全氟烷基化合物、鄰苯二甲酸酯、雙酚類、鎵與銦之環境與食品監測

Food and Environmental Monitoring of Perfluoroalkyl Substances, Phthalate Esters, Bisphenol analogues, Gallium, and Indium

蔡耕文(Keng-Win Tsai)

指導教授 ： 陳家揚

國立臺灣大學/公共衛生學院/環境衛生研究所/碩士(2019年)

https://doi.org/10.6342/NTU201900266

摘要

全氟烷基化合物(Perfluoroalkyl substances, PFASs)廣泛用於防水織品、不沾鍋等器皿。諸多研究已指出PFASs具有肝臟與生殖毒性，且可能干擾人體內分泌系統。鄰苯二甲酸酯 (phthalate esters, PAEs)為塑化劑，其因大量使用而廣布於環境中，且可能影響生殖功能。雙酚A (bisphenol A, BPA) 與其替代品雙酚S (bisphenol S, BPS) 與雙酚F (bisphenol F, BPF)具有雌激素之性質，可能產生負面之生殖影響。鎵(gallium, Ga)與銦(indium, In)則廣泛運用於半導體或是面板產業；這兩種金屬可能導致氧化壓力增加，妨害細胞正常運作。
本研究透過2017年分別由趙冠萍、陳則穎、劉佑辰開發且經驗證之三種分析方法，調查新竹地區河水、底泥、與六類食物中十種全氟烷基化合物（PFBA，PFPeA，PFHxA，PFOA，PFNA，PFDA，PFUnDA，PFDoDA，PFHxs，PFOS），六種鄰苯二甲酸酯（DEP，BBP，DEHP，DNOP，DINP，DIDP），雙酚A、雙酚S、雙酚F，鎵與銦等之濃度。食品包括豬肉、豬肝、豬腎、魚肉（河魚與海魚），蛤蜊和牡蠣等較為容易累積上述物質者。食物樣本採自三個新竹市主要市場，環境樣本則採自客雅溪與頭前溪。其中，客雅溪為新竹科學園區放流水之承受水體。食物及環境樣本分別於2018年之3月、4月、5月進行三次採樣，並完成21個河水、19個底泥、與與63個食物樣本之分析。
有機待測物使用超高效能液相層析/串聯式質譜法(ultra high-performance liquid chromatography/tandem mass spectrometry, UHPLC-MS/MS)進行分析。六種鄰苯二甲酸酯以正離子電灑游離法作為游離源，並利用Ascentis Express F5管柱(30 × 2.1 mm, 2.0 μm)搭配液相層析移動相：(A) 5 mM醋酸氨水溶液(pH = 6.5)、(B)乙腈，進行梯度流析；十種全氟碳化合物和雙酚類以負離子電灑游離法作為游離源，並利用BEH C18管柱(50  2.1 mm, 1.7 μm)，搭配液相層析移動相： (A) 10 mM N-甲基嗎啡林 (pH = 9.6)、(B)甲醇，進行梯度流析。質譜儀以多重反應監測模式獲取質荷比資訊，並偵測最強與次強之離子對，分別做為定量與定性之用。樣本前處理步驟，食品有機分析使用QuEChERS（Quick, Easy, Cheap, Effective, Rugged, and Safe），水樣以固相萃取。鎵與銦使用電感耦合電漿體質譜儀(inductively coupled plasma mass spectrometer, ICP-MS)進行偵測，樣本則使用強酸進行微波消化。
食品中PFASs濃度大多在低ng/g濕重，其中以豬肝濃度相對較高。PAEs在食品中濃度可達g/g濕重；BBP，DEHP，與DINP可見於所有食品樣本，其中以豬肝、豬腎、牡蠣濃度為高。雙酚S與雙酚F濃度為數個ng/g，大多見於魚肉和海產。河水中PFASs與雙酚F、雙 S濃度大多在數個至數十個ng/L，其中客雅溪之濃度較頭前溪高；PAEs在河水中可達數十個μg/L，客雅溪之濃度與頭前溪無明顯區別。底泥中PFASs濃度大多在低ng/g乾重；PAEs在底泥中可達數個μg/g乾重；雙酚A濃度大多在數百ng/g乾重；雙酚F與雙酚S濃度則分別在數十個與低ng/g乾重。三類代測物於底泥中皆有濃度隨上游至下游持續增加之趨勢，其中以客雅溪之最下游處（香雅橋，K3）濃度最高。本研究估計，一般民眾經由六大類食品之暴露量為PFASs每日每公斤體重13.9 ng；PAEs為744 ng/kg b.w./day，其中DEHP佔33% (244 ng)，DINP佔62% (462 ng)；雙酚S與雙酚F則為1.64 ng/kg b.w./day。本研究中所測之PFOA、PFOS、DEHP、BBP、DINP、DIDP、BPA皆符合當前台灣衛生福利部食品藥物管理署所訂定之每日耐受量（TDI）標準。歐盟於2018年對食品中PFOS與PFOA提出每週耐受量（TWI），分別為每公斤體重13與6奈克，本研究之PFOA每週暴露量（每公斤體重8.96奈克）已超過此標準。鎵於蛤蜊和牡蠣濃度（幾何平均分別為65.1與32.4 ng/g濕重）遠高於其他食物(幾何平均介於0.18至2.02 ng/g濕重)。鎵於河水和底泥之濃度可分別達到g/L與mg/kg乾重，且比銦高出千倍。在客雅溪之河水樣本中，銦於新竹科學園區廢水放流口後所測得之濃度遠高於其上游處，說明新竹科學園區之廢水可能對客雅溪的水質造成影響。

關鍵字

全氟烷基化合物 ； 鄰苯二甲酸酯 ； 雙酚A ； 雙酚F ； 雙酚S ； 鎵 ； 銦 ； 超高效能液相層析/串聯式質譜法 ； 電感耦合電漿體質譜儀 ； QuEChERS ； 微波消化 ； 固相萃取 ； 河水 ； 底泥 ； 食品

並列摘要

Perfluoroalkyl substances (PFASs) are widely used in waterproof fabrics and nonstick cookware. Many studies have indicated that PFASs have hepatotoxicity, developmental toxicity, and could disrupt human endocrine systems. Phthalate esters (PAEs), a group of plasticizers, are ubiquitous in the environment and may affect our reproductive organs. Bisphenol A (BPA), bisphenol S (BPS), and bisphenol F (BPF) are estrogenic and may pose adverse reproductive effects. Gallium (Ga) and Indium (In) are commonly used in photonic industries; animal studies have shown that these two metals may induce oxidative stress and interfere with cell functions.
This study determined 10 PFASs, six PAEs, three bisphenols, and two metals of Ga and Indium in food samples (pork, pork liver, pork kidney, fish meat, clam, and oyster) and environmental samples (river water and sediment) with three analytical methods that had been developed and validated by Kuan-Ping Chao, Ze-Ying Chen, and You-Chen Liu in 2017. Food samples were collected from three major traditional markets in Hsinchu City; environmental samples were collected from Keya Stream, in which wastewater from Hsinchu Science Park discharges, and Touchien River in Hsinchu. Food samples and environmental samples were collected three times in April, May, and June 2018, respectively. This study analyzed 63 food samples, 21 river water samples, and 19 sediment samples.
Organic analytes were determined with ultra-high performance liquid chromatography/tandem mass spectrometry (UHPLC-MS/MS). PAEs were separated on an Ascentis Express F5 column (30 × 2.1 mm, 2.0 μm) with mobile phases composed of (B) acetonitrile and (A) 5 mM ammonium acetate(aq) (pH 6.5), and were ionized with positive electrospray ionization (ESI+). The rest organic analytes were separated with a BEH C18 column (50  2.1 mm, 1.7 μm) with mobile phases composed of (B) methanol and (A) 10-mM N-methylmorpholine(aq) (pH 9.6), and were ionized with negative ESI (ESI-). Data were acquired using multiple-reaction monitoring (MRM); the most abundant and the second abundant product ions were selected for quantification and confirmation, respectively.
Food and sediment samples were prepared using QuEChERS (Quick, Easy, Cheap, Effective, Rugged, and Safe) approach for organic analysis. Water samples were processed using solid-phase extraction (SPE).
Gallium and Indium were detected using an inductively coupled plasma mass spectrometer (ICP-MS). Food and sediment samples were digested with acids using microwave-assisted digestion for metal analysis.
PFASs were found in foods at low ng/g w.w. levels with higher concentrations in pork liver. Concentrations of individual PAEs could reach g/g w.w.; BBP, DEHP, and DINP were observed in all of the food samples, and were relatively higher in pork liver, pork kidney, and oyster than those in other food items. Bisphenol S and bisphenol F were observed in fish meat and seafood at low ng/g w.w. PFASs, bisphenol S and bisphenol F in river water were found at few ng/L levels, and the concentrations were higher in Keya Stream than those in Touchien River. PAEs in river water were as high as g/L levels, and the concentrations were similar at Keya Stream and Touchien River. PFASs in sediments were found at low ng/g d.w.; PAEs could reach few μg/g d.w.; bisphenol A were observed in sediments at few hundred ng/g d.w. level; bisphenol F and bisphenol S were found at few ng/g d.w. and low ng/g d.w. level, respectively. Trends of concentrations increased from upstream to downstream in all the three categories of analytes in sediment samples with the highest concentration found at the downstream of Keya Stream at Siangya Bridge (K3).
The estimated exposure through food intake was 13.9 ng/kg bw/day to PFASs. The estimated exposure to PAEs was 744 ng/kg bw/day, which DEHP and DINP contributed 33% (244 ng) and 62% (462 ng), respectively. The total exposure to bisphenols were 1.64 ng/kg bw/day. The levels of exposure to PFOA, PFOS, DEHP, BBP, DINP, DIDP and BPA in this study are well within the standards of tolerable daily intake (TDI) set by TFDA. In 2018, EFSA has proposed tolerable weekly intake (TWI) of 13 ng/kg body weight for PFOS and 6 ng/kg body weight for PFOA in foods. Weekly intake of PFOA (8.96 ng/kg bw) in this study showed the need to control PFOA in Taiwan under these new standards.
Ga was in much higher concentrations in clam and oyster (geometric means, GM, at 65.1 and 32.4 ng/g w.w., respectively), and was observed in all other food samples although in much lower levels (GM between 0.18 and 2.02 ng/g w.w.) Levels of Ga in water and sediment reached g/L and mg/kg d.w., respectively, and were about three orders of magnitude than those of In. Concentrations of Indium in the water of Keya Stream after the effluent from Hsinchu Science Park were much higher than the upstream concentrations. This may indicate the impact on water quality from the wastewater of Hsinchu Science Park.

並列關鍵字

Perfluoroalkyl substances ； phthalate esters ； bisphenol A ； bisphenol F ； bisphenol S ； gallium ； indium ； UHPLC-MS/MS ； ICP/MS ； QuEChERS ； microwave digestion ； solid-phase extraction ； river water ； sediment ； food

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