空氣中人造麝香採樣方法及分析方法開發

Development of Synthetic Musks Analysis and Airborne Synthetic Musks Sampling Methods

王怡婷(I-Ting Wang)

指導教授 ： 蔡詩偉

國立臺灣大學/公共衛生學院/環境衛生研究所/博士(2014年)

https://doi.org/10.6342/NTU.2014.01443

摘要

人造麝香（synthetic musks; artificial musks） 廣泛添加於消費個人產品個人或家用產品，如化妝品、家庭用品及清潔用品等個人照護用品，使產品具有香氣；依化學成份的不同，人造麝香主要分為硝基麝香、多環麝香、大環麝香、及脂環麝香等四類。硝基麝香與多環麝香為目前最廣為使用及討論的人造麝香。硝基麝香因其毒性，已逐漸被禁用或管制，因此多環麝香為目前主要使用的人造麝香。此兩者皆已列管於美國環保署的毒性化學物質資料中，且證據顯示人造麝香會誘發氣喘、內分泌干擾物、及與癌症有相關，人造麝香可能會經由皮膚接觸 、食入、空氣吸入等造成人體暴露。人造麝香廣泛存在於室內空氣及周界環境中，但空氣中人造麝香吸入往往因為其香味而被忽略。截至目前為止，還沒有相當完整的人造麝香於空氣中之分佈狀況，亦沒有相當敏感且易於應用的空氣中人造麝香的採樣分析方法，因此本研究著重於空氣中人造麝香的採樣方法及人造麝香的分析方法，並以建立之分析方法量測市售21種香精，另外以現場採樣評估調查目前台灣生產香氛類用品的工作場所室內人造麝香狀況。
本研究使用泡綿採樣管與玻璃纖維濾紙為採樣介質，經過微波萃取及吹氮濃縮等樣本前處理，再以三重四極柱氣相層析串聯質譜儀建立全掃描及特定多重反應監控離子對化的定性及定量條件，分析常見的10種人造麝香。相較於傳統的單一選擇離子測量，分析靈敏度有大幅度進步，回收率皆在60–120%。搭配採樣方法，採集脫附效率除DPMI因其蒸汽壓較高導致採集脫附效率為53%外，9種人造麝香採集脫附效率為64–120%，因此每分鐘3.5升採集8個小時，空氣濃度僅需達0.48 ng m-3 (DPMI)即可。
針對5家生產不同香氛製品的勞工作業場所進行空氣採樣的結果發現，本研究採樣工廠使用的人造麝香以多環麝香類為大宗（多環麝香以HHCB及AHTN為最常出現且濃度較高的2種，ADBI及DPMI亦有測量到），並有化妝品禁用成分被檢出（如MA、MM)。工作場所空氣中的人造麝香主要以氣狀存在，但在粒狀物亦可觀察到人造麝香粘附的狀況，空氣中氣狀多環麝香平均濃度為3.4×102 ng m-3,，氣狀硝基麝香為1.3×102 ng m-3，粒狀多環麝香為4.4×102 ng m-3,，粒狀硝基麝香則為5.4×102 ng m-3。 另外本研究亦應用已開發的MRM方法定性市售21種香精的人造麝香，其中二十種都含有HHCB及AHTN，與我們的現場樣本結果符合，也與人造麝香的使用量調查相符。
人造麝香需要更多更深入的研究，無論是在環境的影響方面或是健康危害方面，需建立更完整的風險評估模式。本研究完成之作業場所常見10種人造麝香採樣分析方法，可用於未來對於人造麝香分佈調查等評估等應用。

關鍵字

人造麝香 ； 香精 ； 空氣採樣 ； 泡綿採樣器 ； 暴露評估 ； 氣相層析串聯式質譜儀

並列摘要

Synthetic musk creates a variety of scent by different combination of its individual compounds and has been widely used in a large variety of consumer products with relatively lower cost regarding to natural musk, especially pharmaceutical and personal care products (PPCPs). According to the structures of the compounds, synthetic musk can be divided into four groups, nitro musk, polycyclic musk, macrocyclic musk, and alicyclic musk. Being widely used with considerate consumption in the past and presence, nitro musk and polycyclic musk have been the two mainly discussed types of synthetic musk in the literatures. As for the adverse health effects, synthetic musk has been partially filed in the Hazardous Substances Data Bank (HSDBR). In addition, there were studies indicating that synthetic musks might induce asthma as well as act as endocrine disruptors and be correlated to cancers. Synthetic musk is omnipresent in the air, but the exposure via inhalation is often ignored due to pleasant smells. Furthermore, the information with the regards to the understanding for the distribution of synthetic musks in air is limited. Therefore, this study mainly aimed to develop a highly sensitive and widely applicable method for the determinations of airborne synthetic musk. Besides, with the method developed here, we analyzed twenty-one available commercially available fragrances and also focused on the comprehensive evaluation of the indoor air quality about the synthetic musk distribution in the working environment of the scented-products manufacturing sites.
Polyurethane foam (PUF) and filter were employed for active air sampling in the research. As for the sample preparation, microwave assisted extraction (MAE) and nitrogen evaporator were performed for the purpose of time-saving and better efficiency. A gas chromatography coupled with triple quadrupole tandem mass spectrometer (GC-MS/MS) with specific multiple reaction monitoring (MRM) transition pairs were the major technique applied for sample analysis in this study. Compared with using selected ion monitoring (SIM) mode traditionally, the sensitivities were improved in this study about an order at least. The recoveries have been all achieved the range between 60% and 120%. On the other hand, with the sampling preparation and sampling method established here, the collection efficiencies were within the range of 64% to 120%. In terms of air concentration, as low as 0.48 ng m-3 can be determined when sampling at 3.5 L min-1 for 8 hours. The method established was further applied to the analysis of synthetic musk compounds in air samples collected in cosmetics plants.
The field sample results showed that both polycyclic and nitro-musks were observed in the field in gaseous and particle phases. To be more specific, obviously, the airborne concentrations of polycyclic musks found in all the factories were much higher than those nitro musks. In addition, Cashmeran (DPMI), Celstolide (ADBI), Galaxolide (HHCB), and Tonalide (AHTN) were the four major synthetic musks as the dominant musk compounds in the working environment. To be detailed, the average concentrations of gaseous polycyclic musk, gaseous nitro-musk, particle-phase polycyclic musk, and particle-phase nitro musk were 3.4×102, 1.3×102, 4.4×102, and 5.4×102 ng m-3, respectively.
The analysis method could be adopted onto various types of samples. 21 commercially available liquid fragrances were analyzed and identified with their compositions of synthetic musks. All of the samples were found composed of synthetic musks. HHCB and AHTN were the most commonly seen ingredients. This result is consistent with the observation from the air samples and the usage estimation from IFRA.
Synthetic musks definitely deserve further studies and insight into its environmental impacts and potential to cause harm to human beings. The methodology from sampling, sample preparation, to analysis developed in this study could be extensively applied onto various applications.

並列關鍵字

Synthetic Musk ； Fragrances ； Air Sampling ； Polyurethane Foam ； Gas Chromatography Tandem Mass Spectrometers ； Exposure Assessment

參考文獻

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