and 30), Cu (20 and 49), Cr (2.0 and 69.0) and As (0.024 and 0.104). The maximum concentration of Mg in the nuts is observed to be 4956.1 +/- 92.8 microg g(-1), while that of As is below 0.058 +/- 0.003 microg g(-1). Ca and Mg levels in nuts are antagonistic. Further, when bioavailable levels of Fe, Cu and Zn in soil are low, the bioaccumulation factor for Fe in nuts is high. Although, the soil quality parameters have an influence on the elemental uptake by the Macadamia nut, the results show that uptake and distribution of metals in the nuts are primarily dependent on the plants inherent controls that ensure the physiological well-being of the plant. Macadamia nuts prove to have good control on elemental uptake and are low in the toxic metals investigated.

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The total elemental concentrations and proximate chemical composition of five different tree nuts, almond (Prunus dulcus), Brazil (Bertholletia excelsa), pecan (Carya pecan), macadamia (Macadamia integrifolia) and walnut (Juglans nigra) that are consumed in South African households were investigated. In addition, six physicochemical properties of the extracted nut oils, namely acid value, iodine value, saponification value, refractive index, density and specific gravity were evaluated. A high concentration of Se (36.1 +/- 0.4 microg g(- 1)) was found in the Brazil nuts only. With maximum and minimum limits being set by the almond and pecan nut samples, Cr ranging from 0.94 +/- 0.14-2.02 +/- 0.07 microg g(- 1) was detected in the nut samples. Generally, the order of the concentrations of the elements in all the nut samples is found to be Mg > Ca > Fe > Cu > Cr > As > Se. The concentrations of Mn and Zn showed greater variation amongst the different types of nuts. The extracted oils showed low acid values and high saponification values with the macadamia nut sample having the highest oil content (76.0 +/- 0.5 g per 100 g of sample), the lowest acid value (0.42 +/- 0.01 mg KOH per g of oil) and highest saponification value (193.7 +/- 2.4 mg KOH per g of oil). The present findings are useful in calculating the Dietary Reference Intakes of these nutrients.

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The total concentrations of 7 selected metals, namely manganese, iron, zinc, titanium, boron, arsenic and mercury, were monitored for one annual cycle covering four seasons in the seaweed, Gelidium abbottiorum, at four sampling sites at Zinkwasi, Ballito, Treasure beach and Park Rynie along the South-East coastline of KwaZulu-Natal, South Africa to assess the current status of the marine environment. Inductively Coupled Plasma Optical Emission Spectrophotometry, Mercury Cold Vapour AAS, and Hydride Generation AAS were used for the determination of metal concentrations. Mn concentrations were particularly high in the G. abbottiorum species, followed by Fe, As and B concentrations which were in the 3-8 ppm range. Ti and Zn were in the 100-400 ppb range, while Hg was low and below 100 ppb. A typical sample of G. abbottiorum at Treasure beach, a site close to Durban metropolis in winter had Mn (8.6 ppm), Fe (4.6 ppm), As (5.6 ppm), B (3.0 ppm), Ti (420 ppb), Zn (167 ppb) and Hg (7.5 ppb). All metals recorded a decrease in concentrations from winter to spring with the exception of Hg. The Hg levels increased considerably from winter to spring.

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The impact of coal mine dump contaminated soil on the elemental uptake by two edible plants, namely, Amaranthus dubius (red herbs) and Amaranthus hybridus (green herbs), was studied by investigating their response and ability to tolerate and accumulate varying levels of elements in their roots and shoots. The vegetation was grown on varying amounts of contaminated soil, viz. 0%, 5%, 15%, 25% w/w using coal mine dump soil. The soil was analyzed for soil pH, cation exchange capacity (CEC), soil organic matter (SOM), moisture content, and selected heavy metals. The distribution of six metals, namely, Pb, Cd, Hg, Ni, Mn, and Fe, in roots, stem, and leaves of the plants was determined in two stages of growth after 5 weeks and 10 weeks. All soil and plant samples were microwave digested and subjected to heavy metal analysis using the ICP-OES, GFAAS, and CVAAS. The pH of the coal mine dump contaminated soil decreased with an increase in contamination. Both the SOM and CEC values decreased, which increases the availability of elements, by providing more binding sites in the soil. Relatively, the red herbs had higher elemental concentrations than the green herbs. Both plants recorded high manganese accumulation. No mercury was detected in the soils or plants.

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The elemental uptake and the growth response of Spinacia oleracea (spinach) to the soil contaminated with the South African bituminous coal mine dump soil, viz. 0%, 5%, 15%, and 25% w/w, was investigated. The contaminated soils were analyzed for pH, cation exchange capacity (CEC), soil organic matter (SOM), and concentrations of selected heavy metals. The pH, SOM, and CEC decreased with an increase in contamination indicating the acidic nature of coal mine soil and the raise in the soil binding sites. The distribution of Fe, Mn, Ni, Cd, and Pb in the in roots and leaves of the plants was determined in two stages of plant growth. Spinach showed high accumulation of Fe and increased levels of Ni and Cd with an increase in contamination. No plant growth was recorded with 25% contamination.

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BACKGROUND: Metals are not homogeneously distributed in organ tissues. Although most mapping techniques, such as histologic staining methods, have been developed for element imaging on a subcellular level, many suffer from either low precision or poor detection limits. Therefore, small variations in elemental distribution cannot be identified. We developed a method for two-dimensional mapping of trace elements to identify the influence of metabolic zonation by the liver on trace element distribution. METHODS: A prepared homogeneous Certified Reference Material (CRM; LGC 7112, pig liver) was used to characterize the laser ablation-inductively coupled plasma time-of-flight mass spectrometry (LA-ICP-MS) in terms of precision. Different isotopes for copper and zinc were monitored, and the use of carbon as an internal standard was investigated to correct for differences in ablation efficiency to identify the most precise mapping technique for liver samples. RESULTS: For the homogeneous CRM, the reproducibility of the copper and zinc signals was approximately 3-24% depending on spot size and number of pulses. When carbon was used as an internal standard, the reproducibility was improved significantly. Line scan signals over a length of 1.5 mm were more precise [relative SD (RSD), 1.6-6.1% for copper ((63)Cu, (65)Cu) and zinc ((64)Zn, (66)Zn) depending on the spot size, the scanning speed, and the element]. Thin section of sheep liver achieved precisions of 27-59% (raster scan) and 9-47% (line scan) RSD for copper, whereas the precision for zinc was significantly better: 8-18% (raster scan) and 4-21% (line scan) RSD. Long line scans and two-dimensional element maps of the thin sections revealed the zonation of copper in sheep liver containing extremely low copper concentrations. CONCLUSION: Elemental mapping of trace elements generated by LA-ICP-MS can be very precise so that small changes in the elemental concentration in the tissue can be detected and nonuniform spatial distribution of the elements in tissues can be established.

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