市售酒精乾洗手液成分調查與不純物分析

Abstract

乾洗手液在COVID-19疫情期間一直被提倡做為消毒的工具之一，而乾洗手液可能以水或酒精為基底，同時以不同形態呈現，包括：膠狀、泡沫、液態或擦手巾等樣貌。事實上，在疫情之前，國際間即有許多單位及組織，例如：世界衛生組織、美國食藥署、美國藥典委員會等，曾提供如何製備酒精乾洗手液的相關指南，以確保乾洗手液成分當中，酒精至少含60-90%；然而，美國食藥署2020年6月公布的一份報告指出，許多市售酒精乾洗手液可能內含不純物質，長期使用可能會導致包括：皮膚紅腫、刺激、過敏或接觸性皮膚炎等症狀。 在後疫情時代，許多民眾依舊保有使用酒精乾洗手液的習慣。因此，為了保障民眾的健康，本研究收集了市面上85項不同酒精乾洗手液產品，除了辨識當中的不純物質之外(包含：甲醇、乙醛、丙酮、乙酸乙酯、異丁醇、苯、乙縮醛、1-丙醇、2-丁醇、1-丁醇、3-甲基-1-丁醇和戊醇)，同時監測其乙醇或異丙醇濃度，並進行相關之健康風險評估。 本研究使用氣相層析質譜(gas chromatography-mass spectrometry, GC-MS)進行樣本分析。以氦氣作為載流氣體(流速：1ml/min)，主要的升溫條件如下：初始溫度為80℃ (2分鐘)，以每分鐘8℃升溫至120℃，再以每分鐘15℃升溫至240℃；進樣口溫度為235℃且分流比為20:1。分析物的方法偵測極限介於0.0017~3.74 (μg/mL)。高濃度與低濃度的相對標準差皆小於20%且回收率介於80-120%之間。結果顯示，在85個樣本當中有12個樣本的酒精濃度未達60%(v/v)、2個樣本的異丙醇濃度分別為42%與58%。不純物分析部分，苯的平均濃度為0.84 μg/g (範圍: 1.57-33.99)、乙醛的平均濃度為22.39 μg/g (範圍: 30.09-429.03)皆超過美國食藥署的規定。風險評估部分，本研究選擇皮膚接觸作為主要的暴露途徑：不純物的平均皮膚暴露劑量(dermal exposure dose, DED)範圍為3.17×10-2～15.5 μg/kg-bw/day；幾何平均的範圍為2.88×10-4～2.15 μg/kg-bw/day。此外，由於苯被國際癌症研究機構(International Agency for Research on Cancer, IARC)列為對人體有致癌性，因此本研究亦進行非致癌性與致癌性的風險評估；在非致癌性風險評估中，特別是針對孩童的部分，風險值皆大於1(範圍: 1.04-4.66)。一般民眾在高頻率(13.5g/day)的使用酒精乾洗手液的情況下，其風險值也會大於1 (範圍: 1.43-4.66)。在致癌性風險評估中，苯的致癌性風險評估值範圍為1.44×10-8～2.11×10-7(以幾何平均濃度來計算)。 由本研究的結果得知，85種市售商品中存在著酒精含量未達標準的乾洗手液，且可檢出許多不純物質。因此，建議政府機關宜適時進行檢測同時制定相關標準，以確保一般民眾的健康。另外，民眾在選擇產品與使用乾洗手液時也須格外小心，並儘可能以洗手來減少乾洗手液的使用。

During the COVID-19 pandemic, hand sanitizers are promoted to interrupt the transmission of viruses since appropriate hand hygiene is another crucial measure for personal protection following wearing face masks. Hand sanitizers can be of various types, such as anti-microbial-based, alcohol-free, or alcohol-based hand sanitizers (ABHS), in the form of gel, foams, cream spray, or wipes. Some organizations, such as the United States Food and Drug Administration (US FDA) and the United States Pharmacopeia (USP), have also provided the guideline that effective hand sanitizer products should contain 60%–95% of alcohol. However, in 2020, the USFDA warned that some hand sanitizers might have the ingredient leading to specific health effects. Previous studies detected some impurities in the products, including methanol, benzene, and acetaldehyde. In addition, some products contained less than 60% alcohol, which meant they were ineffective at killing viruses. Amidst the COVID-19 pandemic, people must continually use hand sanitizers for an extended period. Therefore, the objectives of this study include: identifying impurities present in commercially available hand sanitizers, monitoring ethanol and isopropanol levels in ABHS, and assessing the associated health risk from exposure to the chemicals detected in the samples. This study focused on two main ingredients, i.e., ethanol and isopropanol, with twelve impurities, including methanol, acetaldehyde, acetone, ethyl acetate, isobutanol, benzene, acetal, 1- propanol, 2-butanol, 1-butanol, 3-methyl-1-butanol, and amyl alcohol. Besides, this study collected 85 commercially available samples, while gas chromatography-mass spectrometry (GC-MS) was used for sample analysis. The MS source and quadrupole temperatures were set at 230°C and 150°C, respectively. The carrier gas was Helium at a flow of 1mL/min. The major GC-MS parameters were set as follows: GC oven temperature program of 80°C for 2 min, then 8°C/min to 120°C and a ramp rate of 15°C/min to 240°C. The injection port temperature was 235°C and a split liner was used with a split ratio 20:1. The findings from 85 various alcohol-based hand sanitizers (ABHS) showed that 12 samples had alcohol concentrations below 60% (v/v), and 2 samples had isopropanol concentrations of 42% and 58%, respectively. In the analysis of impurities, certain impurities were detected in the samples, notably benzene and acetaldehyde. The average concentration of benzene was 0.84 μg/g (range: 1.57-33.99 μg/g), and the average concentration of acetaldehyde was 22.39 μg/g (range: 30.09-429.03 μg/g), both of which exceeded the regulations of the US Food and Drug Administration. Hence, a health risk assessment was conducted to evaluate the risk from the exposure to the chemicals detected in the samples. This study used the formula from the US FDA to calculate the dermal exposure dose (DED) for the exposed impurities. The average dermal exposure doses of impurities ranged from 3.17×10-2 to 15.5 μg/kg-bw/day. Since the International Agency for Research on Cancer (IARC) listed benzene as carcinogenic tohumans, this study also carried out its non-carcinogenic and carcinogenic risk assessments. For the non-carcinogenic risk assessment, especially for children (age: 2-11 years old), the non-carcinogenic risk was greater than 1 (range: 1.04-4.66). For the carcinogenic risk assessment, the cancer risk values of benzene in all groups ranged from 1.44×10-8 to 2.11×10-7 (calculated by the geometric mean concentrations). This study performed qualitative and quantitative analysis of the impurities and alcohol levels in the ABHS. Overall, some samples had alcohol levels lower than requirements, while impurities also occurred, which might contribute to potential health risks. Therefore, the authorities should ensure that the commercially available ABHS meets specific standards or regulations. The general population should be more careful when using ABHS. Besides, regarding personal hygiene, washing hands with soap instead of using ABHS should be promoted.