以極致液相層析/串聯式質譜儀檢測魚體組織中鄰苯二甲酸二乙酯與個人保健品

Determination of Diethyl Phthalate and Personal Care Products in Fish Tissues with Ultra-performance Liquid Chromatography/tandem Mass Spectrometry

洪婉華(Wan-Hua Hung)

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(2018年)

https://doi.org/10.6342/NTU201802422

摘要

鄰苯二甲酸酯(phthalate esters)廣泛使用於工業和消費性產品，個人保健品(personal care products)則包含民眾基於日常健康照護、驅蟲、美容等目的而大量使用的各式各樣的化合物。許多研究顯示鄰苯二甲酸酯和一些個人保健品具有發育毒性且為內分泌干擾物質。這兩類化合物普遍存在於環境中；污水處理廠是它們進入環境的主要途徑之一。一些研究顯示這些化合物可能會累積在魚體內，然而少有研究同時分析不同魚體組織器官裡的鄰苯二甲酸酯或個人保健品成分，且能在魚體組織器官同時檢測這兩大類化合物的分析方法目前仍相當有限。因此，本研究開發檢測魚肉和魚肝內的鄰苯二甲酸二乙酯和十一種個人保健品成分之分析方法。樣本前處理採用基質固相分散法(matrix solid-phase dispersion, MSPD)，以C8作為分散劑，並依序用5毫升甲醇和丙酮沖提樣本管柱和其下所接的矽膠樣本淨化管柱；樣本經濃縮後以極致液相層析串聯式質譜儀，在多重反應監測模式下獲取質荷比資訊，並搭配同位素稀釋技術進行定量分析。鄰苯二甲酸二乙酯和鹼性個人保健品以正離子電灑游離法游離，並使用Ascentis Express F5管柱搭配移動相(A) 5 mM醋酸氨水溶液(pH = 6.40)、(B)甲醇，進行梯度層析；酸性個人保健品則以負離子電灑游離法游離，並使用Waters CORTECS UPLC C18管柱搭配移動相(A) 0.04%乙酸(pH = 3.45)、(B)甲醇，進行梯度層析。
儀器方法最佳化方面，正離子電灑游離法比較了兩種有機移動相和四個游離源溫度，負離子電灑游離法則比較了兩種不同的層析條件。前處理最佳化方面，本研究比較了：(1)兩種沖提溶劑組合；(2)兩種沖提溶劑體積；(3)兩種MSPD分散劑；(4)兩種淨化吸附劑；(5)不同量的淨化吸附劑；(6)不同體積的最終樣本萃取液。魚肉和魚肝的基質效應因子大部分分別落在70.3-95.6% 與24.3-61.9%；魚肉的萃取效率有一半落在62.1-76.6%，魚肝則大部分落在31.6-71.2%。待測物在魚肉和魚肝的方法偵測極限分別為0.57-15.0 ng/g（濕重）及4.37-104 ng/g（濕重）。本分析方法待測物的定量偏差大多低於30%，相對標準偏差則均低於20%。

關鍵字

鄰苯二甲酸二乙酯 ； 個人保健品 ； 魚肉 ； 魚肝 ； 基質固相分散法 ； 極致液相層析串聯式質譜儀

並列摘要

Phthalate esters (PAEs) are widely used in industrial and consumer products; personal care products (PCPs) contain diverse chemicals used at a large scale for daily lives or personal hygiene, which include analgesics, insect repellents, UV filters, and so on. Previous studies indicate that PAEs and some PCP ingredients have developmental toxicity and could disrupt endocrine systems. The two groups of compounds are ubiquitous in the environment, and wastewater treatment plants are one of the major emission sources. Some studies show that PAEs and PCPs may accumulate in fish tissues; however, limited studies determined PAEs or PCPs in different fish tissues simultaneously. Furthermore, few methods are available to analyze PAEs and PCPs together in fish tissues. Thus, this study developed and validated a method to simultaneously determine diethyl phthalate (DEP) and 11 PCPs ingredients in fish muscle and liver. Samples were extracted with matrix solid-phase dispersion (MSPD) using C8 adsorbent; 5-mL methanol and acetone were sequentially passed through the tandem system of a MSPD cartridge piggyback on a silica gel cartridge for cleanup. After concentration, the eluents were analyzed using ultra-performance liquid chromatography/tandem mass spectrometry (UPLC-MS/MS) with multiple reaction monitoring (MRM) and were quantified with isotope dilution techniques. DEP and the basic PCPs were separated on an Ascentis Express F5 column (30 × 2.1 mm, 2.0 μm) with the mobile phases consisting of (A) 5 mM ammonium acetate(aq) (pH = 6.40) and (B) methanol, and were ionized at positive electrospray ionization mode (ESI+). The acidic analytes were separated on a Waters CORTECS UPLC C18 column (30 × 2.1 mm, 1.6 μm) with the mobile phases consisting of (A) 0.04% acetic acid(aq) (pH = 3.45) and (B) methanol, and were ionized at negative electrospray ionization mode (ESI-).
The optimization of the instrumental analysis included the tests of two organic mobile phases and four source temperatures for ESI+, and two chromatographic conditions for ESI-. The sample preparation method was optimized by testing two elution solvent combinations, two elution volumes of solvents at each portion, two adsorbents for MSPD, two adsorbents for cleanup, the amount of cleanup adsorbents, and volumes of the final residues.
The matrix effect factors of most analytes in fish muscle and liver ranged from 70.3-95.6% and 24.3-61.9%, respectively. The extraction efficiencies of half the analytes in muscle were 62.1-76.6%, and those of most analytes in liver were 31.6-71.2%. The limits of detection (LODs) of analytes were 0.57-15.0 ng/g weight wet (w.w) for muscle and 4.37-104 ng/g w.w. for liver, respectively. Most of the quantitative biases were below 30%, and all the relative standard deviations were below 20%.

並列關鍵字

diethyl phthalate ； personal care products ； fish muscle ； fish liver ； matrix solid-phase dispersion ； UPLC-MS/MS

參考文獻

Reference

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