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系統識別號 U0026-2107201515004700
論文名稱(中文) 醛、酮類化合物作業勞工共暴露評估及尿液生物指標建置研究
論文名稱(英文) The concurrent exposure assessment of aldehydes and ketone in manufacturing and operating workers and establishment of urinary biological markers
校院名稱 成功大學
系所名稱(中) 環境醫學研究所
系所名稱(英) Institute of Environmental and Occupational Health
學年度 103
學期 2
出版年 104
研究生(中文) 李文汝
研究生(英文) Wen-Ju Lee
學號 S76024010
學位類別 碩士
語文別 中文
論文頁數 162頁
口試委員 指導教授-李俊璋
口試委員-石東生
口試委員-汪禧年
口試委員-陳秀玲
中文關鍵字 醛類  酮類  共同暴露  暴露風險評估  生物偵測 
英文關鍵字 Aldehyde  Ketone  Concurrent exposure  Exposure risk assessment  Biological monitoring 
學科別分類
中文摘要 化學工業主要使用之醛類及酮類包含甲醛、乙醛、丙酮與甲基異丁酮等。依據環保署毒性化學物質申報資料庫統計,2014年甲醛的製造量和使用量分別為432,980.38和425,815.14公噸;乙醛為20,737.65和19,198.37公噸;甲基異丁酮的製造量和使用量分別為6,678.64公噸與4,348.42公噸,而勞動部勞工作業場所容許暴露標準甲醛、乙醛、丙酮與甲基異丁酮制定濃度有高於其他各國情形,顯示勞工可能暴露較高甲醛、乙醛、丙酮與甲基異丁酮濃度。職業流行病學研究指出暴露甲醛可導致白血病、鼻咽癌與慢性咽喉炎等發生率提高;乙醛暴露與皮膚黏膜刺激、肺水腫有關;暴露於甲基異丁酮及丙酮則與肝腎毒性、感知神經損傷與皮膚刺激有關。回顧過去醛酮暴露之生物偵測文獻,研究指出脂肪代謝異常者經體內內源性乙醛與酮體共同暴露下,於尿中產生良好生物指標物,本研究綜合上述研究背景,亦想探討經外源性醛酮共暴露下,勞工體內是否也能產生一良好生物指標物,而醛酮共同暴露是否會對健康效應產生協同作用。
本研究共完成四家醛酮作業工廠現勘訪視及兩家醛酮作業工廠採樣,有效樣本共68名作業勞工。研究項目包括:(1)勞工個人空氣樣本中甲醛、乙醛、丙酮與甲基異丁酮濃度;(2)個人血液樣本中肝功能指標、腎功能指標、血液常規檢查與脂肪代謝指標;(3)個人周邊神經表現測試;(4)建置個人尿液中醛酮代謝物分析方法,包含3-penten-2-one、4-methyl-2-pentanol與3-methyl-3-penten-2-one。研究結果顯示,個人空氣中甲醛、乙醛、丙酮與甲基異丁酮濃度均符合勞動部勞工作業場所容許暴露標準,其值均低於四分之一勞工作業場所容許暴露標準。為標準化四者暴露濃度健康指標間關係,本研究將勞工甲醛、乙醛、丙酮與甲基異丁酮暴露濃度除以各自之PEL-TWA後相加,作為共同暴露指標(Concurrent exposure index, CEI),以台灣勞動部之PEL-TWA為計算基準之指標為CEI 1;以相較於台灣規範嚴格之日本職業安全衛生(Japan Occupational Safety and Health Resource Cente, JOSH)基準者則為CEI 2;以介於台灣與日本規範之美國工業衛生師協會(American Conference of Governmental Industrial Hygienists, ACGIH)之基準者為CEI 3,並以中位數區分為高、低兩組進行分析。結果發現高共酮暴露組之血液中尿素氮濃度均顯著低於低共同暴露組(p=0.009, 0.033, 0.041),表示高共同暴露可能存在腎功能損傷;CEI 2與CEI 3之球蛋白於兩組間達顯著差異(p=0.034, 0.033),顯示低共同暴露組可能存在肝功能損傷情形。在周邊神經行為影響則發現,高CEI 2組,其慣用手手指靈活度顯著低於低CEI 2組( p=0.041),表示醛、酮類物質的共同暴露可能影響神經行為能力表現。在本研究調查之共暴露指標結果中,發現以暴露標準較為嚴格之日本職業安全衛生(JOSH)規範為基準計算共同暴露指標時,可發現共同暴露不僅會產生腎功能損傷、慣用手之手指靈活度亦受影響。不過,由於本研究為單一時間點採樣,且醛酮物質共同暴露對於人體健康影響機制尚不明確,因此,尚須進行更多相關研究加以證實。
尿中代謝物分析方法建置,本研究參考過去文獻,以氣相層析儀/低解析質譜儀為分析儀器,層析管柱選用DB-WAX (30 × 2.5 mm, 0.25 μm),尿液樣本前處理以二氯甲烷作為液相液相萃取溶劑,萃取次數為兩次,基質添加樣本回收率為70 %-130 %。以Wilcoxon rank sum test比較上、下班前尿中代謝物濃度後發現,下班前代謝物濃度皆顯著高於上班前代謝物濃度 (3-penten-2-one: p = 0.037 ; 4-methyl-2-pentanol: p = 0.002 ; 3-methyl-3-penten-2-one: p=0.044),顯示尿中代謝物在下班時均有顯著增加的情形,表示工作期間暴露醛酮類物質可能會於下班前經由尿液排出。經校正年齡、體脂與胰島素阻抗指標後,結果顯示甲基異丁酮暴露濃度與上班前及下班前尿中3-methyl-3-penten-2-one均達統計上顯著相關(上班前:β=21.426, p=0.003; 下班前:β=25.117, p=0.024),顯示3-methyl-3-penten-2-one具甲基異丁酮暴露之生物指標潛力。有鑒於尿中3種代謝物之半衰期未知,上下班前尿液之統計結果差異,是否與尿中代謝物之半衰期有關,間接影響代謝物的生成時程仍需進一步研究。
以勞工個人空氣中甲醛、乙醛、丙酮與甲基異丁酮濃度計算勞工健康風險,個人的非致癌風險以Hazard Index (HI)表示,結果顯示所有工人之醛酮類非致癌風險均小於1,均屬可接受之風險。而在甲醛及乙醛之總致癌風險部分,結果顯示各廠勞工之致癌風險結果均小於10^-3,亦屬可接受之風險。
英文摘要 The objectives of present study are to set up the pretreatment and analytical technique to analyse urinary biomarkers and then to assess the relationship between exposure profile and health effects for aldehydes and ketone concurrent exposure workers by biological monitoring and environmental monitoring. The personal exposure levels of formaldehyde, acetaldehyde, and acetone and methyl isobutyl ketone were analyses by high-performance liquid chromatography UV/Visible detectors (HPLC-UV). In present study, the concurrent exposure index (CEI) was used to evaluate the relationship between health outcome and airborne exposure levels for workers. The concurrent exposure index was calculated by sum of each chemical exposure concentration divided by the permissible exposure level respectively. The results shows that the blood urea nitrogen concentrations in high CEI 2 exposure group were lower than low CEI 2 exposure group (p=0.033), it means concurrent exposure to aldehyde and ketone may cause kidney damage. Finally, we found that preferred hand finger flexibility in high CEI 2 exposure group was significantly lower than the low CEI 2 exposure group (p=0.041). It means that concurrent exposure of aldehyde and ketone may damage the neurobehavioral performance. In present study, we analyzed urinary biomarkers for aldehydes and ketones exposure by GC-MS with DB-WAX (30 x 2.5 mm, 0.25 μm). The levels of three urinary metabolites in post-shift were all significantly higher than those in pre-shift (3-penten-2-one: p = 0.037 ; 4-methyl-2-pentanol: p = 0.002 ; 3-methyl-3-penten-2-one: p=0.044). After adjusting age, body fat and insulin resistance (HOMA-IR), the significant correlation between 3-methyl-3-penten-2-one and airborne methyl isobutyl ketone was found, it means that 3-methyl-3-penten-2-one may be a good biomarker to represent the exposure to methyl isobutyl ketone. The non-carcinogenic risk, expressed as hazard index (HI), were lower than 1; and the carcinogenic risk were all lower than the acceptable risk (10^-3) for all aldehydes and ketones exposure workers.
論文目次 摘要 I
Extended abstract IV
目錄 XI
圖目錄 XVII
表目錄 XIV
第一章 緒論 1
1.1 研究源起 1
1.2 研究目的 3
第二章 文獻回顧 4
2.1 甲醛、乙醛、丙酮與甲基異丁酮之物化特性 4
2.2 甲醛、乙醛、丙酮與甲基異丁酮之使用與製造 4
2.3甲醛、乙醛、丙酮與甲基異丁酮之代謝路徑與基因毒性 7
2.4 動物實驗研究 8
2.5人類流行病學資料 12
2-5-1 甲醛 12
2-5-2 乙醛 14
2-5-3 丙酮 14
2-5-4 甲基異丁酮 15
2.6 甲醛、乙醛、丙酮與甲基異丁酮的致癌性分類與管制 16
2.7 職業暴露調查 17
2.8 生物指標研究 20
第三章 材料與方法 23
3.1 研究架構 23
3.2 研究對象選取 23
3.3健康、飲食問卷及時間活動模式調查 24
3.4勞工個人空氣採樣及分析 24
3-4-1現場空氣採樣 24
3-4-2標準品與檢量線配製 26
3-4-3空氣樣本前處理 26
3-4-4空氣樣本分析 27
3.5 血液樣本收集與分析 27
3.6 尿中代謝物分析方法開發 28
3-6-1 儀器條件 28
3-6-2 尿液樣本前處理條件 29
3-6-3 分析管柱與萃取溶液選取 29
3.7品保/品管規範 30
3-7-1 空氣樣本品保/品管規範 30
3-7-2 尿液樣本品保/品管規範 32
3.8 神經行為能力測試 34
3-8-1 手指靈活度測試 34
3-8-2 握力 35
3.9 健康風險評估 35
3.10 統計分析 38
第四章 結果與討論 39
4.1勞工採樣與人口學資料分布與分析 39
4.2 個人空氣樣本分析 41
4-2-1 個人空氣樣本品保/品管成果 41
4-2-2個人空氣甲醛、乙醛、丙酮及甲基異丁酮濃度分布 41
4.3血液常規、肝腎功能指標及脂肪代謝異常檢測 44
4.4 共同暴露與健康指標之影響 46
4-4-1甲醛、乙醛、丙酮及甲基異丁酮共暴露對血液常規指標之影響 46
4-4-2甲醛、乙醛、丙酮及甲基異丁酮共暴露對周邊神經表現之影響 48
4.5 尿中代謝物方法開發 48
4-5-1 質譜儀條件設定 48
4-5-2 氣相層析分析條件 49
4-5-3 基質添加樣本測試 50
4-5-4 檢量線建置及品保/品管規範 51
4.6 勞工尿中代謝物濃度分布 52
4.7 勞工個人健康風險評估 54
4-7-1 勞工非致癌風險評估 54
4-7-2 致癌性風險評估 54
第五章 結論與建議 56
5.1 結論 56
5.2 建議 59
第六章 參考文獻 61
第七章 附錄 153
附件一、勞工個人問卷 153
附件二、受試者同意書 159
附件三、同意臨床試驗證明書 162
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