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標題: | 銻物種分析方法建立與三氧化二銻職業暴露評估 Method Development for Antimony Speciation Analysis and Assessment of Occupational Exposure to Antimony Trioxide |
作者: | Ying-Der Hsiao 蕭英德 |
指導教授: | 林嘉明 |
關鍵字: | 三氧化二銻,暴露評估,物種分析,生物偵測,半衰期,高效率液相層析感應偶合電漿質譜儀, antimony trioxide,exposure assessment,species analysis,biological monitoring,half-life,HPLC-ICP/MS, |
出版年 : | 2011 |
學位: | 博士 |
摘要: | 三氧化二銻化合物是一種防火添加劑,廣泛應用於工業。動物研究顯示三氧化二銻(Sb2O3)可使老鼠生成肺癌與心肺疾病,高濃度之氫化銻化合物會具有中樞神經毒害作用與溶血性作用。美國工業衛生師協會(ACGIH)、國際癌症研究機構(IARC)、歐盟將三氧化二銻分別列為A2級、2B級及第三級致癌物。本研究認為有必要開發方便可靠的方法,以便同步分析銻的化學物種,並且應用於冶煉和使用銻的工廠之暴露評估。暴露評估於一家銻冶煉工廠(A)和兩家工程塑膠工廠(B、C)進行空氣採樣分析及生物偵測。
研究首先發展無機三價銻(Sb(Ⅲ))、五價銻(Sb(Ⅴ))與有機三甲機銻(TMSb)物種同步分析方法,以HPLC-ICP-MS建立銻物種分析方法,沖提液使用20 mM EDTA、10%甲醇與去離子水,採取階梯沖提。結果顯示Sb(Ⅲ)、Sb(Ⅴ)、TMSb可以本法獲得良好分離,滯留時間分別為9.86、6.20、2.40分鐘,偵測極限分別為0.79、0.22與1.23 μg/L。應用於尿中銻物種分析可獲得到良好層析圖譜,但尿中出現的代謝除了Sb(Ⅲ)、Sb(Ⅴ)與TMSb外,尚有二種未知銻物種有待鑑定。 進而以A廠進行一週五天的採樣分析,將全廠員工分為包裝組、氧化爐組、管理組、分析組和會計組,各組五天的平均空氣暴露濃度(標準差)分別為3.36(2.35)、1.86(1.69)、0.12(0.14)、0.03(0.03)和0.03(0.02) mg/m3,尿液平均濃度(標準差)分別為266.2(88.4)、178.1(72.1)、51.4(40.5)、42.4(33.2)和28.8(22.6) μg Sb/g cre.,頭髮濃度(標準差)分別為12.52(1.85)、1.44(0.83)、0.41(0.47)、0.07(0.08)、0.03(0.005) mg Sb/g hair。將各組暴露結果進行Kruskal-Wallis One Way Analysis of Variance on Ranks,具有統計明顯差異(p <0.001),尿液濃度或頭髮濃度(Y) 與暴露濃度(X)之相關線性分別為Y=42.76X + 67.31,r=0.6377及Y=2.011X - 0.0611,r=0.6926,達統計顯著相關。 其後,又於三氧化二銻製造廠(A)、工程塑膠製造廠(B)和工程塑膠製造廠(C)進行一天的採樣,比較直接接觸三氧化二銻的勞工暴露程度,平均濃度(標準差)分別為,5.31(5.88)、0.50(0.31)和0.45(0.79) mg/m3。當天尿液計算平均值(標準差)分別為313.7(437.4)、40.1(32.8)、14.7(7.3) μg Sb/g cre.。空氣暴露濃度方面,A廠作業勞工普遍嚴重超過我國法規0.5 mg/m3規定的10倍容許濃度,B、C廠平均濃度接近法規標準。另外在C廠進行短時間投料時間的採樣,整體平均為3.92(4.40) mg/m3,超過法規8倍,表示投料是一種極高暴露工作。 再者,以A廠高暴露勞工3人進行星期五至星期一的生物偵測採樣分析,每位勞工從星期五上班前至星期一下班後,每人每天收集二次,每人共收集8次尿液,再以星期五下班後尿中總銻濃度為啟始濃度推算銻之生物半衰期。分析結果顯示個人暴露有5次遠超過法定容許濃度,1次超過行動值。平均濃度(標準差)為4.43(3.37) mg/m3,生物半衰期為60小時,變異係數14.8%。三氧化二銻暴露員工尿液銻的物種含有三甲基銻、三價銻、五價銻及二種未知銻物種。三甲基銻濃度隨時間的變化不大,且濃度偏低,五價銻濃度隨三氧化二銻暴露而增加,三價銻濃度於暴露結束後開始上升,在暴露結束後的2400分鐘達最高點,另二種未知物種濃度亦隨著暴露時間增加而增加,當暴露結束後第1000分鐘的濃度仍增加,隨後再降低,直到下一次再暴露後,濃度才再增加。 本研究已建立有機三甲基銻、無機三價銻與五價銻的同步分析方法,適用於環境樣本與尿液樣本分析的銻物種。未來的研究建議進一步鑑定尿中未知銻物種以及研擬銻暴露預防的方法。 Antimony trioxide (Sb2O3) is a fire retardant with various applications widely used in industry. Animal studies have shown that antimony trioxide is a carcinogen associated with lung cancer and cardiopulmonary diseases in rats. Antimony hydride compounds of high concentrations may cause central nervous system damage and hemolysis. The American Conference of Governmental Industrial Hygienists (ACGIH), International Agency for Research on Cancer (IARC) and the European Union have classified the carcinogenesis of antimony trioxide at A2 level, 2B level and the third category, respectively. A convenient and robust analytical method is required for determining various antimony species. This study attempted to develop an analytical method to simultaneously determine antimony species and to measure human exposure at industries, such as manufacturing or using chemicals containing antimony. For the on-site exposure assessment, we conducted “biological monitoring” at three plants: one antimony smelting plant A, and two engineering plastic plants B and C. This study first developed and established an analytical protocol to simultaneously determine three antimony species in urine samples, including: inorganic trivalent antimony (Sb(III)), pentavalent antimony (Sb(V)) and organic trimethylantimony (TMSb), using HPLC-ICP-MS. We employed 20 mM EDTA, 10% methanol and de-ionized water as the elution buffer for the gradient elution. The results showed that Sb (III), Sb (V) and TMSb were appropriately separated with the retention times of 9.86, 6.20 and 2.40 min, and the detection limits of 0.79, 0.22 and 1.23 μg/L, respectively. We have obtained good chromatograms for these three species of antimony in urine, but there were two other unknown antimony species in the sample deserving determination. For the on site survey, we collected air samples at work places and workers’ urine samples at Plant A for 5 week days by 5 subgroups: packaging group, oxidation furnace group, management group, quality control and analysis group, and accounting group. The convenient hair samples were also collected from workers. The results showed that the 5-day average antimony concentrations in the air (standard deviations) were: 3.36 (2.35), 1.86 (1.69), 0.12 (0.14), 0.03 (0.03) and 0.03 (0.02) mg/m3, respectively. The corresponding average concentrations (standard deviation) were 266.2 (88.4), 178.1 (72.1), 51.4 (40.5), 42.4 (33.2) and 28.8 (22.6) μg Sb/g cre in urine samples, and 12.52 (1.85), 1.44 (0.83), 0.41 (0.47), 0.07 (0.08) and 0.03 (0.005) mg Sb/g in hair samples. The mean concentrations of Sb among the 5 survey sites at the Plant A were significantly different for each type of sample (p < 0.001, by Kruskal-Wallis One Way Analysis of Variance by Ranks). The relationships between Sb concentrations in the air samples and Sb concentrations in the urine samples was in the function of Y = 42.76X + 67.31, r = 0.6377. The corresponding association for hair samples was Y = 2.011X - 0.0611, r = 0.6926. Both indicate a good relationship. We also collected the air samples at the work place for one-day and urine samples from workers at the antimony trioxide plant (A), engineering plastics plant (B) and engineering plastics plant (C). The average concentrations (standard deviation) of antimony trioxide in the air samples were: 5.31 (5.88), 0.50 (0.31) and 0.45 (0.79) mg/m3, respectively. The average concentrations (standard deviation) in the urine samples collected from the respective plants on that single day were 313.7 (437.4), 40.1 (32.8) and 14.7 (7.3) μg Sb/g cre. The average Sb level in the air samples of Plant A was 10-fold greater than Taiwan’s standard for permissible exposure to Sb of 0.5 mg/m3. The average air concentrations of Sb at plants B and C were both near the permissible level. Air samples were also taken from Plant C for a short period during the operation of “feeding” antimony ore; and the overall average concentration (standard deviation) was 3.92 (4.40) mg/m3, which was 8-fold greater than the permissible level. This is another extreme high level for workers to expose to. We have carried out a “biological monitoring” and analysis study on 3 workers who exposed to high levels of Sb at work except Saturdays & Sundays. The air samples at work were collected on a Friday and the following Monday. Each worker provided 8 urine samples starting from the Friday before work until Monday by the end of the daily duty. We monitor the change of antimony concentration in urine in order to calculate the half-life of metabolism of the antimony. The average (standard deviation) concentration of the airborne Sb the workers exposed to was 4.43 (3.37) mg/m3. Among the air samples, 5 samples greatly surpassed the “permissible exposur limits” and 1 sample exceeded the “action level”. The antimony species identified from the urine samples for the workers who exposed to antimony trioxide consisted of trimethyl antimony, trivalent antimony, pentavalent antimony and two unknown species. The half-life of antimony trioxide was 60hrs with a coefficient of variation of 14.8%. The analysis of the metabolites in the urine samples showed that the concentration of trimethyl antimony was much lower than other two species. On the other hand, the concentration of pentavalent antimony increased as the antimony trioxide exposure increased. The urinary concentration of trivalent antimony began to rise at the end of exposure and reached to a peak at 2400 min after the exposure. The concentrations of the two unknown species increased as the exposure duration increased; the increasing trends continuously proceeded for 1000 min after the exposure and then declined until another exposure occurred. In conclusion, we have established an analytical method to determine inorganic trivalent antimony, pentavalent antimony and organic trimethylantimony in environmental samples and urinary samples. Future study should emphasize exposure reduction at work place and identify the two unknown species. |
URI: | http://tdr.lib.ntu.edu.tw/jspui/handle/123456789/44565 |
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