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研究生: 劉于瑄
Liu, Yu-Hsuan
論文名稱: 居家環境介質中有機磷耐燃劑成份特徵分析及孩童暴露評估研究
Characterization and children exposure assessment of organophosphate flame retardants in indoor environment
指導教授: 李俊璋
Lee, Ching-Chang
共同指導: 張偉翔
Chang, Wei-Hsiang
學位類別: 碩士
Master
系所名稱: 醫學院 - 環境醫學研究所
Department of Environmental and Occupational Health
論文出版年: 2020
畢業學年度: 108
語文別: 中文
論文頁數: 192
中文關鍵詞: 有機磷耐燃劑室內空氣室內灰塵濃度分布可能來源暴露評估
外文關鍵詞: organophosphate flame retardant, indoor air, house dust, possible sources, influence factors, exposure assessment
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  • 有機磷酸耐燃劑(Organophosphate flame retardant, OPFRs)為一群化合物,具穩定性、耐燃及增塑等功能,自2011年歐盟正式公告禁用溴化耐燃劑(RoHS 2.0)以來,開始被許多國家採用,作為溴化耐燃劑之主要替代品。OPFRs屬於添加型耐燃劑,具半揮發性,產品使用及廢棄過程中可能因磨損、逸散或揮發遷移至環境中。各國研究指出於室內/外環境介質(空氣、懸浮顆粒物和灰塵/水、雪、土壤、底泥及遠洋空氣等)中皆可檢出OPFRs,而其於大氣中具持久性及遠距離傳輸之特性;同時在生物群、人類母乳、人體胎盤和尿液中亦可檢出OPFRs或其代謝物,具生物可利用性。近年來,動物研究發現部分OPFRs具有潛在的神經、腎臟、肝臟、生殖毒性、可能引起哮喘、過敏性鼻炎和可能具致癌性等不良健康效應。由於OPFRs毒性及廣泛使用於日常生活用品中,且人們平均有80-90%的時間待在室內環境中,人體可藉由吸入、攝入或皮膚接觸暴露OPFRs。因此,迫切需要調查國內室內環境介質中OPFRs濃度分布、可能來源及環境中影響因子,並評估國內敏感性族群(孩童)於室內環境中是否會接觸OPFRs及其暴露程度。
    本研究於2018至2020年調查台南地區60間家戶及60位3-12歲孩童,簽署人體試驗同意書後,使用XAD-2空氣採樣管收集室內空氣樣本及專業吸塵器搭配特製金屬吸頭(內放置圓筒濾紙)收集家戶孩童主要活動空間及次要活動空間之灰塵樣本,以氣相層析質譜分析11種OPFRs。同時架設溫度、溼度監測儀及PM2.5採樣器,利用紅外線測距儀,量測空間、房門、窗戶、建材等尺寸。並以標準化問卷調查建築物特性、室內裝潢、生活習慣及孩童時間活動模式等,評估有機磷耐燃劑可能的來源、影響因子及孩童暴露情形。結果發現孩童主要及次要活動空間空氣中OPFRs皆以TCIPP(181.93±4.34 ng/m3 及 143.97±4.34 ng/m3)濃度最高,其次為TEP(26.30±4.17 ng/m3及19.46±3.42 ng/m3)、TiBP(22.81±3.71 ng/m3及19.50±2.90 ng/m3)及TBOEP (21.17±3.67 ng/m3及18.87 ± 3.71 ng/m3)。主要及次要活動空間灰塵中OPFRs皆以TBOEP (20.35±2.40 μg/g及20.82±2.32 μg/g)濃度最高、其次為TCIPP(1.16±3.36 μg/g及1.87±3.16 μg/g)、TDCIPP(1.00±3.62 μg/g及1.29±3.87 μg/g)及TPHP(0.90±3.54 μg/g及1.00±3.98 μg/g),主要及次要活動空間面積較大、有天花板破損或壁癌情形者、OPFRs應用之材質面積較大及電器數目較多之空間,室內空氣及灰塵中OPFRs濃度顯著較高(P<0.05)。主成分分析結果指出TCIPP於兩空間中為主要化合物,TDCIPP、TPHP及TBOEP化合物之間可能具有相似來源和/或物化特性。
    以多重線性回歸分析並校正影響因子(溫度及濕度)後顯示,孩童主要活動空間中傢俱裝潢之木質及泡棉材質表面積與空氣中TEP濃度呈顯著正相關 (β=0.278, P=0.030;β=0.356, P=0.030),傢俱裝潢之塑膠材質表面積與空氣中TBP濃度呈顯著正相關 (β=0.359, P=0.033);次要活動空間中傢俱裝潢之木質材質表面積與空氣中TCIPP、TBOEP及Σ11OPFRs濃度呈顯著正相關 (β=0.308, P=0.012、β=0.345, P=0.007及β=0.395, P=0.001),傢俱裝潢之塑膠材質表面積與灰塵中TBOEP濃度呈顯著正相關 (β=0.382, P=0.013)。孩童主要活動空間中地板打掃頻率與空氣中TBOEP及灰塵中TPHP呈顯著負相關 (β=-0.325, P=0.012及β=-0.345, P=0.012),傢俱打掃頻率與空氣中TBOEP呈顯著負相關(β=-0.376, P=0.016);次要活動空間中地板打掃頻率與空氣中TCIPP、TBOEP及Σ11OPFRs呈顯著負相關 (β=-0.325, P=0.012、β=-0.400, P=0.003及β=-0.315, P=0.025),與灰塵中TPHP呈顯著負相關 (β=-0.287, P=0.037)。孩童主要活動空間,室內溫度與空氣中TiBP、TCIPP及Σ11OPFRs呈顯著正相關(β=0.541, P<0.001、β=0.350, P=0.008及β=0.348, P=0.014);與灰塵中TCIPP呈顯著負相關(β=-0.229, P=0.033)。次要活動空間,室內濕度與空氣中TiBP呈顯著負相關(β=-0.281, P=0.037);與灰塵中TDCIPP、TPHP、TBOEP及Σ11OPFRs呈顯著正相關 (β=0.271, P=0.049、β=0.271, P=0.044、β=0.284, P=0.032及β=0.371, P=0.004)。
    進一步探討各項影響室內空氣及灰塵中OPFRs濃度之預測因子,孩童主要活動空間,室內溫度與空氣中TCIPP及TBOEP呈顯著正相關 (β=0.516, P<0.001及β=0.644, P<0.001)。木製材質表面積與灰塵中TEP及TDCIPP呈顯著正相關(β=1.083, P=0.001及β=0.772, P=0.009)。泡棉材質表面積與灰塵中TDCIPP濃度呈顯著正相關(β=0.489, P=0.026)。次要活動空間,僅塑膠表面積與灰塵中TBOEP呈顯著正相關 (β=0.821, P<0.008)。25間同時調查暖季及冷季之家戶中孩童主要活動空間,空氣中Σ11OPFRs濃度於暖季皆高於冷季,其中TCEP (P=0.032)及TBOEP (P=0.001)呈顯著差異,灰塵中Σ11OPFRs濃度於冷季高於暖季,其中TiBP (P=0.045)具顯著差異。次要活動空間,空氣中Σ11OPFRs濃度於暖季高於冷季,其中TCEP (P=0.006)、TBEOP (P<0.001)及Σ11OPFRs (P=0.016)呈顯著差異,灰塵中Σ11OPFRs濃度於冷季高於暖季,其中TCIPP呈顯著差異(P=0.004)。最後,分別以3-<6歲孩童、6-12歲男生及6-12歲女生三個族群進行估算Σ11OPFRs之平均暴露劑量,經吸入途徑之平均暴露劑量分別為136.85、124.73及128.41 ng/kg bw/day;經攝入灰塵途徑之平均暴露劑量分別為15.34、11.61及13.07 ng/kg bw/day。
    綜合上述結果,可知家戶中孩童主要及次要活動空間,空氣中OPFRs皆以TCIPP濃度最高,其次為TEP、TiBP及TBOEP;灰塵中OPFRs皆以TBOEP濃度最高,其次為TCIPP、TDCIPP及TPHP。孩童主要活動空間中,室內溫度為影響室內空氣中OPFRs濃度之重要因子,而木質及泡棉材質表面積為貢獻室內空氣及灰塵中OPFRs之重要來源;次要活動空間中,塑膠材質表面積為貢獻灰塵中OPFRs之重要來源。室內空氣及灰塵中OPFRs分布,可同時歸因於化合物之物化特性、室內環境特徵(溫度、濕度及PM2.5)及室內裝潢與家用消費性產品等多種可能的暴露來源及影響因子。3-12歲孩童OPFR暴露評估則發現吸入途徑為主要暴露途徑,但攝入灰塵之暴露途徑乃不可忽略,而其中以TBOEP、TPHP及TDCIPP為主要貢獻因子。

    The objectives of present study are to explore the profile and distribution, possible sources and influence factors of OPFRs in the indoor environment and to assess the OPFRs exposure doses via indoor air and house dust for children. 60 children’s households and their residents (one child matched their caregiver) were randomly recruited in South Taiwan. TCIPP (181.93±4.34 ng/m3 and 143.97±4.34 ng/m3) and TBOEP (20.35±2.40 μg/g and 20.82±2.32 μg/g) are the dominant compounds in indoor air and house dust in the primary and secondary activity spaces, respectively. Principle component analysis (PCA) of OPFRs concentrations revealed that TCIPP was the most dominant compound in the two spaces. TDCIPP, TPHP and TBOEP compounds may have similar sources and/or physicochemical properties. For larger spaces, broken ceilings or wall mold, OPFRs applications, and more electrical appliances had significantly higher concentrations of OPFRs in indoor air and house dust than those space without them (P<0.05). The surface area of wood and foam materials and indoor temperature are important factors which affecting the OPFRs concentration in indoor air and house dust. The seasonal variations of OPFR concentrations in indoor air whereby higher concentrations were observed in warm season especially for TCIPP, TCEP, TDCIPP and TBOEP. Inhalation is the main pathway of children exposure to OPFRs but OPFR exposure through house dust ingestion cannot be ignored.

    摘要 I Extended Abstract IV 致謝 IX 目錄 XI 表目錄 XV 圖目錄 XIX 第一章 前言 1 1-1. 研究緣起 1 1-2. 研究問題 3 1-3. 研究目的 3 1-4. 研究意義 3 第二章 文獻回顧 5 2-1. 有機磷耐燃劑物化特性 5 2-2. 有機磷耐燃劑於產品中應用 6 2-3. 有機磷耐燃劑毒性 8 2-3-1. 動物毒性 8 2-3-2. 人體健康影響 9 2-4. 有機磷耐燃劑環境流布及暴露源 10 2-4-1. 室外環境流布 10 2-4-2. 室內環境流布 11 2-4-3. 暴露來源 13 2-5. 影響有機磷耐燃劑濃度因子 15 2-5-1. 產品中有機磷耐燃劑遷移 15 2-5-2. 不同環境條件下有機磷耐燃劑濃度變化 15 2-5-3. 室內通風情形及居民生活習慣對機磷耐燃劑濃度之影響 16 2-6. 有機磷耐燃劑管制規範 17 2-7. 環境介質中有機磷耐燃劑分析方法回顧 18 2-8. 有機磷耐燃劑參考劑量 19 2-9. 有機磷耐燃劑暴露劑量及健康風險評估 20 第三章 材料與方法 22 3-1. 研究架構 22 3-2. 家戶及研究對象選取 22 3-3. 居家環境中有機磷耐燃劑可能來源及孩童暴露源調查 23 3-4. 室內環境介質採樣策略及分析方法 23 3-4-1. 標準品及溶劑 24 3-4-2. 室內空氣中有機磷耐燃劑採樣及分析方法 25 3-4-3. 室內灰塵中有機磷耐燃劑採樣及分析方法 27 3-4-4. 儀器分析及方法 28 3-5. 有機磷耐燃劑分析品保品管 29 3-6. 有機磷耐燃劑暴露評估 32 3-7. 非致癌風險特徵描述 34 3-8. 統計分析 35 第四章 結果與討論 36 4-1. 樣本分析之各項管制指標查核執行結果 36 4-2. 孩童居家室內環境中有機磷耐燃劑暴露來源調查之標準化問卷解析結果 39 4-2-1. 孩童住家環境特徵分布情形 39 4-2-2. 家戶孩童主要及次要活動空間特徵分布情形 39 4-3. 室內環境空氣及灰塵中有機磷耐燃劑濃度及分布 41 4-3-1. 室內空氣中有機磷耐燃劑濃度及分布情形 41 4-3-2. 室內灰塵中有機磷耐燃劑濃度及分布情形 42 4-3-3. 室內空氣及灰塵中有機磷耐燃劑組成分析 43 4-3-4. 室內空氣及灰塵中有機磷耐燃劑濃度之相關性 44 4-4. 室內環境空氣及灰塵中有機磷耐燃劑可能的來源 46 4-4-1. 有機磷耐燃劑濃主成分分析 46 4-4-2. 有機磷耐燃劑濃度與家用產品及裝潢材質分析結果 47 4-4-3. 有機磷耐燃劑濃與材質表面積差異性比較結果 49 4-4-4. 有機磷耐燃劑濃與材質表面積相關性分析 51 4-5. 影響室內環境空氣及灰塵中有機磷耐燃劑濃度之因子 53 4-5-1. 空間使用習慣對有機磷耐燃劑濃度之影響 53 4-5-2. 室內溫度、濕度及PM2.5濃度對有機磷耐燃劑濃度之影響 55 4-6. 探討影響室內環境空氣及灰塵中有機磷耐燃劑濃度之多重預測因子 57 4-7. 成對家戶室內空氣及灰塵中有機磷耐燃劑濃度之季節性差異 58 4-8. 孩童有機磷耐燃劑之日暴露劑量及風險評估 59 4-8-1. 孩童基本資料 59 4-8-2. 孩童暴露評估參數 59 4-8-3. 孩童經吸入及攝入途徑暴露有機磷耐燃劑之平均每日暴露劑量 60 4-8-4. 有機磷耐燃劑對平均每日暴露總風險之貢獻比率 61 4-8-5. 非致癌性風險評估 61 第五章 結論與建議 62 5-1. 結論 62 5-2. 建議 64 研究限制 65 參考文獻 66 附件一 同意人體研究證明書 153 附件二 說帖 156 附件三 人體試驗同意書 158 附件四 建築特性及室內環境中有機磷耐燃劑暴露調查及生活習慣調查問卷 163

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