Determination of adsorbable organically bound fluorine (AOF) and adsorbable organically bound halogens as sum parameters in aqueous environmental samples using combustion ion chromatography (CIC).

Because of their toxicity and biomagnification potential individual perfluoroalkyl and polyfluoroalkyl substances (PFAS) are regularly examined in food and environmental matrices by LC-MS/MS. The combustion ion chromatography (CIC) can be used to determine adsorbable organic fluorine (AOF) in aqueous samples. This report describes the optimization and validation of an automated, robust, cost-efficient and rapid CIC method for the determination of AOF. The analysis of 25 fluorinated organic reference substances was performed with recoveries between 16% and 121%. Water from selected surface waters (n = 74), municipal (n = 116) and industrial wastewaters (n = 33) as well as ground water (n = 93) were analyzed by means of CIC. The AOF values of surface water varied between 2.3 and 24.5 µg/L. The concentrations of AOF in 85% of the wastewater discharges were between 2.0 and 8.5 µg/L, while 15% of the samples were below the limit of quantitation (LOQ = 2 µg/L AOF). In 56% of the ground water samples the values were below the LOQ. In 44% of the surface water samples (n = 41) the values were between 2.0 and 6.1 µg/L AOF. CIC analysis was performed in 22 samples from a chemical company wastewater treatment plant, and 14 individual PFAS were determined by LC-MS/MS. AOF values up to 555 µg/L were found in these samples while the total of the individual PFAS, calculated as fluorine, was 8.8 µg/L. This provides evidence, that CIC covers a huge range of fluoroorganic compounds that are presently not detected by LC-MS/MS. Furthermore, the CIC method allowed the determination of four halogens in 26 surface water samples. This demonstrated that the CIC technique can be used as a powerful screening test to support LC-MS/MS methods, and is also useful to detect organic chlorine, bromine and iodine compounds (AOCl, AOBr and AOI).

Migration of aluminum from food contact materials to food-a health risk for consumers? Part III of III: migration of aluminum to food from camping dishes and utensils made of aluminum.

BACKGROUND: When cooking on a barbecue grill, consumers often use aluminum grill pans. For one, the pan catches the fats and oils that would drip into the embers causing the formation of potentially noxious smoke, and the pan also protects the food from being burned by direct heat from the coals. In addition, new aluminum products for use in ovens and grills are becoming increasingly popular. Due to their light weight and excellent heat transfer camping, utensils made of aluminum are, for example, often used by fishermen and mountain climbers. Preparing food in aluminum utensils can, however, result in migration of the aluminum to the foodstuffs. RESULTS/CONCLUSIONS: In this study presented here, it was found that the transfer limit of 5.00 mg/L for aluminum is not exceeded using simulants for oil or for tap water; however, with an aqueous solution of 0.5% citric acid, the limit is clearly exceeded at 638 mg/L. This means that the Tolerable Weekly Intake (TWI) is exceeded by 298% for a child weighing 15 kg and for an adult weighing 70 kg it is equivalent to 63.8% of the TWI, assuming a daily uptake of 10 mL marinade containing lemon juice over a period of 1 week. Preparation of a fish dish with a marinade containing lemon juice in camping dishes would result in the TWI being exceeded by 871% for a child weighing 15 kg and by 187% for an adult weighing 70 kg assuming a daily uptake of 250 g over a period of 1 week.

Migration of aluminum from food contact materials to food-a health risk for consumers? Part II of III: migration of aluminum from drinking bottles and moka pots made of aluminum to beverages.

BACKGROUND: Drinking bottles and stove-top moka pots made of aluminum have become very popular. Storing drinks in bottles and preparing coffee in a moka pot may result in the migration of aluminum to the beverage. RESULTS/CONCLUSIONS: In a systematic study of aluminum drinking bottles, it has been shown that drinking a mixture of apple juice and mineral water in an aluminum bottle may reach 86.6% of the total weekly intake (TWI) for adults, and drinking tea from an aluminum bottle may exceed the TWI (145%) for a child weighing 15 kg. In contrast, preparing coffee in an aluminum moka pot results in a maximum of 4% to TWI, if an average of 3.17 L coffee is consumed per week, even if the pots are washed in the dishwasher, against the explicit instructions of the manufacturer.

Migration of aluminum from food contact materials to food-a health risk for consumers? Part I of III: exposure to aluminum, release of aluminum, tolerable weekly intake (TWI), toxicological effects of aluminum, study design, and methods.

BACKGROUND: In spite of the prevalence of aluminum in nature, no organism has been found to date which requires this element for its biological functions. The possible health risks to human beings resulting from uptake of aluminum include detrimental effects to the hemopoietic system, the nervous system and bones. Aluminum is used in many fields and occurs in numerous foodstuffs. Food contact materials containing aluminum represent an anthropogenic source of dietary aluminum. RESULTS: As a result of their frequent use in private households a study was undertaken to detect migration of this metal to foodstuffs from drink containers, coffee pots, grill pans, and camping cookware made of aluminum. CONCLUSIONS: An estimate of the health risk to consumers is calculated, based on the tolerable weekly intake (TWI) specified by the European Food Safety Authority of 1 mg/kg body weight for all groups of people. In some instances the TWI is significantly exceeded, dependent upon the food contact material and the food itself.

Perfluoroalkyl Acid Concentrations in Livers of Fox (Vulpes vulpes) and Chamois (Rupicapra rupicapra) from Germany and Austria.

The concentrations of 11 perfluorinated alkyl acids (PFAAs) were measured in the livers of foxes (Vulpes vulpes) from Germany, a primarily carnivorous species, and chamois (Rupicapra rupicapra) from Austria, an herbivorous species. Perfluorooctanesulfonate (PFOS) at concentrations [all results refer to wet weight (ww)] of 3.2-320 µg/kg were detected in all 40 fox livers tested, yielding an arithmetic mean of 46.6 µg/kg and a median of 29.8 µg/kg. Long-chain PFAAs were detected at concentrations of 1.7 µg/kg perfluorononanoic acid (PFNA) to 2.4 µg/kg perfluorodecanoic acid (PFDA) and perfluorododecanoic acid (PFDoDA). Of the short-chain PFAAs tested, only perfluorohexanoic acid (PFHxA) was found in 1 fox liver at a concentration of 1.4 µg/kg, and perfluorohexane sulfonate (PFHxS) was found in 2 fox livers at a concentration of 1 µg/kg each. PFOS and PFNA concentrations higher than limit of quantification (LOQ) were detected in 90.9 and 81.8 % of chamois livers, respectively. The arithmetic mean for PFOS concentrations was 2.2 µg/kg (median 2.4 µg/kg), a factor of 21 (median factor of 12) lower than in fox livers. The arithmetic mean for PFNA concentrations was 2.0 µg/kg (median 1.9 µg/kg). Perfluorobutanoic acid, PFHxA, perfluorooctanoic acid, perfluorobutanesulfonate, and PFHxS were not detected at concentrations higher than the LOQ in any of the samples. The various results are compared with one another and with the results of other studies of herbivorous, carnivorous, and omnivorous wild animals. The highest concentrations of PFAA, in particular PFOS, were found in omnivorous animals followed by carnivores. The lowest levels were present in herbivores.

Accumulation potentials of perfluoroalkyl carboxylic acids (PFCAs) and perfluoroalkyl sulfonic acids (PFSAs) in maize (Zea mays).

Uptake of perfluoroalkyl acids (PFAAs) by maize represents a potential source of exposure for humans, either directly or indirectly via feed for animals raised for human consumption. The aim of the following study was, therefore, to determine the accumulation potential of perfluoroalkyl carboxylic acids (PFCAs) and perfluoroalkyl sulfonic acids (PFSAs) in maize (Zea mays). Two different concentrations of PFAAs were applied as aqueous solution to the soil to attain target concentrations of 0.25 mg or 1.00 mg of PFAA per kg of soil. Maize was grown in pots, and after harvesting, PFAA concentrations were measured in the straw and kernels of maize. PFCA and PFSA concentrations of straw decreased significantly with increasing chain length. In maize kernels, only PFCAs with a chain length ≤ C8 as well as perfluorobutanesulfonic acid (PFBS) were detected. The highest soil-to-plant transfer for both straw and kernels was determined for short-chained PFCAs and PFSAs.

Tissue specific uptake and elimination of perfluoroalkyl acids (PFAAs) in adult rainbow trout (Oncorhynchus mykiss) after dietary exposure.

Tissue specific uptake and elimination of perfluoroalkyl acids (PFAAs) were studied in rainbow trout (Oncorhynchus mykiss). Adult trout were exposed to perfluorobutane sulfonic acid (PFBS), perfluorohexane sulfonic acid (PFHxS), perfluorooctane sulfonic acid (PFOS), perfluorooctanoic acid (PFOA) and perfluorononanoic acid (PFNA) via food over a time period of 28d. In the following 28-d depuration period the fish were fed PFAA-free food. At defined sampling times four animals were removed from the experimental tank, euthanized and dissected. Muscle, liver, kidneys, gills, blood, skin and carcass were examined individually. At the end of the accumulation phase between 0.63% (PFOA) and 15.5% (PFOS) of the absolute, applied quantity of PFAAs was recovered in the whole fish. The main target organ was the liver with recovery rates between 0.11% (PFBS) and 4.01% (PFOS) of the total amount of ingested PFAAs. Perfluoroalkyl sulfonic acids were taken up more readily and had longer estimated elimination half-lives than perfluoroalkyl carboxylic acids of the same chain length. The longest estimated elimination half-lives were found to be for PFOS between 8.4d in muscle tissue and 20.4d in the liver and for PFNA between 8.2d in the blood and 11.6d in the liver.

Effects of chain length and pH on the uptake and distribution of perfluoroalkyl substances in maize (Zea mays).

Maize is the most important grain crop grown for human nutrition, animal fodder and biogas production worldwide. Nonetheless, no systematic studies have been undertaken on these plants to examine the uptake mechanisms for perfluoroalkyl substances (PFASs) dependent upon chain length and pH value. The aim of the present study was therefore to determine the influence of chain length (C4 to C10) and pH value (pH 5, pH 6, pH 7) on the uptake and distribution of seven perfluoroalkyl carboxylic acids (PFCAs) and three perfluoroalkane sulfonic acids (PFSAs) by maize in nutrient solution experiments under controlled conditions in a climate chamber. A pH-dependent uptake was observed for perfluorodecanoic acid (PFDA) with an uptake rate of 2.51 µg g(-1) at pH 5 compared to 1.52 µg g(-1) root dry weight (DW) per day (d) at pH 7. Perfluorobutanoic acid (PFBA) had the highest uptake rate within the group of PFCAs with an average of 2.46 µg g(-1) root DWd(-1) and perfluorooctane sulfonic acid (PFOS) had the highest uptake rate (3.63 µg g(-1) root DWd(-1)) within the group of PFSAs. The shoot:root ratio for shorter-chain PFCAs (≤ C7) and PFBS (C4) was >2.0, which indicates that shorter-chain PFASs are transferred predominantly and at higher concentrations to the shoot. In contrast, long-chain PFCAs such as perfluorooctanoic acid (PFOA), perfluorononanoic acid (PFNA) and perfluorodecanoic acid (PFDA) as well as the PFASs perfluorohexane sulfonic acid (PFHxS) and perfluorooctane sulfonic acid (PFOS) accumulated at higher concentrations in the roots of maize plants with a shoot:root ratio of <1.0.

Temporal and spatial trends of perfluoroalkyl substances in liver of roe deer (Capreolus capreolus).

For more than 50 years perfluoroalkyl substances (PFASs) have found worldwide industrial and household uses. Some PFASs are presumed to be persistent and bioaccumulative. Roe deer (Capreolus capreolus) are thought to be a suitable bioindicator for the accumulation of organic xenobiotics. Due to the ubiquitous nature of PFASs in the environment a retrospective study on temporal trends was carried out. A total of 110 deer liver pools collected from 1989 to 2010 in Germany were analyzed for their levels of PFASs. The highest concentrations were measured for perfluorooctane sulfonate (PFOS) (median 6.3 µg/kg). Perfluorooctanoic acid (PFOA), perfluorononanoic acid (PFNA) and perfluorodecanoic acid (PFDA) were detected with median concentrations of 0.5 µg/kg, 1.2 µg/kg and 0.3 µg/kg, respectively, while concentrations of the other PFASs were below the limit of quantification. PFOS concentrations decreased significantly (r(s) = -0.741; p = <0.0001) from 9.2 µg/kg in 2000 to 1.8 µg/kg in 2010.