使用固相微萃取及氣相層析質譜儀測定消費產品中的潛在揮發性有機物

Abstract

在室內環境中常被使用的各種消費產品，其所添加的香料在近年來被認為可能造成健康危害；而這類產品主要用於清潔且包羅萬象，包括：個人清潔產品、化妝品以及廚浴清潔用品等。研究指出，消費產品中的香氛物質可能導致黏膜組織刺激、氣喘以及偏頭痛等；常見的香氛物質，如α-蒎烯（α-pinene）、α-松油醇（α-terpineol）以及樟腦（Camphor）等，可能會引起皮膚刺激外，香氛物質在室內環境中與臭氧等自由基反應亦可能產生甲醛以及二次有機氣膠。由於乙醛（Acetaldehyde）、二噁烷（1,4-dioxane）以及二氯甲烷（Dichloromethane）等可能致癌物也在其他研究中被檢測出，因此消費產品也被視為潛在致癌的來源之一。此外，在室內環境中室內外濃度比值（I/O ratio）較高的物質，如：乙酸正丁酯（n-Butyl acetate）、庚醛（Heptanal）、2-苯氧乙醇（2-Phenoxyethanol）以及肉桂醛（Cinnamal）等，也被指出消費產品是可能的室內產生源。 為了瞭解上述十種潛在危害物質在產品中的分佈狀況，本研究首先建立簡易且可行的同步分析方法。研究中所取得的消費產品樣本，皆以去離子水稀釋，並加入氯化鈉及擬似標準品，再以50/30μm CAR/DVB/PDMS固相微萃取纖維進行頂空吸附；而萃取前亦先加入O-（2,3,4,5,6-五氟芐基）羥胺鹽酸鹽，並在45℃進行15分鐘衍生反應，接著纖維會在樣本頂空進行30分鐘的萃取後，注入氣相層析串聯質譜儀中進行脫附以及分析。 本研究進行了固相微萃取操作之方法優化；透過調整衍生化時間及溫度、衍生試劑添加量以及萃取時間等參數，提供可接受的靈敏度與穩定度以測定各種產品中的待測物。本研究所建立的分析方法，檢量線的R平方值皆高於0.99、分析物的相對偏差為 1.49%-14.46%、分析物最低偵測極限可到0.1 ng/mL (ppb)，而回收率約在61.7%-118.6之間。 本研究分析了 111 種消費產品，其中α-松油醇、乙醛、α-蒎烯以及樟腦有較高的檢出率，分別為77.48%、63.06%、32.43%以及18.92%。各類產品中，以沖洗產品以及香水較常被檢出較高濃度的待測物；例如：α-松油醇、乙醛、α-蒎烯以及樟腦在所有產品中的平均濃度分別為96.6、7.4、91.5以及61.2 μg/g；在香水中，乙醛以及α-油醇被檢測出最高的平均濃度（分別為110.91 μg/g以及556.76 μg/g）。根據歐盟Scientific Committee on Consumer safety (SCCS)建議，2-苯氧乙醇在嬰兒相關產品的濃度應低於0.4%，然而本研究中收集到的兩樣嬰兒沐浴乳均超過限量（4915.4 μg/g和9258.8 μg/g）（本研究中2-苯氧乙醇的檢出率為16.22%）。此外，儘管乙醛在消費者產品中沒有任何濃度限制，但歐盟SCCS指出在各消費者產品中的乙醛含量達100 ppm時將具有潛在的致癌風險的；而本研究結果顯示，有三種香水以及一項浴室清潔劑中的乙醛濃度超過100 μg/g，最高濃度約為346.0 μg/g。 本研究分析不同消費產品中潛在揮發性有機物的濃度分佈狀況，而所獲結果將可用於未來之健康風險評估。另外，部份樣本中2-苯氧乙醇及乙醛的含量超過歐盟SCCS的標準，因此建議應針對嬰幼兒產品訂定濃度限制，並規範將化學物質的含量列於產品標籤上。

Consumer products normally added with fragrance ingredients were considered as potential health concerns in indoor environments recently. Various products, such as self-cleaning products, cosmetics and household products, are frequently applied in our everyday life for purifying and beautification. However, previous studies reported that fragrance chemicals in products could be related to mucosal irritation, asthma and headache. For instance, terpenes like α-pinene, α-terpineol and camphor, may cause skin irritation. Furthermore, the presence of these compounds indoors can lead to the formation of formaldehyde and secondary organic aerosols (SOAs) by ozonolysis. Potential cancer risk is possible since the fact that studies have detected possible, including acetaldehyde, 1,4-dioxane and dichloromethane in consumer products. Compounds with high I/O ratio such as n-butyl acetate, heptanal, 2-phenoxyethanol and cinnamal were also reported existing in products. To determine the distributions of the ten compounds mentioned above in the consumer products in Taiwan, the purpose of this study was to develop a simple and sensitive analytical method for the measurements. The samples of the consumer products were first dissolved in dd-water. Sample preparation was carried out by SPME with 50/30 μm CAR/DVB/PDMS SPME fiber. Samples were all added with sodium chloride and surrogate. In-situ derivatization of acetaldehyde with O‐(2,3,4,5,6‐pentafluorobenzyl) hydroxylamine hydrochloride was also performed. Extraction in headspace of samples was set at 45℃ for 30 minutes, followed by the desorption in GC port for the analysis with gas chromatography tandem mass spectrometry (GC/MS-MS). By optimizing parameters including pre-incubation time, pre-incubation temperature, extraction time and amount of derivatization reagent, the method established in this study can be used to determine the analytes with acceptable sensitivity. The R-squared values were all above 0.990 for the calibration curves. While RSDs were 1.49%-14.46%, the method detection limit of some analytes were as low as 0.1 ng/mL, and the recoveries ranged from 61.7% to 118.6%. A total 111 consumer products were included in this study. Higher detection rate for α-terpineol, acetaldehyde, α-pinene and camphor was found with 77.48%, 63.06%, 32.43% and 18.92%, respectively. Rinse-off products and perfumes were found with more prevalent presence of the analytes. Mean concentration of α-terpineol, acetaldehyde, α-pinene and camphor in all products were 96.6, 7.4, 91.5 and 61.2 μg/g, respectively. Highest mean concentration of acetaldehyde and α-terpineol was found in perfumes (110.91 μg/g and 556.76 μg/g, respectively). For 2-phenoxyethanol, according to the advice from EU Scientific Committee on Consumer Safety (SCCS), the content in baby related products should be lower than 0.4%. In this study, two baby body washes were found with the concentration of 2-phenoxyethanol over the limitation (4915.4 μg/g 9258.8 μg/g, respectively). In addition, three perfumes and one bathroom cleaning products were found with the concentration of acetaldehyde over 100 ppm (highest: 346.0 μg/g), while it was recommended elsewhere that 100 ppm of acetaldehyde in all products may lead to potential life-time cancer risk. In conclusion, the findings demonstrated that perfumes and rinse-off products were more likely to contain the analytes discussed in this study, while the results can be applied for the assessments of health risks in the future. Nevertheless, the contents of 2-phenoxyethanol and acetaldehyde in some products were with the levels above the recommendations from EU SCCS. Hence, labelling the ingredients and the associated concentrations on the products should be enforced to protect people’s health.