環境與生活產品中常見環境荷爾蒙之分析技術研究

Research for Analytical Techniques of Common Environmental Hormones in the Environment and Commodities

張士強(Chang Shih-Chiang)

指導教授 ： 吳家誠

國立臺灣師範大學/理學院/化學系/博士(2016年)

https://doi.org/10.6345/NTNU202204858

摘要

「環境荷爾蒙」一詞是指外因性干擾生物體內分泌的化學物質，這一類物質可能模仿生物體內的天然荷爾蒙，與荷爾蒙的受體結合，影響體內荷爾蒙含量的增減，或直接刺激、抑制內分泌系統，使內分泌系統失調，進而阻礙生殖、發育等機能，甚至有引發惡性腫瘤與生物絕種的危害。例如常用的鄰苯二甲酸酯類 (phthalate esters) 塑化劑，其中數種已被世界各國如：日本、美國、歐盟列為疑似環境荷爾蒙物質，甚而禁用。然因石化業的發展、原油的煉製，使用在人類生活環境中的塑膠品多含有塑化劑成分，在廣泛的使用下，非常容易流佈於環境中，經由空氣吸入或食入或接觸而危害我們的身體健康。台灣在2011年也曾經爆發過食品中塑化劑事件，此一議題也重重傷害我國民眾的健康與國際形象。本研究主要針對常見的鄰苯二甲酸酯、三氯沙 (triclosan)、壬基酚 (4-n-nonylphenol)等環境(或疑似)荷爾蒙之化學污染物進行研究。研究中針對環境中各種基質：土壤、水質、日常生活產品進行檢測方法的技術性研究，以發展後的技術來了解各種環境中存在的狀況。
研究中之攪拌子萃取(stir bar sorptive extraction)技術是由改善固相微萃取技術所衍生而來，其特點為：使用更少的樣品需求量與少量的溶劑來達成微量分析之目的，本研究發展分析技術於生活產品等多樣基質中的環境荷爾蒙檢測，結果顯示對於各種日用品等基質，如：牙膏、清潔劑、肥皂等皆得到良好的方法適用性，在使用HPLC-DAD偵測下，方法檢測極限亦可達如質譜分析之ppb等級(1.2 (DBP) to 90.8 (DEHP) ng/mL)。此技術非常適合綠色、簡單、快速等環境友善的檢測方法發展，也預期可將其材料應用於分散式微量固相萃取(dispersive SPE)或QuEChERS (Quick, Easy, Cheap, Effective, Rugged, and Safe)樣品前處理技術上。
人類最常接觸環境荷爾蒙的方式為間接食入受污染的食物，例如存在於食物保鮮膜中的鄰苯二甲酸塑化劑，雖然近年來的產品皆標榜無塑毒的使用，但本研究發展以高靈敏GC-MS的技術檢測下，達10種鄰苯二甲酸酯的目標物在多達22種樣品中皆有被微量檢出，且亦發現目標物之外的塑化劑使用，顯示人類無時不刻暴露在高風險的環境下。
塑化劑的大量使用，最後有大部分是累積於環境土壤中，本研究中以次臨界水(subcritical water)在250℃、100 bar條件下來處理受鄰苯二甲酸酯污染的土壤，此條件下萃取處理的效率最高可達到80~90%以上：顯示對土壤中的鄰苯二甲酸酯污染具有良好的移除率。此外，次臨界水對部分鄰苯二甲酸酯具有分解作用，其後續效益值得深入探討。
本研究中所發展檢測的技術涵蓋了人類環境中各種可能接觸的樣品基質，從環境中的水、土壤到日常用品與食物接觸用品，很遺憾的是各種不同來源的樣品種類皆發現我們所欲檢測的環境荷爾蒙目標物，一來顯示研究中所發展檢測技術的適用性，二來也顯示化學品與環境污染物深入我們日常生活的嚴重性，現今的地球環境已是無處不化學、無處不污染的狀態。在研究結果呈現的同時，我們也希望藉由研究結果的展現能將檢測技術更為精進，朝向更環保的方式來發展，也可達到符合現代生活科學實用、應用所需的檢驗範疇。

關鍵字

環境荷爾蒙 ； 內分泌干擾物 ； 塑化劑 ； 鄰苯二甲酸酯 ； 三氯沙 ； 壬基酚 ； 攪拌子萃取

並列摘要

"Environmental hormone" refers to exogenous chemicals that interfere with endocrine organism. These chemicals may mimic native hormones and bind with hormone receptor. The impact is to change the content of hormones or direct stimulation, inhibition of the endocrine system, endocrine system disorders, thereby impeding the reproductive, developmental and other functions, even extinctions caused by cancer and harm. For example, some of commonly used plasticizer phthalate esters (PAEs), which have been restricted around the world such as: Japan, the United States, and the European Union as suspected endocrine disrupting substances. Due to the development of its petrochemical industry and oil refining, they may be easily transferred to human bodies through inhalation or ingestion. In 2011, Taiwan has an outbreak of food plasticizer event which causes the harm for numerous people health and international attentions. In this research, phthalates, triclosan (TCS), and 4-nonylphenol (4-n-NP) have been detected in various matrices such as soil, water, daily life products by using our developed analytical schemes.
The technique, stir bar sorptive extraction (SBSE), is the approach of solid phase micro-extraction (SPME). This approach uses less solvent and sample amount to achieve the goal of greener, simpler, and environmental friendly of analytical method. The targeted analytes could be rapidly determined with limits of quantification (LOQs) ranging from 1.2 (DBP) to 90.8 (DEHP) ng/mL in real samples such as bottled waters, personal care products, soaps, lotions, and urine. The developed analytical scheme is solvent-saving, efficient, and capable of fast screening samples for these common endocrine disrupting chemicals (EDCs). In the further, we hope it can be expectedly utilized for the material approach in the methods of dispersive SPE) or QuEChERS (Quick, Easy, Cheap, Effective, Rugged, and Safe).
The most common way of human exposure to environmental hormones is indirect ingestion of contaminated food. Although the new age types of product announced that there were non-toxic plasticizers inside, our research results indicate that up to 10 different plasticizers were detected in 22 samples even in non-PVC food wraps through the developed GC-MS method. We even discovered the non-targeted plasticizers present in the certain samples.
We used subcritical water with the conditions of 250℃、100 bar to treat the PAE-contaminated soils for the remediation process. Accelerated solvent extraction (ASE) coupled with HPLC-UV were utilized for the evaluation of removal efficiencies. The results indicated removal efficiency ranges of 80–90% for PAEs spiked in soil samples.
In this research, most common matrices such as waters, soils, and life products were selected to be samples for the development of analytical method. Unfortunately, some of targeted environmental hormones were presented in different sample sources, which showed that the developed analytical schemes were suitable and permanent for those various samples. Nowadays, there are contaminates and chemicals around our surrounding, we hope the development of analytical scheme can be more precise, greener for the applications of life science.

並列關鍵字

environmental hormone ； endocrine disrupting chemical ； plasticizer ； phthalate ester ； triclosan ； nonylphenol ； stir bar sorptive extraction

參考文獻

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