尿中銻之採樣與分析

Antimony Analyzing and Sampling in Urine

10.7005/JOSH.201206.0205

蕭英德(Ying-Der Hsiao)

三氧化二銻 ； 生物偵測 ； 物種分析 ； 高效率液相層析感應偶合電漿質譜儀 ； Antimony trioxide (Sb2O3) ； Biological monitoring ； Species analysis ； HPLC-ICP/MS

勞工安全衛生研究季刊

20卷2期（2012 / 06 / 01）

205 - 230

繁體中文

三氧化二銻化合物是一種防火添加劑，廣泛應用於工業。本研究以銻冶煉工廠高暴露勞工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2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起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/m^3，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2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2,400分鐘達最高點，另2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1,000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。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 (Sb(subscript 2)O(subscript 3)) is a fire retardant with various applications widely used in industry. This study chose an antimony smelting plant 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. Future study should emphasize exposure reduction at work place and identify the two unknown species.

1. 行政院勞工委員會：作業環境空氣中有害物質標準分析參考方法。第一版；1994。
2. (2010)。2010台灣化學品進口商名錄。台灣:台灣化工資訊服務社。
3. (1989).American Conference of Governmental Industrial Hygienists. 1989; 47:291. 2003.
4. European Parliament, Council. 67/548/EEC Annex 1; 2003.
5. Adeloju, S.B.,Young, T.M.,Jagner, D.,Batley, G.E.(1998).Anodic stripping potentiomental determination of antimony on a combined electrode.The Analyst,123,1871-4.
6. American Conference of Governmental Industrial Hygienists=ACGIH(2003).2003 TLVs and BEIs. Threshold Limit Values for Chemical Substances and Physical Agents, Biological Exposure Indices.Cincinnati, OH:
7. Bellido-Martin, A.,Gomez-Ariza, J.L.,Smichowsky, P.,Sanchez-Rodas, D.(2009).Speciation of antimony in airborne particulate matter using ultrasound probe fast extraction and analysis by HPLCHG-AFS.Analytica Chimica Acta,649,191-5.
8. Bregoli, L.,Chiarini, F.,Gambarelli, A.,Sighinolfi, G.,Gatti, A.M.,Santi, P.(2009).Toxicity of antimony trioxide nanoparticles on human hematopoietic progenitor cells and comparison to cell lines.Toxicology,262,121-9.
9. Cavallo, D.,Iavicoli, I.,Setini, A.,Marinaccio, A.,Perniconi, B.,Carelli, G.(2002).Genotoxic risk and oxidative DNA damage in workers exposure to antimony trioxide.Environmental and Molecular Mutagenesis,40,184-9.
10. Ceriotti, G.,Amarasiriwardena, D.(2009).A study of antimony complexed to soil-derived humic acids and inorganic antimony species along a Massachusetts highway.Microchemical Journal,91,85-93.
11. Chen, B.,Krachler, M.,Shotyk, W.(2003).Determination of antimony in plant and peat samples by hydride generation-atomic fluorescence spectrometry(HG-AFS).Journal of Analytical Atomic Spectrometry,18,1256-62.
12. Chen, L.H.,Yang, J.L.(2007).Acute Toxicity of Antimony Chloride and its Effects on Oxygen Consumption of Common Carp (Cyprinus carpio).Bulletin of Environmental Contamination and Toxicology,78,459-62.
13. Craig, P.J.,Sergeeva, T.,Jenkins, R.O.(2003).Determination of inorganic Sb(Ⅴ) and methylantimony species by HPLC with hydride generationatomic fluorescence spectrometric detection.Mikrochimica Acta,137,221-7.
14. Duester, L.,Diaz-Bone, R.A.,Kösters, J.,Hirner, A.V.(2005).Methylated arsenic, antimony and tin species in soils.Journal of Environmental Monitoring,7,1186-93.
15. Duester, L.,Vink, J.P.M.,Hirner, A.V.(2008).Methylantimony and -arsenic Species in Sediment Pore Water Tested with the Sediment or Fauna Incubation Experiment.Environmental science and technology,42,5866-71.
16. Feng, Y.L.,Narasaki, H.,Chen, H.Y.,Tian, L.C.(1999).Speciation of antimony(Ⅲ) and antimony(Ⅴ) using hydride generation inductively coupled plasma atomic emission spectrometry combined with the rate of pre-reduction of antimony.Analytica Chimica Acta,386,297-304.
17. Gebel, T.,Claussen, K.,Dunkelberg, H.(1998).Human biomonitoring of antimony.International Archives of Occupational and Environment Health,71,221-4.
18. Hansen, H.R.,Pergantis, S.A.(2008).Analytical techniques and methods used for antimony speciation analysis in biological matrices.Journal of Analytical Atomic Spectrometry,23,1328-40.
19. Harbison, R.D.(1998).Hamilton and Hardy's Industrial Toxicology.Mosby.
20. Hathaway, G.J.(1996).Proctor and Hughes' Chemical Hazards of the Workplace.John Wiley & Sons, Inc.
21. Hext, P.M.,Pinto, P.J.,Rimmel, B.A.(1999).Subchronic feeding study of antimony trioxide in rats.Journal of Applied Toxicology,19,205-9.
22. Iavicoli, I.,Caroli, S.,Alimonti, A.,Petrucci, F.,Caretli, G.(2002).Biomonitoring of a worker population exposed to low antimony trioxide levels.Journal of Trace Elements in Medicine and Biology,16,33-9.
23. International Agency for Research on Cancer=IARC(1989).,France:The Institute.
24. Jones, R.D.(1994).Survey of antimony workers: mortality 1961-1992.Occupational and Environmental Medicine,51,772-6.
25. Jones, S.R.,Atkin, P.,Holroyd, C.,Lutman, E.,Batlle, J. Vives,Wakeford, R(2007).Lung cancer mortality at a UK tin smelter.Occupational Medicine,57,238-45.
26. Kiml, H.A.,Heo, Y.,Oh, S.Y.,Lee, K.J.,Lawrence, D.A.(1999).Altered serum cytokine and immunoglobulin levels in the workers exposed to antimony.Human and Ex-perimental Toxicology,18,607-13.
27. Kirkland, D.,Whitwell, J.,Deyo, J.,Serex, T.(2007).Failure of antimony trioxide to induce micronuclei or chromosomal aberrations in rat bone-marrow after sub-chronic oral dosing.Mutation Research,627,119-28.
28. Krachler, M.,Emons, H.(2001).Urinary antimony speciation by HPLC-ICP-MS.Journal of Analytical Atomic Spectrometry,16,20-5.
29. Krachler, M.,Emons, H.,Zheng, J.(2001).Speciation of antimony for the 21st century: promises and pitfalls.Trends in Analytical Chemistry,20,79-90.
30. Kubota, T.,Kawakami, A.,Sagara, T.,Ookubo, N.,Okutani, T.(2001).Determination of antimony content in natural water by graphite furnace atomic absorption spectrometry after collection as antimony(Ⅲ)-pyrogallol complex on activated carbon.Talanta,53,1117-26.
31. Lauwerys, Robert R.,Hoet, Perrine(2001).Industrial chemical exposure: guidelines for biological monitoring.CRC Press.
32. Marconia, E.,Caneparia, S.,Astolfia, M.L.,Perrino, C.(2011).Determination of Sb(III), Sb(V) and identification of Sb-containing nanoparticles in airborne particulate matter.Procedia Environmental Sciences,4,209-17.
33. Marlies, D.B.,Micheline, K.V.,Dominique, L.(2003).Cobalt and antimony: genotoxicity and carcinogenicity.Mutation Research,533,135-52.
34. Miravet, R.,Herna''ndez-Nataren, E.,Sahuquillo, A.,Rubio, R.,Lo''pez-Sa''nchez, J.F.(2010).Speciation of antimony in environmental matrices by coupled techniques.Trends in Analytical Chemistry,29,28-39.
35. Müller, K.,Daus, B.,Mattusch, J.,Stärk, H.J.,Wennrich, R.(2009).Simultaneous determination of inorganic and organic antimony species by using anion exchange phases for HPLC-ICPMS and their application to plant extracts of Pteris vittata.Talanta,78,820-6.
36. Newton, P.E.,Bolte, H.F.,Daly, I.W.,Pillsbury, B.D.,Terrill, J.B.,Drew, R.T.(1994).Subchronic and chronic inhalation toxicity of antimony trioxide in the rat.Fundamental and Applied Toxicological,22,561-76.
37. Popp, M.,Hann, S.(2010).Environmental application of elemental speciation analysis based on liquid or gas chromatography hyphenated to inductively coupled plasma mass spectrometry-A review.Analytica Chimica Acta
38. Pulido, M.D.,Parrish, A.R.(2003).Metal-induced apoptosis: mechanisms.Mutation Research,533,227-41.
39. Radwan, M.A.,Al Jaser, M.H.,Al Rayes, Z.R.(2007).The effects of induced diabetes and cutaneous Leishmania infection on the pharmacokinetics of antimony in hamsters.Annals of Tropical Medicine and Parasitology,101,133-42.
40. Schnorr, T.M.,Steenland, K.,Thun, M.J.,Rinsky, R.A.(1995).Mortality in a cohort of antimony smelter workers.American Journal of Industrial Medicine,27,759-70.
41. Stemmer, K.L.(1976).Pharmacology and toxicology of heavy metals: antimony.Pharmacology and Therapeutics Part A.,1,157-60.
42. U.S. Dcpartment of Labor.OSHA Analytical Methods Manual.Salt Lake City:Occupational Safety Anayltical Laboratory.
43. Ulrich, N.(1998).Speciation of antimony(Ⅲ), antimony(Ⅴ) and trimethylstiboxide by ion chromatography with inductively coupled plasma atomic emission spectrometric and mass spectrometric detection.Analytica Chimica Acta,359,245-53.
44. Wehmeier, S.,Raab, A.,Feldmann, J.(2004).Investigations into the role of methylcobalamin and glutathione for the methylation of antimony using isotopically enriched antimony(V).Applied Organometallic Chemistry,18,631-9.
45. Yu, C.,Cai, Q.,Guo, Z.,Yang, Z.,Khoo, S.B.(2002).Antimony speciation by inductively coupled plasma mass spectrometry using solid phase extraction cartridge.The Analyst,127,1380-5.
46. Zheng, J.,Ohata, M.,Furuta, N.(2000).Studies on the speciation of inorganic and organic antimony compounds in airborne particulate matter by HPLC-ICP-MS.The Analyst,125,1025-8.