利用固相微萃取技術分析人保健用品中之致敏性香料

香料、香精被廣泛地添加在我們的日常用品中，包括：洗髮精、沐浴露、乳液、香水等個人保健用品及洗碗精、洗衣精等家用清潔劑，而現代社會的消費習慣也使得我們暴露於香料、香精的機會增多，然而長久使用這些帶有香味的產品後，暴露於香料產生的不良健康效應，如：皮膚炎、咳嗽、引發哮喘及偏頭痛…等症狀也漸漸浮現。為了保障民眾的健康，歐洲化妝品及非食品產品科學委員會(European Scientific Committee on Cosmetic Products and Non-Food Products, SCCNFP)列出了26種具有致敏性的香料成份，此外，歐盟法規也要求：若此致敏性香料在產品成分中超過一定濃度，則必須於產品標籤中明確標示該化合物的名稱，不可僅以「Perfume、Fragrance」等字樣標示之。儘管如此，市面上大多數的產品仍含有香料，甚至標榜「無添加香精」的產品也可能由於其防腐功效或為了掩蓋原物料異味等目的而添加香料物質。至目前為止，台灣關於個人衛生用品、化粧品、清潔消毒用品及香水等消費性產品中可能存在的致敏性香料成份之資訊仍相當有限，對於產品標示也未有明確規範；而使用個人保健用品是消費者接觸此26種致敏性香料的最大暴露來源，為了瞭解國人接觸致敏性香料、香精可能造成的健康風險，研擬可行的管理策略且建立一套有效並可分析致敏性香料濃度於不同種類之個人保健用品中的方法是必要的。本研究針對SCCNFP提出的致敏性香料成份(除了天然混合物樹苔與橡苔)，以頂空固相微萃取(HS-SPME)前處理步驟搭配氣相層析串聯質譜儀(Triple Quadrupole GC/MS/MS)同步偵測24種致敏性香料，以建立省時、簡便且較環保的分析方法；首先將個人保健用品以二次水稀釋，萃取步驟使用65μm PDMS / DVB萃取纖維搭配頂空萃取模式，以60℃萃取20分鐘，在達平衡後直接將萃取纖維插入氣相層析儀之進樣口進行10分鐘之熱脫附，脫附效率皆達99.8%以上；偵測端使用串聯質譜儀的多重反應監測模式(Multiple Reaction Monitoring, MRM)偵測，24種致敏香料之定量線性範圍依其特性各有不同，方法偵測極限範圍為0.0014 ng/ml至187.76 ng/ml，檢量線呈現良好的線性(R2>0.99)及精準度(RSD≦10%)，而實際檢測樣本的結果顯示，在以二次水稀釋樣本40倍後無明顯基質效應。共計89項、九大類有效樣本於本研究中進行致敏性香料定量分析，結果顯示24種致敏性香料皆可以在個人保健用品中檢測出；整體來說，各物質的出現頻率在不同種類產品中的趨勢十分類似，其中，苯甲醇(Benzyl alcohol)、芳樟醇(Linalool)、d-檸檬烯、(d-Limonene)及鈴蘭醛(Lyral)在產品中被檢測出的頻率皆大於80%；而洗去型產品(洗髮精、沐浴乳及洗面乳)不論是在香料種類或濃度方面表現皆大於駐留型產品(乳液類)；嬰兒及敏感性肌膚專用之產品在本實驗中也被證實含有較少致敏性香料種類及較低濃度；此外，實驗發現共計14件產品有錯誤標示的情況，其在成分標籤中未提到含有香料或香精。本研究以固相微萃取技術搭配氣相層析串聯質譜儀之檢測方法，提供九大類個人保健用品中之致敏性香料濃度，未來此方法可以應用在更多不同種類之產品上以獲得更完整之致敏性香料濃度資訊，進而評估國人之暴露健康風險。

關鍵字

固相微萃取；致敏性；香料香精；個人保健用品；氣相層析串聯質譜儀

並列摘要

Fragrances are widely used nowadays. For example, most of the personal care products (PCPs), cosmetics and household products contain fragrance ingredients. And, the chance of exposure to these chemicals is increasing due to modern life style. More and more health concerns related to the exposures to fragrances have been observed elsewhere, including rashes, dermatitis, coughing, asthma attacks, and migraine, …etc. In 1999, the European Scientific Committee on Cosmetic Products and Non-Food Products (SCCNFP) identified a set of 26 fragrance allergens. The European Union also regulates the labels of these chemicals on the cosmetics. In Taiwan, there is still no information about the market distributions of fragrance allergens. The presence of these chemicals is not required to be labeled on the cosmetic products, either. Hence, there is a need to develop a convenient and sensitive method for the determinations of these allergens in PCPs before we can assess the possible health risks. In this study, the SPME procedure coupled with gas chromatography-tandem mass spectrometry (GC-MS/MS) in multireaction monitoring (MRM) MRM mode was successfully applied to simultaneously analyze the 24 fragrance allergens in personal care products. 65μm Polydimethylsiloxane /Divinylbenzene (PDMS/DVB) fiber was exposed to the headspace over the sample. The extraction was performed at 60℃ for 20 minutes with 500 rpm followed by the 10 minute desorption. The sensitivities of the method for the fragrance allergens were low enough to determine the concentrations in PCPs. Good linearity and precision of the 24 analytes were found, and the matrix effects were compensated by the dilution process. A total of 89 PCPs were determined in this study. The results show high prevalence of fragrance allergens in this study, especially Benzyl alcohol, Linalool, d-Limonene, and Lilial which were found in more than 80% of the PCPs. Generally speaking, the patterns of the various fragrance allergens occurrences in different types of PCPs are quite similar. Leave-on products, except for perfume, have fewer samples with high concentrations than those for the rinse-off products. In addition, the products designed for the susceptible population such as babies or people with sensitive skin contain less fragrance allergens and lower concentrations. 16.85% of the products were found to be mislabeled in this study. In conclusion, a time-saving and eco-friendly method for determining the fragrance allergens in different types of PCPs was established in this study. For future work, this analytical method could be applied to more types of products. With more complete concentration information, health risks associated with exposures to fragrance allergens could be assessed.