1. Ubiquitous Occurrence of Fluorotelomer Alcohols in Eco-friendly Paper-made Food Contact Materials and Their Implication for Human Exposure Guanxiang YUAN, Hui PENG, Chong HUANG, and Jianying HU Laboratory for Earth Surface Processes, College of Urban and Environmental Sciences, Peking University, Beijing 100871, China The occurrence of fluorotelomer alcohols (FTOHs) was investigated in 87 food contact materials (FCMs). 6:2FTOH (<0.17-1111 ng/g), 8:2FTOH (<0.13-1370 ng/g), and 10:2FTOH (<0.01-2772 ng/g), were detected in most FCM samples, and four longer- chain C 14-20 FTOHs were, for the first time, identified with relatively high concentrations (<0.01-2678 ng/g for 12:2FTOH, <0.01-1644 ng/g for 14:2FTOH, <0.01-372 ng/g for 16:2FTOH, and <0.01-130 ng/g for 18:2FTOH). There were three typical profil es of FTOHs which were dominated by 6:2FTOH (95.6±8.1% in 13 FCMs), 8:2FTOH (51.2±21.2% in 23 FCMs), and 10:2FTOH (45.4±22.8% in 25 FCMs), respectively, indicating the congener-specific usage of FTOHs for different commercial purposes. The concentration of total FTOHs in eco-friendly paper tableware was 4081±3244 ng/g, much higher than in microwave popcorn bags (845±958 ng/g) and in other FCMs (<0.42-38.71 ng/g), and more than 20-fold higher than concentrations of fifteen perfl uorinated carboxylic acids (PFCAs) (119±47 ng/g and 40.9±61.5 ng/g) in the same FCMs. FTOHs could migrate from paper bowls, with migration rates of 0.004-0.24% into water, 0.004-0.24% into 10% ethanol, 0.009-2.79% into 30% ethanol and 0.06-13. 0% into 50% ethanol (v/v) simulants. Migration rates decreased with increasing carbon chain lengths of FTOHs. The estimated daily intake of FTOHs (4.73 ng into water, 4.16 ng into 10% ethanol, 152 ng into 30% ethanol, and 2542 ng into 50% ethanol) fr om a single paper bowl was comparable to the daily inhalation (34 ng) of FTOHs via air in China. This study reported the ubiquitous occurrence of FTOHs in eco-friendly paper-made FCMs, highlighting the potential contribution to human exposure to PFC s. Environmental pollution from perfluorinated compounds (PFCs) has received wide attention due to their persistence and ubiquity in the environment and known toxicities. PFCs were widely used in food packaging materials, and their residues in food contact materials (FCMs) have attracted attention considering their potential migration into foodstuff. Of PFCs, only perfluorinated carboxylic acids (PFCAs) have been widely detected in paper-made FCMs. Fluorotelomer alcohols (FTOHs) are an important class of PFCs which are incorporated into the production of a majority of commercial fluorochemicals, and increasingly important in consumption products since 2003. FTOHs have been suggested to be important precursors of PFCAs, and can impair reproductive and developmental functions. The occurrence of FTOHs in matrices of common exposure routes to humans was limited to air. Residues of FTOHs were examined in 62 daily-use paper-made FCMs produced in China and 25 FCMs produced in the USA, and migration tests from FCMs (paper tableware) to food simulants were further conducted for well understanding the implications of human exposure. INTRODUCTION MATERIALS AND METHODS RESULTS ABSTRACT After being cut into pieces, the food contact materials were extracted with methanol. The extracts were purified by passing through Oasis WAX cartridage (3cc, 60mg), which were eluted with 1 mL acetonitrile firstly for FTOHs, and were eluted with 2 mL methanol containing 0.5% ammonium hydroxide secondly for PFCAs. The PFCA elutes were dried and dissolved in 100 μL methanol for UPLC-ESI(-)-MS/MS analysis. FTOHs were further derivated with 200 μL dansyl chloride/4-(dimethylamino)- pyridine at 65°C for 90 min, and purified by Silica (6cc, 1g) cartridge, which was eluted with 8 mL hexane: dichloromethane (v/v, 1:1). The eluent was blown to dryness and dissolved in 200 μL acetonitrile for UPLC-MS/MS and/or UPLC-QTOF-MS analysis. Migration Tests: Food simulants including water and ethanol/water solutions (v/v, 10/90, 30/70, 50/50) were preheated to 100°C in sealed screw-cap glass tubes. Ten milliliters (10 mL) of food simulants were transferred to paper bowls and kept for 15 min at room temperature. All seven FTOHs were detected in 82% of FCMs (51/62) from China, and the total concentrations of the 4 longer-chain FTOHs (484±1160 ng/g) were comparable to those of the 3 traditional shorter-chain FTOHs (551±1178 ng/g). The concentration of total FTOHs in paper tableware (4081±3244 ng/g) was much higher than in microwave popcorn bags (845±958 ng/g) and in other FCMs (<0.42- 38.71 ng/g), and more than 20-fold higher than concentrations of fifteen PFCAs (119±47 ng/g and 40.9±61.5 ng/g) in the same FCMs. Residues of FTOHs and PFCAs in FCMs were largely dependent on the raw material and coating, and eco-friendly paper tableware which was made of plant fiber showed significantly high residues of FTOHs and PFCAs, suggesting that a comprehensive assessment of eco-friendliness of FCMs and health risks of multiple chemicals in FCMs is necessary when formulating policy regarding the use of consumer products. Extracted ion chromatograms of FTOHs in food contact materials on UPLC-QTOF-ESI-MS in full scan from 500 to 1200 Da. Peak 1: 12:2FTOH, Peak 2: 14:2FTOH; Peak 3: 16:2FTOH, and Peak 4: 18:2FTOH. Concentrations of FTOHs and PFCAs in food contact materials (FCMs) made in China. Chemicals Paper bowls (ng/cm 2 ) Water10% ethanol30% ethanol50% ethanol MREIMREIMREIMREI 6:2FTOH7.100.242.590.242.592.7930.113.0140 8:2FTOH96.40.0081.170.0060.880.791169.471389 10:2FTOH90.90.0070.970.0050.690.0446.087.331013 12:2FTOH63.20.0060.580.0040.380.0111.062.84273 14:2FTOH35.40.0050.270.0040.220.0100.540.4624.8 16:2FTOH6.360.0040.0390.0040.040.0090.090.060.58 PFBA0.06418.31.7718.11.7521.41.4928.72.78 PFPeA0.07511.61.329.561.0915.11.7230.13.42 PFHxA0.395.813.425.723.3611.56.7632.519.1 PFHpA0.212.080.662.330.745.981.9031.710.1 PFOA1.580.831.991.062.552.435.8428.768.9 PFNA0.260.240.0950.380.151.200.4826.710.6 PFDA1.180.0970.170.240.431.051.8810.518.8 PFUnDA0.210.0210.0070.0830.0270.290.0949.813.17 PFDoDA1.000.0050.0080.0340.0530.200.304.767.26 PFTriDA0.084----0.170.0221.740.22 PFTeDA0.63----0.0560.0540.710.68 PFPeDA0.04----0.010-0.410.027 PFHxDA0.17------0.260.065 PFHpDA0.012------0.280.005 PFODA0.063------0.190.018 Migration Rates (MR, %) and Esitimated Intake (EI, ng) of FTOHs and PFCAs from Paper Bowls to Food Simulants Migration rates of FTOHs and PFCAs from paper bowls into water and ethanol solutions were dependent on their carbon chain lengths, decreasing with increasing carbon chain lengths. Migration rates of FTOHs and PFCAs into ethanol solutions significantly increased with the component ratio of ethanol: 0.004-0.24% and 0.034-18.1% for 10% ethanol, 0.009-2.79% and 0.010-21.4% for 30% ethanol, and 0.06-13.0% and 0.18-32.5% for 50% ethanol. Daily intake of 6:2FTOH, 8:2FTOH and 10:2FTOH (34.0 ng) via breath for Chinese was 7.2-fold higher than intake of the three FTOHs which migrated from a paper bowl into water, but 75-fold lower than FTOHs which migrated to 50% alcohol, implying the importance of FCMs to human exposure to FTOHs.