錳是人體所必須的微量元素，同時它也是已知的神經毒性物質。當人暴露於高濃度錳的環境中時，會造成身體的傷害及罹患疾病。錳中毒的病人會出現與帕金森氏症相似的病症，故錳被懷疑與此種疾病有關。
由於錳被廣泛應用在鋼鐵工業上、電池中、殺蟲劑及油漆成份等等，在日常生活中有很多機會接觸到含錳的物質。適量的錳是人體所必須的，而過量的錳卻會造成人體的傷害。所以錳以必要的檢測技術去瞭解是相當重要的。
鑑於文獻中有關有機態錳物種的分析報導甚少，早期的文獻大多檢測生物樣品的總錳含量。本實驗係將尿液分成七類物種分析：全量尿液中的錳物種、液相尿液中的錳物種、固相尿液中的錳物種、液相尿液中的鉗合性錳物種及非鉗合性錳物種、全量尿液中的鉗合性錳物種及非鉗合性錳物種七類物種。分類的技術主要是利用薄膜過濾，將尿液分成全量、液相及固相三類。另外，前兩類再利用Chelex-100樹脂的鉗合萃取特性，將可鉗合的二價錳離子留置在樹脂中，再利用酸萃出分析；其餘的非鉗合性錳物種，以微波消化的方式，將其轉變為可鉗合的二價錳離子，再利用上述步驟分析。因此共可分成七類錳物種。實驗結果顯示，人體尿液中存在的錳以液相尿液中的錳含量最高，佔尿液中總錳含量的 70 % 以上。而液相尿液中鉗合性錳物種於液相尿液中，分佈的比例規律性不高。但是可以發現將近五成液相尿液樣品中，鉗合性的錳物種佔90 % 以上。表示在液相尿液中二價錳離子的存在是居大多數的。在分析方法的精密度與準確度方面，以標準參考尿液 ( SRM-2670 ) 經過消化及Chelex-100管柱前濃縮後，再利用石墨爐式原子吸收光譜儀偵測，以確認精密度與準確度。

Manganese is an essential trace element for mammals; however, exposed to high concentrations of manganese, human’s body could get certain diseases due to its neurotoxic excess. Some of these effects are irreversible. Extremely high concentration of manganese will induce Manganese intoxication and the symptoms are similar to those of Parkinson’s disease. Therefore, manganese is considered to be possibly related to Parkinson’s disease. Manganese is widely applied in the processes of manufacturing of iron alloys, dry batteries and is also found in many organo-manganese compounds. Not much information can be obtained on the distribution and speciation of manganese in human body. Therefore, it’s important to develop techniques to determine and speciate manganese in human’s body.
In this study, Graphite Furnace Atomic Absorption Spectrometry ( GFAAS ) is used to determine manganese in the urine. We use membrane filtration and chelating extraction techniques to speciate manganese in urine samples. We can define seven manganese species with analytical procedures－total manganese in urine, solid form of manganese in urine, soluble form of manganese in urine, chelating-extractable manganese in liquid urine, non-chelating-extractable manganese in liquid urine, chelating-extractable manganese in total urine and non-chelating-extractable manganese in total urine. Our research showed that more than 70% of the total manganese in urine was in soluble form and the rest was in solid form. The amount of manganese in soluble form of urine extractable with chelex-100 resin is irregular. The irregularity may relate to life style and diet habit of each individual. Spike recovery tests of EDTA-Mn in standard urine confirmed that stable organo-manganese does not react with chelex-100. The results from digested and column-preconcentrated standard reference urine confirmed the accuracy and precision of the analytical scheme.

1. Roels, H.; Sarhan, M. J.; Hanotiau, I.; de Fays, M.; Genet, P.; Bernard, A.; Buchet, J. P. and Lauwerys, R., ”Preclinical Toxic Effects of Manganese in Workers from a Mn Salts and Oxides Producing Plant”, The Science of the Total Environment, 1985, 42, 201-206.
2. Lucchini, P.; Bergamaschi, E.; Smargiassi, A.; Festa, D. and Apostoli, P., “Motor Function, Olfactory Threshold, and Hematological Indices in Manganese-Exposed Ferroalloy Workers”, Environmental Research, 1997, 73, 175-180.
3. Mergler, D.; Huel, G.; Bowler, R.; Iregren, A.; Bélanger, S.; Baldwin, M.; Tardif, R.; Smargiassi, A. and Martin, L., “Nervous System Dysfunction Among Workers with Long-Term Exposure to Manganese”, Environmental Research, 1994, 64, 151-180.
4. Garrett, R. H. and Grisham, C. M., “Coenzymes”, Biochemistry, Saunders college Pub., Fort Worth, Philadelphia, San Diego, New York, Orlando, Austin, San Antonio, Toronto, Montreal, London, Sydney, Tokyo, 1994, 356-356.
5. Iregren, A., “Using Psychological Tests for the Early Detection of Neurotoxic Effects of Low Level Manganese Exposure”, Neuro Toxicology, 1994, 15(3), 671-678.
6. Whitlock, C. M.; Amuso, S. J. and Bittenbender, J. B., “Chronic Neurological Disease in Two Manganese Steel Workers”, American Industrial Hygiene Association Journal, september-October 1966, 454-459.
7. Cook, D. G.; Fahn, S. and Brait, K. A., “Chronic Manganese Intoxication”, Arch Neurol, Jan 1974, 30, 59-64.
8. Adrian, H. and John, H., “A New Functional Test of Manganese Status”, Journal of Nutritional Medicine, 1990, 1(3), 209-215.
9. Chia, S. E.; Foo, S. C.; Gan, S. L.; Jeyaratnam, J. and Tian, C. S., “Neurobehavioral Functions among Workers Exposed to Manganese ore”, Scand J Work Environ Health, 1993, 19, 264-270.
10. Brenda, A., “7 Supplements for Better Bones”, Better Nutrition, 2000, 62(7), 72-76.
11. Couper, J., “On the Effect of Black Oxide of Manganese when Inhaled into the Lungs”, Br. Ann. Med. Pharma. 1837, 1, 41-42.
12. Greger, J. L., “Symposium: Between a Rock and a Hard Place: Dietary and Toxicological Standards for Essential Minerals”, J. Nutr., 1998, 128, 368S-371S.
13. Scheer, J. F., “Multi-Minerals Multi-Benefits”, Better Nutrition, Nov 1998, 60 (1), 52-57.
14. Finley, J. W. and Davis, C. D., “Manganese Deficiency and Toxicity: Are High or Low Dietary Amounts of Manganese Cause for Concern ?”, Biofactors, 1999, 10(1), 15-24.
15. Van Ormer, D. G. and Purdy, W. C., “The Determination of Manganese in Urine By Atomic Absorption Spectrometry”, Anal. Chim. Acta, 1973, 64, 93-105.
16. Buchet, J. P.; Lauwerys, R. and Roels, H., “Determination of Manganese in Blood and Urine by Flameless Atomic Absorption Spectrophotometry”, Clin. Chim. Acta, 1976, 73, 481-486.
17. Watanabe, T.; Tokunaga, R.; Iwahana, T.; Tati, M. and Ikeda, M., “Determination of Urinary Manganese by the Direct Chelation-Extraction Method and Flameless Atomic Absorption Spectrophotometry”, Brit. J. Ind. Med., 1978, 35, 73-77.
18. Halls, D. J. and Fell, G. S., “Determination of Manganese in Serum and Urine by Electrothermal Atomic Absorption Spectrometry”, Anal. Chim. Acta, 1981, 129, 205-211.
19. Subramanian, K. S. and Meranger, J. C., “Graphite Furnace Atomic Absorption Spectrometry with Nitric Acid Deproteinization for Determination of Manganese in Human Plasma”, Anal. Chem., 1985, 57, 2478-2481.
20. Saavedra, J., “Changes in Manganese and Small Cobalt Blood Levels of Lead-Exposed Workers”, Arch. Invest. Med. (Mex.), 1991, 22, 57-61.
21. Minoia, C.; Sabbioni, E.; Apostoli, P.; Pietra, R.; Pozzoli, L.; Gallorini, M.; Nicolaou, G.; Alessio, L. and Capodaglio, E., “Trace Element Reference Values in Tissues from Inhabitants of The European Community I. A Study of 46 Elements in Urine, Blood and Serum of Italian Subjects”, The Science of the Total Environment, 1990, 95, 89-105.
22. Krushevska, A.; Barnes, R. M. and Amarasiriwaradena, C., “Decomposition of Biological Samples for Inductively Coupled Plasma Atomic Emission Spectrometry Using an Open Focused Microwave Digestion System”, Analyst, 1993, 118, 1175-1181.
23. Friberg, L. and Nordberg, G., “Manganese”, Handbook on the Toxicology of Metal, Volume II, Amsterdam: Elsevier, 1986, 354-386.
24. Adrian, H. and John, H., “A New Functional Test of Manganese Status”, Journal of Nutritional Medicine, 1990, 1(3), 209-215.
25. Klimis-Tavantzis, D. J.; Taylor, P. N. and Wolinsky, I., “Fatty Acid Biosynthesis”, Manganese in Health and Disease, Klimis-Tavantzis, D. J. Ed., CRC Press, Boca Raton, Fla., 1994, 89-91.
26. USEPA, “Manganese”, USEPA IRIS Substance File-Manganese, 1988.
27. Lauwerys, R.; Roels, H.; Genet, P.; Toussaint, G.; Bouckaert, A. and De Cooman, S., “Fertility of Male Workers Exposed to Mercury Vapor or to Manganese Dust: A Questionnaire Study”, American Journal of Industrial Medicine, 1985, 7, 171-176.
28. Gennart, J. P.; Buchet, J. P.; Roels, H.; Ghyselen, P.; Ceulemans, E. and Lauwerys, R., “Fertility of Male Workers Exposed to Cadmium, Lead, or Manganese”, American Journal of Epidemiology, 1992, 135(11), 1208-1219.
29. Roels, H. A.; Ghyselen, P.; Buchet, J. P. and Lauwerys, R. R., “Assessment of the Permissible Exposure Level to Manganese in Workers Exposed to Manganese Dioxide Dust”, British Journal of Industrial Medicine, 1992, 49, 25-34.
30. Harvard Medical School Health, “Parkinson’s Disease is not Parkinsonism”, Harvard Health Letter, 1993, 18(7), 2-2.
31. Buchet, J. P.; Magos, C.; Roels, H.; Ceulemans, E. and Lauwerys, R., “Urinary Excretion of Homovanillic Acid in Workers Exposed to Manganese”, Int arch Occup environ Health, 1993, 65, 131-133.
32. Kaji, H.; Ohsaki, Y.; Rokujo, C.; Higashi, T.; Fujino, A. and Kamada, T., “Determination of Blood and Urine Manganese (Mn) Concentrations and the Application of Static Sensography as the Indices of Mn-Exposure Among Mn-Refinery Workers”, J UOEH, 1993, 15(4), 287-296.
33. Chia, S. E.; Gan, S. L.; Chua, L. H.; Foo, S. C. and Jeyaratnam, J., “Postural Stability Among Manganese Exposed Workers”, Neuro Toxicology, 1995, 16(3), 519-526.
34. Michael, A., “Manganese: Brain Transport and Emerging Research Needs”, Environmental Health Perspectives Supplements, Jun 2000, 108(3), 429-432.
35. National Wildlife Federation, “Another Health Hazard in Gasoline?”, National Wildlife, June/July 1997, 35(4), 11.
36. Tsalev, D. L. and Zaprianov, Z. K., “Manganese”, Atomic Absorption Spectrometry in Occupational and Environmental Health Practice, Volume I, Tsalev, D. L. Ed., CRC Press, 1983, 153-153.
37. Tanaka, S. and Lieben, J., “Manganese Poisoning and Exposure in Pennsylvania”, Arch Environ health, Nov 1969, 19, 674-684.
38. Sierra, P.; Loranger, S.; Kennedy, G. and Zayed, J., “Occupational and Environmental Exposure of Automobile Mechanics and Nonautomotive Workers to Airborne Manganese Arising From the Combustion of Methylcyclopentadienyl Manganese Tricarbonyl (MMT)”, American Industrial Hygiene Association Journal, 1995, 56, 713-716.
39. Zhao, S.; An, H. and Chen, S., “A Study of a High-power, Ammonium Chloride Zinc/Manganese Dioxide Dry Battery”, Journal of power sources, 1998, 76, 218-220.
40. Mergler, D. and Baldwin, M., “Early Manifestations of Manganese Neurotoxicity in Humans: An Update”, Environmental Research, 1997, 73, 92-100.
41. Butcher, D. J.; Zybin, A.; Bolshov, M. A. and Niemax, K., “Speciation of Methylcyclopentadienyl Manganese Tricarbonyl by High-Performance Liquid Chromatography-Diode Laser Atomic Absorption Spectrometry”, Analytical Chemistry, 1999, 71, 5379-5385.
42. Headley, J. V.; Massiah, W.; Laberge, D. and Purdy, J. R., “Rapid Screening for Mancozeb in Exposure Trials by Inductively Coupled Plasma-Atomic Emission Spectrometric Determination of Manganese”, Journal of AOAC International, 1996, 79(5) 1184-1188.
43. Michael, A., “Manganese: Brain Transport and Emerging Research Needs”, Environmental Health Perspectives Supplements, Jun 2000, 108(3), 429-432.
44. Role, H.; Lauwerys, R.; Genet, P.; Sarhan, M. J.; Hanotiau, I. and Buchet, J. P., “Relationship Between External and Internal Parameters of Exposure to Manganese in Workers from a Manganese Oxide and Salt Producing Plant,” American Journal of Industrial Medicine, 1987, 11, 297-305.
45. Lauwerys, R. R. and Hoet, P., “Biological Monitoring of Exposure to Inorganic and Organometallic Substances: Manganese”, Industrial Chemical Exposure, Guidelines for Biological Monitoring, Lewis Publishers, Boca Raton, Ann Arbor, London, Tokyo, 1993.
46. 勞委會民國八十四年公佈「勞工業境空氣中有害物質容許濃度標準」。
47. Mertz, W., “Manganese in Human Foods and Dietaries”, Trace Elements in Human and Animal Nutrition, Volume I, 4th ed., Academic Press, 1986, 211-212.
48. 行政院環境保護署八十七年公佈「飲用水水質標準」。
49. IUPAC, “Sample Collection Guidelines for Trace Elements in Blood and Urine”, Pure and Applied Chemistry, 1995, 67, 1575-1608.
50. Tsalev, D. L. and Zaprianov, Z. K., “Manganese”, Atomic Absorption Spectrometry in Occupational and Environmental Health Practice, Volume I, Tsalev, D. L. Ed., CRC Press, 1983, 153-158.
51. Mertz, W., “Manganese in Animal Tissues and Fluids”, Trace Elements in Human and Animal Nutrition, Volume I, 4th ed., Academic Press, 1986, 185-186.
52. Zief, M. and J. W. Mitchell, “The Laboratory”, Contamination Control in Trace Element Analysis, New York, Wiley, 1976, 46-68.
53. Wang, J.; Houk, R. S.; Dreessen, D. and Wiederin, D. R., “Identification of Inorganic Elements in Proteins in Human Serum and in DNA Fragments by Size Exclusion Chromatography and Inductively Coupled Plasma Mass Spectrometry with a Magnetic Sector Mass Spectrometer”, J. Am. Chem. Soc., 1998, 120, 5793-5799.
54. Dungs, K. and Neidhart, B., “Analysis of Urine Samples by Electrothermal Atomisation-Atomic-Absorption Spectrometry: a Comparison of Natural and Control Material”, Analyst, July 1984, 109, 877-880.
55. Iversen, B. S.; Panayi, A.; Camblor, J. P. and Sabbioni, E., “Simultaneous Determination of Cobalt and Manganese in Urine by Electrothermal Atomic Absorption Spectrometry. Method Development Using a Simplex Optimization Approach”, Journal of analytical atomic spectrometry, August 1996, 11, 591-594.
56. Mertz, W., “Manganese Metalloenzymes”, Trace Elements in Human and Animal Nutrition, Volume I, 4th ed, Academic Press, 1986, 196-196.
57. Walton, A. P.; Wei, G. T.; Liang, Z.; Liang, Z. and Michel, R. G., “Laser-Excited Atomic Fluorescence in a Flame as a High-Sensitivity Detector for Organomanganese and Organotin Coumpounds Following Separation by High-Performance Liquid Chromatography”, Analytical Chemistry, 1991, 63, 232-240.
58. Usui, A.; Kato K.; Murase, M.; Maeda, M.; Koyama, T.; Tanaka, M.; Takeuchi, E. and Abe, T., “Manganese-Containing Superoxide Dismutase in Blood and Urine During Open-Heart Surgery”, Japanese Circulation Journal, 1992, 56, 1206-1213.
59. Wang, J.; Houk, R. S.; Dreessen, D. and Wiederin, D. R., “Speciation of Trace Elements in Proteins in Human and Bovine Serum by Size Exclusion Chromatography and Inductively Coupled Plasma-Mass Spectrometry with a Magnetic Sector Mass Spectrometer”, JBIC, 1999, 4, 546-553.
60. 李慶昌，海水中錳元素之分析與物種鑑定，國立台灣師範大學研究所碩士論文，吳家誠教授指導，1993。
61. Angerer, S. S., “The Pre-Analytical Phase of Toxicological Monitoring Examinations in Occupational Medicine”, Trends in Analytical Chemistry, 1983, 2(11), 257-261.
62. Kristiansen, J.; Christensen, J. M.; Iversen, B. S. and Sabbioni, E., “Toxic Trace Element Reference Levels in Blood and Urine: Influence of Gender and Lifestyle Factors”, The Science of the Total Environment, 1997, 204, 147-160.
63. Tsalev, D. L. and Zaprianov, Z. K., “Manganese”, Atomic Absorption Spectrometry in Occupational and Environmental Health Practice, Volume I, Tsalev, D. L. Ed., CRC Press, 1983, 52-52.
64. 陳浩琦，人體尿液中鎘之測定與物種分類研究，國立台灣師範大學研究所碩士論文，吳家誠教授指導，1996。
65. 陳虹珍，人體尿液中鉻之測定與物種分類研究，國立台灣師範大學研究所碩士論文，吳家誠教授指導，1996。
66. USEPA, “Microwave Assisted Acid Digestion of Aqueous Samples and Extracts”, USEPA Method 3015, 1994.
67. USEPA, “Microwave Assisted Acid Digestion of Sediments, Sludges, Soil, and Oils”, Method 3051, 1994.
68. USEPA, “Microwave Assisted Acid Digestion of Siliceous and Organically Based Matrices”, Method 3052, 1996.
69. Bio-Rad Lab, “Chelex-100 and Chelex-20 Chelating Ion Exchange Resin Instruction Manual”, Bio-Rad Lab.
70. 行政院環境保護署環境檢驗所，八十七年公佈「環境檢測標準方法驗證程序準則」。