以固相萃取搭配極致液相層析/串聯式質譜儀分析水中全氟碳化合物、鄰苯二甲酸酯、壬基酚與雙酚A

Determination of Perfluoroalkyl Substances, Phthalate Esters, Nonylphenol, and Bisphenol A in Water by Solid-Phase Extraction and UPLC-MS/MS

陳則穎(Ze-Ying Chen)

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(2017年)

https://doi.org/10.6342/NTU201703938

摘要

全氟碳化合物、鄰苯二甲酸酯、壬基酚與雙酚A普遍存在於環境中，這些物質被廣泛的使用於日常消費性產品，如防水衣物塗料、油漆、塑膠產品、清潔劑及食品容器。許多研究指出，這些物質具有肝毒性、發展毒性與生殖毒性。除此之外，這些物質也都屬於內分泌干擾物質，具有影響人體賀爾蒙系統的性質。此四類物質主要藉由水在環境中傳播，因此就有需要監測此四類物質於環境水體中的濃度。本研究將探討10種全氟碳化合物 (PFBA, PFPeA, PFHxA, PFOA, PFNA, PFDA, PFUnDA, PFDoDA, PFHxS, and PFOS)、6種鄰苯二甲酸酯 (DEP, BBP, DEHP, DNOP, DINP and DIDP)、壬基酚、雙酚A於水中的濃度。此研究將以極致液相層析搭配串聯式質譜儀進行分析，並以固相萃取做為樣本前處理方法。水樣在分析前會先以30 μL 88%甲酸酸化至pH 3。固相萃取吸附劑在操作前依序以5 mL異丙醇、甲醇及Milli-Q水進行活化，以5 mL/min通過100 mL水樣後，以0.6 mL 10%甲醇/90% Milli-Q水清洗吸附劑兩次，之後氮氣吹淨45秒。最後依序使用2 mL甲醇、2 mL異丙醇，以流速1 mL/min各沖提兩次，並全部收集。萃取溶液濃縮至1.0 mL後以0.22 μm尼龍過濾器過濾，並再次濃縮至近乾，最後以100 μL甲醇回溶並上機分析。實驗結果顯示，6種鄰苯二甲酸酯的基質效應介於88%到116%之間。全氟碳化物方面，PFBA, PFNA, PFDA, PFUnDA, PFDoDA的基質效應介於77%到85%之間，PFPeA, PFHxA, PFOA, PFHxS, PFOS的基質效應分別為64%、33%、55%、60%、10%。壬基酚與雙酚A的基質效應則為79%與93%。

關鍵字

全氟碳化物 ； 鄰苯二甲酸酯 ； 壬基酚 ； 雙酚A ； 固相萃取 ； 極致液相層析/串聯式質譜儀

並列摘要

Perfluoroalkyl substances (PFASs), phthalate esters (PAEs), nonylphenol (NP), and bisphenol A (BPA) are ubiquitous in the environment. These chemicals are widely used in consumer products, such as protective coatings for textiles, paint, plastic products, detergents, and food containers. Many studies show that these compounds have hepatotoxicity, reproductive toxicity, and developmental toxicity, and they are endocrine-disrupting compounds, which means they can alter the function of our hormone system. Water is the primary way for these chemicals to spread in the environment. Thus, it is necessary to monitor these compounds in the water. This study will determine 10 PFASs (PFBA, PFPeA, PFHxA, PFOA, PFNA, PFDA, PFUnDA, PFDoDA, PFHxS, and PFOS), 6 PAEs (DEP, BBP, DEHP, DNOP, DINP, and DIDP), nonylphenol, and bisphenol A in river water with ultra-high performance liquid chromatography/tandem mass spectrometry. Solid-phase extraction (SPE) with HLB cartridges will be chosen as sample preparation method. Water samples were acidified to pH 3 by adding 30 μL of 88% formic acid before SPE. In SPE procedures, the cartridgess were conditioned with 5 mL of isopropyl alcohol, 5 mL of methanol and 5 mL Milli-Q water sequentially. After loading 100 mL water samples at the flow rate of 5 mL/min, the cartridges were washed with 0.6 mL of MeOH/Milli-Q water (1:9, v/v) twice, then dried with nitrogen gas (N2) for 45 seconds. Elution was conducted by 2 mL of methanol followed by 2 mL of isopropyl alcohol, each solvent eluted at flow rate of 1 mL/min twice, and was collected together. The extracts were concentrated to 1.0 mL, and were filtrated through 0.22 μm nylon filters. The filtered extracts were concentrated to barely dried, and then were reconstituted with 100 μL of methanol prior to instrumental analysis. The results showed that the matrix effect factors of six PAEs were 88%-116%. In PFASs, the matrix effect factors of PFBA, PFNA, PFDA, PFUnDA and PFDoDA were 77%-85%, and PFPeA, PFHxA, PFOA, PFHxS and PFOS were 64%, 33%, 55%, 60% and 10%, respectively. Matrix effects of nonylphenol and BPA were 79% and 93%, respectively.

並列關鍵字

Perfluoroalkyl substances ； phthalate esters ； nonylphenol ； bisphenol A ； solid-phase extraction ； UPLC-MS/MS

參考文獻

1. Y.C. Chang, W.L. Chen, F.Y. Bai, P.C. Chen, G.S. Wang, and C.Y. Chen, Determination of perfluorinated chemicals in food and drinking water using high-flow solid-phase extraction and ultra-high performance liquid chromatography/tandem mass spectrometry. Analytical and Bioanalytical Chemistry, 2012. 402(3): p. 1315-1325.

2. R. Loos, G. Locoro, T. Huber, J. Wollgast, E.H. Christoph, A. de Jager, B. Manfred Gawlik, G. Hanke, G. Umlauf, and J.M. Zaldivar, Analysis of perfluorooctanoate (PFOA) and other perfluorinated compounds (PFCs) in the River Po watershed in N-Italy. Chemosphere, 2008. 71(2): p. 306-313.

3. Y.Y. Pan, Y.L. Shi, and Y.Q. Cai, Determination of perfluorinated compounds in human blood samples by high performance liquid chromatography-electrospray tandem mass spectrometry. Fenxi Huaxue/ Chinese Journal of Analytical Chemistry, 2008. 36(10): p. 1321-1326.

5. J.S. Boone, B. Guan, C. Vigo, T. Boone, C. Byrne, and J. Ferrario, A method for the analysis of perfluorinated compounds in environmental and drinking waters and the determination of their lowest concentration minimal reporting levels. Journal of Chromatography A, 2014. 1345: p. 68-77.

6. C. Lau, J.L. Butenhoff, and J.M. Rogers, The developmental toxicity of perfluoroalkyl acids and their derivatives. Toxicology and Applied Pharmacology, 2004. 198(2): p. 231-241.