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研究生: 劉香君
Liu, Hsiang-Chun
論文名稱: 印刷作業勞工鄰苯二甲酸酯類暴露評估研究
Exposure assessment of phthalate esters for workers in printing industry
指導教授: 李俊璋
Lee, Ching-Chang
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: 2011
畢業學年度: 99
語文別: 中文
論文頁數: 106
中文關鍵詞: 鄰苯二甲酸酯類職業暴露生物偵測印刷業荷爾蒙
外文關鍵詞: Phthalate esters, Occupational exposure, Biological monitoring, Printing industry, Hormone
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  • 鄰苯二甲酸酯類 (phthalate esters, PAEs)具有良好的油溶性,可添加於印刷油墨中做為分散劑,降低色料碳粒之聚集,達到印刷製品顏色分佈均勻之目的,印刷作業現場勞工可能經由呼吸吸入、皮膚吸收等途徑,暴露過量之PAEs粉塵與蒸氣,進而引起相關之健康危害。本研究目的為針對印刷業勞工進行PAEs暴露評估,並探討PAEs暴露對於生殖荷爾蒙、甲狀腺荷爾蒙之影響。研究對象選自兩間中型印刷廠,女性及男性人數分別為20與31人,每位勞工均進行個人呼吸區空氣濃度採樣與分析、個人血液生殖及甲狀腺荷爾蒙分析、上下班前尿液PAEs代謝物分析、個人生活與職場時間活動模式問卷調查。以職稱與可能暴露濃度劃分組別,高暴露組(現場作業、包裝人員)共34人,低暴露組(辦公行政、美工人員)共17人。研究結果顯示,在男性勞工中,高暴露組(現場作業、包裝人員)與低暴露組(辦公室行政、巡廠人員)之空氣中DEHP濃度(0.5 μg/m3 vs 0.3 μg/m3, p<0.05),以及下班前尿中MBP濃度(94.8 μg/g-Cre vs. 67.6 μg/g-Cre, p<0.05)皆達顯著差異。此外,再比較下班前與上班前之尿中PAEs代謝物濃度,於高暴露組男性勞工中,亦觀察到顯著之差異情形:MBP (94.8 μg/g-Cre vs. 66.6 μg/g-Cre, p<0.05)、MEHP (14.0 μg/g-Cre vs. 5.9 μg/g-Cre, p<0.05)、 MEOHP (39.0 μg/g-Cre vs. 15.9 μg/g-Cre, p<0.05)、MEHHP (85.4 μg/g-Cre vs. 32.7 μg/g-Cre, p<0.05)、MECPP (69.7 μg/g-Cre vs. 27.9 μg/g-Cre, p<0.05),表示現場作業勞工確實有較明顯之職業暴露。進一步以用空氣PAEs之濃度(Daily Intake, DI Air)及尿液中PAEs代謝物濃度推估PAEs日攝取劑量 (Daily Intake, DI Urine),結果顯示,高暴露組勞工之DEHP DI Air(0.03 μg/kg/day vs. 0.02μg/kg/day, p<0.05)及DBP DI Urine(4.3μg/kg/day vs. 3.0μg/kg/day, p<0.05)顯著高於低暴露組。空氣濃度與尿液中代謝物濃度之相關性,高暴露組男性勞工空氣中DEHP濃度與尿液中MEOHP、MECPP濃度皆達統計上顯著相關 (p<0.05),相關係數為分別為0.4930及0.5696,可知印刷作業場所中空氣暴露係為勞工PAEs之暴露途徑之一。以尿液中PAEs代謝物中位數濃度分組時,高濃度組平均DBP及DEHP DISkin佔總攝取量之66.2 %及63.7 %,顯示皮膚吸收對於印刷業勞工而言,其重要性遠較呼吸吸入途徑為高。計算其勞工經由空氣之暴露危害指標,計算高、低濃度組經由空氣中DBP及DEHP之危害指標,以U.S. EPA和EFSA為參考劑量標準時,全體勞工經由空氣中PAEs濃度所計算而得HI值皆遠小於1,則可得知印刷作業場所中,其經由空氣PAEs暴露所致的危害風險甚低。並由尿液中DBP及DEHP之濃度計算其危害指標,高、低濃度組其HI中位數值皆小於1,以U.S. EPA為參考劑量標準時,尿液中DEHP代謝物總和計算之HI有4位勞工大於1,另外若以EFSA為參考劑量標準時,尿液中DBP代謝物計算之HI有5位勞工大於1,尿液中DEHP代謝物計算則僅有一名勞工其HI值大於1,進一步比較高、低濃度組勞工暴露PAEs之危害指標,則有統計上顯著差異(p<0.0001),顯示高濃度組有較高之PAEs暴露對於勞工所產生的危害風險明顯高於低濃度組。檢測生殖及甲狀腺荷爾蒙濃度之結果,高濃度組男性勞工以尿液中MEOHP及MEHHP中位數濃度分組時,血液中抑制素(Inhinbin B)的濃度皆顯著高於低濃度組(71.3 pg/mL vs. 46.7 pg/mL, p=0.0361 (MEOHP); 70.2 pg/ mL vs. 46.7 pg/mL, p=0.0452 (MEHHP)),其inhibin B濃度過高可能影響體內生殖荷爾蒙平衡,亦以sum of DEHP、MEHP及MEHHP中位數濃度分組時,血液中四碘甲狀腺素(T4)濃度皆顯著低於低濃度組(7.8 μg/dL vs. 9.1 μg/dL, p=0.0459 (sum of DEHP); 7.7 μg/dL vs, 9.1 μg/dL, p=0.0249 (MEHP); 7.8 μg/dL vs. 9.1 μg/dL, p=0.0237 (MEHHP)),以MEHP分組時血液中三碘甲狀腺素(T3)濃度顯著高於低濃度組(116.6 ng/dL vs. 138.4 ng/dL, p=0.0117 (MEHHP)),顯示PAEs之暴露可能會誘導體內荷爾蒙分泌異常。研究發現空氣中PAEs暴露濃度遠低於法定的容許暴露值 (5 mg/m3),亦指出皮膚吸收PAEs可能為印刷作業勞工重要暴露來源,且發現PAEs之暴露可能會影響血液中生殖及甲狀腺荷爾蒙,因此建議勞工PAEs暴露容許值應以生物暴露指標訂定較具代表性。

    Phthalate esters (PAEs) were widely added in printing ink as dispersing agent to increase quality of printing products. The aim of this study is to assess the occupational PAEs exposure for workers in printing industry. 20 female and 31 male workers in two printing plants were recruited as subjects. The personal airborne PAEs and urinary PAEs metabolites measurement, blood hormone examination, investigation of personal, occupational exposure data and time activity pattern for all selected workers has been completed. For male workers, the airborne DEHP concentration (0.5 μg/m3 vs 0.3 μg/m3, p<0.05) and urinary MBP level (94.8 μg/g-Cre vs. 67.6 μg/g-Cre, p<0.05) of high-exposure workers (operator, paking) were significantly higher than those of low-exposure workers (officer, patrolling workers). The post- and pre-shift urinary levels of PAEs metabolites of high-exposure male workers shows significant difference: MBP( 94.8μg/g-Cre vs. 66.6μg/g-Cre, p<0.05), MEHP (14.0 μg/g-Cre vs. 5.9 μg/g-Cre, p<0.05), MEOHP (39.0 μg/g-Cre vs. 15.9 μg/g-Cre, p<0.05), MEHHP (85.4 μg/g-Cre vs. 32.7 μg/g-Cre, p<0.05), MECPP (69.7 μg/g-Cre vs. 27.9 μg/g-Cre, p<0.05). The daily intake (DIAir and DIUrine) of PAEs for each worker was calculated with airborne PAEs concentrations and urinary PAEs metabolites levels respectively. The DEHP DIAir (0.03 μg/kg/day vs, 0.02 μg/kg/day, p <0.05) and DBP DIUrine (4.3 μg/kg/day vs 3.0 μg/kg/day, p<0.05) for high-exposure group were significantly higher than low-exposure group. Significant correlation between airborne DEHP concentration and urinary MEOHP (r=0.4930, p<0.05), MECPP (r=0. 5696, p<0.05) were found. Furthermore, the skin absorption of PAEs for workers was estimated. According to the median concentration of PAEs metabolites were classifided to high concentration group and low concentration group. The estimated skin absorption percentiles of DBP and DEHP (DIskin) in high-concentration group were 66.2 % and 63.7 % of DIUrine, respectively. It means the dermal absorption may still as an important potential exposure route for printing workers. Each worker’s Hazard index (HI) which was calculated with airborne PAEs concentrations were all less than 1. The hazard index (HI) of PAEs for each worker was calculated with urinary PAEs metabolites levels. When RfD conducted by USEPA was regarded as reference dose, the calculated hazard index of DEHP for four workers were higher than one. The HI of DBP and DEHP for five and one workers was higher than the TDI set EFSA. For hormone disruption, we found that the Inhinbin B of high-concentration group of male workers were higher than those of low concentration group (71.3 pg/mL vs. 46.7 pg/mL, p=0.0361 (MEOHP); 70.2 pg/ mL vs. 46.7 pg/mL, p=0.0452 (MEHHP)). The T4 of high concentration group of male workers (7.8 μg/dL vs. 9.1 μg/dL, p=0.0459 (sum of DEHP); 7.7 μg/dL vs, 9.1 μg/dL, p=0.0249 (MEHP); 7.8 μg/dL vs. 9.1 μg/dL, p=0.0237 (MEHHP)) and T3 (116.6 ng/dL vs. 138.4 ng/dL, p=0.0117 (MEHHP) were lower than those of low concentration group. We concluded the airborne PAEs concentrations were lower than PEL-TWA (OSHA: 5 mg/m3), although skin absorption of PAEs is important route for printing. The reproductive hormone and thyroid hormone of workers may be disrupted by the PAEs exposure. Therefore, we suggest that the biological exposure index (urinary PAEs metabolites) is more represented the PAEs exposure profile for workers.

    摘要 I ABSTRACT III 誌謝 V 目錄 VII 表目錄 X 圖目錄 XII 第一章 序論 1 1.1研究緣起 1 1.2 DBP之職業暴露重要性 2 1.3 研究目的 3 1.4 研究意義 3 第二章 文獻回顧 4 2.1 PAES之物化特性及使用 4 2.2 PAES之暴露途徑 5 2.3 PAES之代謝作用 6 2.4.PAES之毒性效應 7 2.4.1動物相關研究 7 2.4.2人類流行病學研究 7 2.5職業族群暴露 9 2.6 PAES及其代謝物採樣及分析方法 12 2.6.1空氣中PAES採樣及分析方法 12 2.6.2 尿液中PAES代謝物採樣及分析方法 13 2.7 PAES日暴露劑量建議值 14 2.8 各國 PAES職業暴露管制規範 15 第三章 研究材料與方法 17 3.1研究架構 17 3.2研究對象選取 17 3.2.1印刷流程說明 17 3.2.2研究對象篩選 18 3.3採樣策略 18 3.3.1個人空氣樣本採集 18 3.3.2尿液採樣 19 3.3.3血液樣本及甲狀腺、生殖荷爾蒙檢查 19 3.3.4問卷調查 20 3.4樣本分析流程 20 3.4.1空氣中PAES分析 20 3.4.1.1空氣樣本前處理 20 3.4.1.2空氣樣本分析儀器 21 3.4.2 尿液中PAES代謝物之分析 22 3.4.2.1尿液樣本前處理 22 3.4.2.2尿液樣本分析儀器 23 3.5實驗室數據品保與品管規範 24 3.5.1GC/MS品保與品管規範 24 3.5.2 LC/MS/MS品保與品管規範 27 3.6 PAES日攝取劑量之推估 30 3.6.1以空氣中PAES濃度推估PAES日攝取劑量 30 3.6.2尿液中PAES代謝物濃度推估PAES日攝取劑量 31 3.6.3推估皮膚吸收之日攝取劑量 31 3.7健康風險評估 32 3.8統計分析方法 32 第四章 結果與討論 34 4.1品保品管執行結果 34 4.1.1空氣樣品分析之品保品管結果 34 4.1.2尿液樣品品保品管結果 35 4.2研究對象問卷調查及基本統計結果 36 4.2.1基本資料、職業史、生活習慣、健康史之基本統計資料 36 4.2.2衛生用品使用及飲食情形資料分布 37 4.3研究對像個人空氣中PAES濃度分析結果 38 4.4研究對象尿液中PAES代謝物濃度分析結果 39 4.5研究對象個人空氣中PAES濃度與尿液中PAES代謝物濃度相關性 40 4.6PAES日攝取劑量推估結果 41 4.6.1以個人空氣中PAES暴露濃度推估勞工經由吸入PAES日攝取劑量 41 4.6.2以個人尿液中PAES代謝物濃度推估勞工PAES日攝取劑量 41 4.6.3推估勞工皮膚吸收之日攝取劑量 41 4.7勞工PAES暴露健康風險評估 43 4.7.1 高、低濃度組勞工直接暴露空氣中PAES濃度之危害指標 (HI) 43 4.7.2以下班前尿液中PAES代謝物計算高、低濃度組勞工暴露PAES之危害指標(HI) 43 4.8研究對象個人生殖及甲狀腺荷爾蒙檢查結果 43 第五章結論與建議 45 5.1結論 45 5.2建議 46 參考文獻 48 附件一 人體試驗委員會同意臨床試驗證明書 97 附件二 臨床試驗同意書 98 附件三 印刷製程作業勞工健康調查問卷 100

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    行政院勞工委員會勞工安全衛生研究所,網版印刷勞工乙二醇乙醚醋酸酯暴露調查,IOSH94-A313,中華民國九十四年。
    行政院勞工委員會勞工安全衛生研究所,網版及塑膠印刷業職業衛生輔導技術建立(二) ,IOSH96-A303,中華民國九十六年。
    行政院勞工委員會勞工安全衛生研究所,美容業人員鄰苯二甲酸酯類暴露評估研究, IOSH97-A311,中華民國九十七年。
    許昺奇、李諭昇,PVC塑膠粒製造業男性勞工生殖危害評估,IOSH98-M306,中華民國九十八年。
    李芳錦,PVC塑膠皮布製造及加工作業勞工DEHP之暴露評估研究,成功大學工業衛生暨環境醫學研究所/碩士論文,民國九十九年。
    呂怡萱, PVC塑膠粒製造勞工之鄰苯二甲酸酯類暴露評估研究,成功大學工業衛生暨環境醫學研究所/碩士論文,民國九十九年。
    吳婉玲,淋浴期間飲水中揮發性致癌物質吸收性健康風險評估,中國醫藥學院 / 環境醫學研究所 / 碩士論文,中華民國九十一年七月。
    陳佳飛,食品容器及包裝用塑膠材質之塑化劑溶出研究,國立陽明大學公共衛生系/碩士論文,民國九十一年。
    詹秀慧,化妝品銷售鄰苯二甲酸酯類暴露評估研究,國立成功大學/環境醫學研究所 / 碩士論文,中華民國九十四年七月。
    謝俊明、林維炤,美容業人員鄰苯二甲酸酯類暴露評估研究,IOSH97-A311,民國九十七年。

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