生鮮及加工肉品中新菸鹼類農藥、對羥基苯甲酸酯類及雙酚類之 ID-UPLC-MS/MS 方法開發、含量測定及 暴露評估研究

Method development, determination and exposure assessment of neonicotinoids, parabens and bisphenols in fresh and processed meat by ID-UPLC-MS/MS

陳依禧(Yi-Hsi Chen)

指導教授 ： 盧冠宏

共同指導教授 ： 陳鑫昌(Hsin-Chang Chen)

國立臺灣大學/公共衛生學院/食品安全與健康研究所/碩士(2022年)

https://doi.org/10.6342/NTU202203700

摘要

隨著人類生活需求、農業及經濟發展，諸多化學物質如新菸鹼類農藥(Neonicotinoids, NEOs) 、對羥基苯甲酸酯類 (Esters of para-hydroxybenzoic acid, parabens) 及雙酚類化合物(Bisphenols) 等新興環境危害物已被廣泛使用。NEOs為系統性殺蟲劑，能被植物吸收運送到整株，並可能因此進入食物鏈中對生態造成影響，且可能影響人類生殖及腦部神經發展；parabens為一類廣效型抑制微生物滋長之防腐劑；bisphenols 主要作為環氧樹脂及聚碳酸酯塑料之原料，但 parabens及 bisphenols 因具潛在內分泌干擾效應，被視為環境荷爾蒙。然而，這些化學物質可能因使用而殘留於食品中或經環境遷移而污染食品，並透過食物鏈對人體健康造成潛在危害。為了解生鮮肉品及加工肉品中此三類多重新興環境危害物之背景濃度與分佈，本研究建立一套同位素稀釋極致效能液相層析串聯質譜法(IDUPLC-MS/MS)分析方法，同時測定生鮮肉品及加工肉品中 7 種 NEOs、9 種parabens 及 5 種 bisphenols。
本研究依據國家攝食資料庫及實地市場調查資料，於美式賣場、超市及傳統市場、線上商店採集 27 件生鮮肉品及 30 件加工肉品，以改良之 QuEChERS 樣品前處理搭配 ID-UPLC-MS/MS 檢測肉品中 NEOs、parabens 及 bisphenols 濃度。分析方法確效結果顯示，各分析物之基質匹配檢量線相關係數 r2 > 0.990，呈良好線性關係，其定量極限為 0.022 - 0.635 ng/g；同日間與異日間試驗中，各分析物在肉類基質中均有良好之準確度(回收率 89.20%–112.00%與 90.33%–115.67%)與精密度(相對標準偏差 1.67%–7.88%與 0.42%–11.70%)，符合國際食品法典委員會之確效規範。確效之分析方法應用於 27 件生鮮肉品檢測，其定量結果顯示 bisphenols 中bisphenol A 及 bisphenol S 具有最高的偵測率(皆為 81.5%)，濃度範圍為 n.d. - 2.374 ng/g；NEOs 僅有 imidacloprid 與 acetamiprid 檢出微量濃度；parabens 中 ethyl paraben 具有最高偵測率(96.3%)；30 件加工肉品結果顯示 bisphenols 中 bisphenol A 具 有 最 高 的 偵 測 率(56.7%)，濃度範圍為 n.d. - 1.728 ng/g；NEOs 僅檢出 imidacloprid ( 0.099 ng/g)、acetamiprid( 0.228 ng/g)與thiamethoxam ( 18.436 ng/g)；Parabens 之濃度  2.966 ng/g。風險評估結果顯示 imidacloprid 之新鮮肉類平均每日暴露劑量(Average Daily Dose) 最高的是男性 6-12 歲組 (2.3×10-7 mg/kg-bw/day)，而最低的是女性>65 歲組 (7.9×10-8 mg/kg-bw/day)，但皆低於 U.S. Environmental Protection Agency 參考劑量之標準。Acetamiprid 與 BPA 在各性別年齡組之間，亦有相同的趨勢。危害指標 Hazard Index 包含 parabens 及 bisphenol A 在各性別年齡組皆小於 1，介於 3.2×10-5 至 6.7×10-5，顯示暴露濃度低於會產生危害效應之閾值。然而此結果僅呈現六種生鮮肉品的累積風險，因此必須更保守的推算，未來也可納入更多種類的食品。本研究成功建立市售生鮮肉品及加工肉品中三類新興環境危害物之定量分析方法並檢測 57 件肉類食品以了解其背景濃度及暴露風險評估。

關鍵字

新菸鹼類農藥 ； 對羥基苯甲酸酯類 ； 雙酚類化合物 ； QuEChERS

並列摘要

Many chemicals have been widely used to meet the needs of humans, such as neonicotinoids (NEOs), parabens (Esters of para-hydroxybenzoic acid, parabens), and bisphenols. A systemic insecticide, NEOs may enter the environment and food chain after spraying, posing risks to ecology and human health, including brain and nerve development; parabens are a broad-spectrum preservative that inhibits the growth of microorganisms; bisphenols are mainly used as raw materials for epoxy resins and polycarbonate plastics, and both parabens and bisphenols are regarded as environmental hormones due to their potential endocrine-disrupting effects. These chemicals may remain in food as a result of their use or migration through the environment, contaminating food and posing a potential health risk for humans. It is important to understand the background concentration and distribution of these three types of multiple emerging environmental hazards in fresh and processed meats. This study established a set of isotope dilution ultra-performance liquid chromatography-tandem mass spectrometry (ID-UPLC-MS/MS) analysis methods to simultaneously determine 7 NEOs, 9 parabens, and 5 bisphenols in fresh and processed meat.
Based on the national food intake database and field market survey data, 27 pieces of fresh meat and 30 pieces of processed meat were collected from supermarkets, traditional markets, and online shops from November 2021 to February 2022. The results of analytical method validation showed that the good linearity achieved with the correlation coefficient (r2) all above 0.990 in matrix-matched calibration line. Limits of detection (LODs) and limits of quantification (LOQs) ranged from 0.007 to 0.191 ng/g and 0.022 to 0.635 ng/g, respectively. The accuracy and precision in the assessment of intra- and inter-day met the criteria of TFDA, with accuracy ranging from 89.20% to 115.67%, and precision ranging from 0.42 to 11.70%. Finally, the validated method was applied to analyze 57 marketed meat products. Results in fresh meats products indicated that bisphenol A and bisphenol S were found in most collected samples (81.5%), with the concentration of n.d. to 2.374 ng/g; among the NEOs, only imidacloprid (≤ 0.124 ng/g), acetamiprid (≤ 0.051 ng/g) were detected; methylparaben can be quantified in most collected samples (85.2%), with the concentration of n.d. to 6.221 ng/g. Similar to the result in fresh meat, bisphenol A had a higher detection frequency in processed meats products (56.67%); imidacloprid (≤ 0.099 ng/g), acetamiprid (≤ 0.228 ng/g), and thiamethoxam (≤ 18.436 ng/g) were detected among NEOs; concentration of parabens ≤ 2.966 ng/g. The HQ of bisphenols, NEOs, and parabens pose no risks from dietary intake of fresh meat. In this study, a quantitative analysis method was successfully developed and could be applied for 21 analytes in commercial meat products. Furthermore, risk assessment was also carried out in this study. Risk assessment results showed that the average daily exposure dose of imidacloprid in fresh meat was highest in male aged 6-12 years (2.3×10-7 mg/kg-bw/day), and lowest in female over 65 years of age (7.9×10-8 mg/kg-bw/day), but all were lower than the USEPA reference dose. Acetamiprid and bisphenol A showed similar patterns. In all genders and age groups, the Hazard Index is less than 1, indicating that the exposure concentration is below the threshold for harmful effects. Despite this, the combined effect of multiple chemicals, multiple exposure routes, and long-term exposures may be concerns in the future. An analysis method was developed and successfully applied to three types of emerging environmental hazards in meat products. The study also found background concentrations and exposure risk assessments in commercially available meat products.

並列關鍵字

Neonicotinoids ； Esters of para-hydroxybenzoic acid ； Bisphenols ； QuEChERS

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