利用固相微萃取技術搭配氣相層析串聯質譜儀分析消費產品中的抗紫外線成分

Abstract

日常使用的產品中，為了減少紫外線對產品影響而添加了抗紫外線劑(ultraviolet filters)成份；其不僅可以保護人體皮膚免於紫外線的傷害，還可以防止產品光降解，以保持產品的功能。在抗紫外線劑中，二苯甲酮1(benzophenone-1, BP1)、二苯甲酮3(benzophenone-3, BP3)、二苯甲酮8(benzophenone-8, BP8)、水楊酸乙基己酯 (ethylhexyl salicylate, EHS)、甲基水楊醇(homosalate, HMS)、辛二烯(octocrylene, OC)、甲氧基肉桂酸辛酯(octyl methoxycinnamate, OMC)、4-甲基亞芐基樟腦(4-methylbenzylidene camphor, 4-MBC)和阿伏苯宗(butyl methoxydibenzoyl methane, BMDM)等，是被廣泛用於個人護理產品或化妝品中的化學成份。由於長期被大量使用，研究指出可以在地表水中檢測到抗紫外線劑；而這些物質會引起一般毒性和干擾內分泌作用，因此抗紫外線劑不僅被視為新興污染物，也被視為內分泌干擾物。 抗紫外線劑的主要暴露途徑是來自消費品的皮膚吸收，而許多國家已對標有防曬係數(sun protection factor, SPF)的產品規範了抗紫外線劑的最高容許含量；不過， 除了具有防曬功能的產品外，一般產品沒有強制規範需標記這些成分。 至目前為止，台灣各類消費產品中的抗紫外線劑成份及濃度分佈等相關資訊仍然有限。因此，為了估計民眾的可能暴露量，本研究首先以固相微萃取(solid-phase microextraction, SPME)結合氣相層析串聯質譜(GC-MS /MS)建立可同時量測產品中9種不同抗紫外線劑的分析方法。 本研究所取得的消費產品樣本，經純水稀釋後，添加1％ (w/ v)的碳酸鉀及100 µL乙酸酐以進行衍生反應，並利用35％ (w/ v）的氯化鈉產生鹽析作用；樣本在100℃下加熱15分鐘後(以利進行衍生反應)，將85 µm聚丙烯酸酯(Polyacrylate, PA)纖維暴露在樣品上方的頂部空間以500rpm萃取30分鐘，之後於300℃下進樣脫附5分鐘。本研究所建立的方法，其分析之線性範圍包括：BMDM和OC為0.02-20 ng / mL，OMC為0.1-10 ng / mL，EHS、HMS、BP-3和4-MBC為0.1-20 ng / mL及BP-1和BP-8為1-200 ng / mL等。各個分析物的方法偵測極限為0.0013至0.5 ng / mL；低濃度和高濃度的相對標準差皆小於20％。本研究共分析了132種樣品，將其分類為16種產品，回收率在70％至148％之間。 本研究結果顯示，身體乳液、臉部乳液、護髮產品、粉底液、香水和防曬霜是抗紫外線劑的主要暴露來源。所量測的9種物質中，HMS (14％)、BP-3 (13％)和OMC (35％)在總樣品中的檢出率相對較高；而高濃度的紫外線過濾劑主要存在於防曬霜、粉底液、香水和護髮產品中。雖然所有產品皆未超過最大允許濃度，但有些無標示具防曬功能的產品與具防曬功能產品有相似濃度的抗紫外線劑(例如：護髮產品和香水)。由於無標示防曬功能的產品，其紫外線過濾劑的濃度並未受到法規限制(BP-3除外)，故當使用此類產品時可能增加超乎預期的暴露風險。 本研究利用所測得之抗紫外線過濾劑在各類產品的幾何平均濃度，估算人體皮膚之暴露情況約為4×〖10〗^(-6)至5.71 µg / kg-bw / day。整體而言，化妝品中的檢出率與濃度皆高於免洗產品(leave-on product)，而免洗產品高於沖洗產品(rinse-off product)。另外，身體乳液、防曬霜和護髮產品則是抗紫外線過濾劑的主要暴露來源。

ABSTRACT Ultraviolet (UV) filters are added in consumer products to reduce the influence of UV rays, not only to protect human skin but also to prevent light-induced degradation of the products. Among UV filters, benzophenone-1 (BP1), benzophenone-3 (BP3), benzophenone-8 (BP8), ethylhexyl salicylate (EHS), homosalate (HMS), octocrylene (OC), octyl methoxycinnamate (OMC), 4-methylbenzylidene camphor (4-MBC) and butyl methoxydibenzoyl methane (BMDM) are widely used in personal care products or cosmetics. Due to the widespread usage, UV filters have been detected in the environmental media, such as surface water. Some studies have explored the general toxicity and the endocrine-disrupting effects of the organic UV filters. Therefore, they have been identified as the endocrine disrupting chemicals (EDCs), and also have been considered as the contaminants of emerging concern (CECs). The maximum level of UV filters in the consumer products are regulated in many countries. Nevertheless, the regulation only applies to the products labeled with sun protection factor (SPF). On the other hand, to the best of our knowledge, the information regarding the concentrations of UV filters in various categories of the consumer products was still limited in Taiwan. Hence, to estimate the associated exposures, there is a need to determine the distributions of UV filters in the consumer products. In this study, the solid-phase microextraction (SPME) coupled with gas chromatography with tandem mass spectrometry (GC-MS/MS) was applied to analyze nine different UV filters in consumer products simultaneously. Parameters which might have the effects on the extraction efficiency were considered. The pre-incubation was performed at 100°C for 15 minutes, followed by the headspace extraction for 30 minutes with 85 µm Polyacrylate (PA) fiber at 500 rpm. Afterwards, the SPME fiber was desorbed at 300°C for 5 minutes. By adding 1% (w/v) potassium carbonate, 100 µL acetic anhydride (derivative agent), and 35% (w/v) sodium chloride, this method was sensitive enough to determine the target analytes in various consumer products. The linear range was 0.02-20 ng/mL for BMDM and OC, 0.1-10 ng/mL for OMC, 0.1-20 ng/mL for EHS, HMS, BP-3 as well as 4MBC, and 1-200 ng/mL for BP-1 and BP-8. The relative standard deviation was found to be below 20% for low and high concentrations. A total of 132 samples which were categorized into sixteen kinds of products were analyzed in this study. The recoveries for the analysis ranged from 70 to 148%. The results showed that HMS (14%), BP-3 (13%), and OMC (35%) had higher occurrences in the samples. High concentrations of UV filters were mainly found in sunscreen, liquid makeup foundation, perfume, and hair care products. All the products tested in this study were not above the maximum allowable concentrations. Nevertheless, the products without SPF, such as hair care products and perfume, were still found with similar levels of UV filters as the products with SPF. The results indicated that body lotion, face lotion, hair care products, liquid makeup foundation, perfume, and sunscreen were the major exposure sources of UV filters. In addition, only the concentration of BP-3, among all the UV filters, was regulated in personal care products, currently. Therefore, chances are people might be exposed to UV filters more than expected. The human exposures via dermal absorption to the UV filters from consumer products were estimated based on the findings in this study. The daily exposures were found to be 4×〖10〗^(-6) to 5.71 µg/kg-bw/day. The occurrences and concentrations of UV filters in cosmetics were higher than those in the leave-on products, while the levels for the leave-on products were higher than those for the rinse-off products. Among various categories of the products, body lotion, sunscreen, and hair care products were the major exposure sources of UV filters.