Perfluorinated compounds (PFCs) have been used for many years, and are distributed all over the world. This study focused on occurrences of PFCs, especially perfluorooctane sulfonate (PFOS) and perfluorooctonoic acid (PFOA) in Thai rivers and industrial estate discharges, while comparing results with rivers of other Asian countries (Japan, China, and Malaysia). Surveys were conducted in Chao Phraya River, Bangpakong River and three industrial estates. A solid phase extraction (SPE) and HPLC-ESI-MS/MS were used for the analysis of these chemicals. The average concentrations of PFOS and PFOA were 1.9 and 4.7 ng/L, respectively in Chao Phraya River, while lower concentrations were detected in Bangpakong River with the averages of 0.7 ng/L for both PFOS and PFOA. Higher concentrations were detected in all industrial estate discharges with the averages of 64.3 ng/L for PFOA and 17.9 ng/L for PFOS., Total loadings from three industrial estates were 1.93 g/d for PFOS and 11.81 g/d for PFOA. The concentration levels in Thai rivers were less than rivers in Japan, China, and Malaysia. However, PFCs loading rate of Chao Phraya River was much higher than Yodo River (Japan), due to the higher flow rate. The other six PFCs were found above the Limit of Quantification (LOQ) in most samples. PFHxS and PFNA were also highly detected in some river samples.
The occurrence of perfluorinated compounds (PFCs) in human blood is known to be widespread; nevertheless, the sources of exposure to humans, including infants, are not well understood. In this study, breast milk collected from seven countries in Asia was analyzed (n=184) for nine PFCs, including perfluorooctanesulfonate (PFOS) and perfluorooctanoate (PFOA). In addition, five brands of infant formula (n=21) and 11 brands of dairy milk (n=12) collected from retail stores in the United States were analyzed, for comparison with PFC concentrations previously reported for breast milk from the U.S. PFOS was the predominant PFC detected in almost all Asian breast milk samples, followed by perfluorohexanesulfonate (PFHxS) and PFOA. Median concentrations of PFOS in breast milk from Asian countries varied significantly;the lowest concentration of 39.4 pg/mL was found in India, and the highest concentration of 196 pg/mL was found in Japan. The measured concentrations were similarto or less than the concentrations previously reported from Sweden, the United States, and Germany (median, 106-166 pg/mL). PFHxS was found in more than 70% of the samples analyzed from Japan, Malaysia, Philippines, and Vietnam, at mean concentrations ranging from 6.45 (Malaysia) to 15.8 (Philippines) pg/mL PFOA was found frequently only in samples from Japan; the mean concentration for that country was 77.7 pg/mL. None of the PFCs were detected in the infant-formula or dairy-milk samples from the U.S. except a few samples that contained concentrations close to the limit of detection. The estimated average daily intake of PFOS by infants from seven Asian countries, via breastfeeding, was 11.8 +/- 10.6 ng/kg bw/ day; this value is 7-12 times higher than the estimated adult dietary intakes previously reported from Germany, Canada, and Spain. The average daily intake of PFOA by Japanese infants was 9.6 +/- 4.9 ng/kg bw/day, a value 3-10 times greater than the estimated adult dietary intakes reported from Germany and Canada. The highest estimated daily intakes of PFOS and PFOA by infants from seven Asian countries studied were 1-2 orders of magnitude below the tolerable daily intake values recommended by the U.K. Food Standards Agency.
Perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA) are widely used in products, and are known for their water and grease repellent properties. The persistence nature and potential toxicity of these substances have raised substantial concerns about health effects. Regarding humans, food consumption has reportedly been a significant source of exposure for both compounds. Hence, this study was performed to develop and validate an analytical method for PFOS and PFOA in egg yolks using liquid chromatographic tandem mass spectrometry (LC-MS/MS) followed by the determination of concentration of both compounds in the yolk of poultry eggs in Malaysia. A total of 47 poultry egg yolk samples were extracted by a simple protein precipitation technique using acetonitrile. The analytical method was developed using LC-MS/MS and validated based on the Food and Drug Administration (FDA)'s Bioanalytical Method Validation guidelines. The results revealed that PFOS was quantitatively detected in six samples, with the concentration range between 0.5 and 1.01 ng g-1. Among these, five samples were from home-produced chicken eggs, and one sample was from a quail egg. The levels of PFOA in all samples were below the quantifiable limit (<0.1 ng g-1). This indicated that the contamination of PFCs in poultry eggs were mostly attributed to the nature of free foraging animals, which had direct contact with the contaminants in soil and feed. In conclusion, a fast and robust analytical method for analyzing PFOS and PFOA in egg yolk samples using LC-MS/MS was successfully developed and validated. The presence of these emerging contaminants in this study signified widespread pollution in the environment.
Perfluorinated surfactants (PFSs) in Asian freshwater fish species were analyzed to investigate tissue distribution, temporal trends, extent of pollution, and level of PFS exposure through food intake. Freshwater fish species, namely carp, snakehead, and catfish, were collected in Japan, Vietnam, India, Malaysia, and Thailand, and 10 PFSs, including perfluorooctanesulfonate (PFOS) and perfluorooctanoate, were analyzed by liquid chromatography-tandem mass spectrometry. PFSs in carp in Tokyo were more concentrated in kidneys (Σ10 PFSs = 257 ± 95 ng/g wet weight [ww]) and livers (119 ± 36 ng/g ww) than in ovaries (43 ± 2 ng/g ww) and muscles (24 ± 17 ng/g ww). Concentrations of PFOS and its precursor, perfluorooctane sulfonamide, in livers of carp and in waters in Tokyo showed a dramatic decrease during the last decade, probably because of 3 M's phasing-out of the manufacture of perfluorooctanesulfonyl-fluoride-based products in 2000. In contrast, continuing contamination by long-chain perfluorocarboxylates (PFCAs) with ≥ 9 fluorinated carbons was seen in multiple media, suggesting that these compounds continue to be emitted. PFS concentrations in freshwater fish species in tropical Asian countries were generally lower than those in developed countries, such as Japan, e.g., for PFOS in muscle, Vietnam < 0.05-0.3 ng/g ww; India < 0.05-0.2 ng/g ww; Malaysia < 0.05-0.2 ng/g ww; Thailand < 0.05 ng/g ww; and Japan (Tokyo) = 5.1-22 ng/g ww. Daily intake of short-chain PFCAs with ≤ 8 fluorinated carbons from freshwater fish species in Japan was approximately one order of magnitude lower than that from drinking water, whereas daily intake of PFOS and long-chain PFCAs with ≥ 9 fluorinated carbons from freshwater fish species was comparable with or greater than that from drinking water. Because the risk posed by exposure to these compounds through intake of fish species is a matter of concern, we recommend the continued monitoring of PFS levels in Asian developing countries.