臺灣博碩士論文加值系統

為了對泥水作業勞工六價鉻暴露作準確的評估，本研究選取台南縣市53位泥水業勞工進行空氣及皮膚樣本採集，估計勞工吸入及皮膚接觸水泥的六價鉻暴露總量。在暴露測定進行時，以問卷調查勞工工作史及工作時皮膚接觸水泥的頻率，並收集這些勞工尿液及血液檢體進行生物偵測，分析其真正進入人體的總量。採集的空氣與皮膚樣本以紫外可見光分光譜儀(Ultra Violet-Visible Spectroscopy, UV-Vis)進行六價鉻濃度分析，尿液與血液樣本則由原子吸收光譜儀(Atomic Absorption Spectrometer, AA)進行總鉻濃度分析。分析結果顯示，勞工空氣暴露遠低於Occupational Safety and Health Administration (OSHA)制定的Permissible Exposure Limits(PELs)對空氣中六價鉻的八小時暴露容許濃度值5 ?慊/m3，但卻有47%的勞工工作後尿中總鉻濃度大於American Conference of Governmental Industrial Hygienists(ACGIH)所制定的尿中鉻Biological Exposure Index(BEI)值25 μg/L，根據此結果推論皮膚途徑是泥水業勞工六價鉻暴露的主要來源。執行勞工工作後尿中總鉻濃度與一些暴露影響因子的多變量線性迴歸分析後，發現有無嚼食檳榔習慣與工作前尿中總鉻濃度此兩因子，在估計工作後尿中總鉻濃度達統計上顯著意義(R2= 0.3041)。血液分析方面，大部份勞工血中總鉻濃度都非常低，接近一般大眾血中總鉻濃度背景值。而無論是血漿或紅血球樣本，總鉻濃度大都低於偵測下限，但尿中總鉻濃度大於BEI值的比例卻是高的，表示泥水業勞工有一定量的六價鉻暴露，但沒有大於血漿中對六價鉻約2 ppm的還原能力，所以當勞工吸收六價鉻進入到血液時，會先被血漿還原後經由尿液排除，無法進ㄧ步進入紅血球中累積。建議防範泥水業勞工六價鉻暴露，應該從阻絕接觸和減少吸收著手，可行的方法除考慮在水泥中添加硫酸亞鐵等，使六價鉻在水泥中先還原成三價鉻外，或可在勞工皮膚上塗抹含還原能力的護手霜，讓六價鉻還原成三價鉻，減少六價鉻皮膚吸收量，進而降低勞工六價鉻暴露。

In this study, fifty three cement workers were recruited from Tainan City and County. Both air and skin sampling were taken to accurately assess the total exposure of Cr6+ from inhalation and dermal contact routes for these cement workers. During the exposure sampling time, a questionnaire was used to investigate the work history and the frequency of dermal contact to cement in a regular work day for each worker. In addition, both urine and blood samples were collected from the workers to estimate the total doses of Cr6+ in their bodies. The concentrations of Cr6+ in the air and skin samples were determined by Ultra Violet-Visible Spectroscopy (UV-Vis). The concentrations of total chromium in the urine and blood samples were measured by Atomic Absorption Spectrometer (AA). The results showed that the measured Cr6+ concentrations in air were far less than the permissible exposure limit of 5 ?慊/m3 in an 8-hour work shift established by Occupational Safety and Health Administration (OSHA). However, the concentrations of total chromium in the end of shift urine samples were 47% greater than 25 μg/L, the Biological Exposure Index (BEI) recommended by American Conference of Governmental Industrial Hygienists(ACGIH). It was concluded that dermal contact was the main route of Cr6+ exposure for cement workers. The relationship between the concentrations of total chromium in the post-shift urine samples and some exposure determinants was explored by conducting a multiple linear regression analysis. It was found that betel nut chewing and the concentrations of total chromium in the pre-shift urine samples were significantly important (R2= 0.3041) in estimating the concentrations of total chromium in the post-shift urine samples. Regarding the analysis of blood samples, the concentrations of total chromium of most workers were very low which was close to the background level of total chromium of general population. No matter the concentrations of total chromium in the samples of blood plasma and red blood cells were lower than the detection limit of total chromium, but the proportion of the concentrations of total chromium in urine samples greater than the BEI value was high. This indicated that the cement workers had certain amount of Cr6+ exposure. However, this amount was not higher than the reduction capacity, 2 ppm, of Cr6+ in blood plasma. When the Cr6+ was absorbed through the skin into the blood, most of the Cr6+ was reduced into Cr3+ which could not cumulate in red blood cells and was excreted by urine. It was suggested that the the protection of cement workers from Cr6+ exposure should focus on the cut-off of dermal absorption of Cr6+. The addition of ferrous sulfate to cement is an appropriate approach to decreasing the dermal exposure to Cr6+ for cement workers. Other alternative of applying cream with some substances which can reduce Cr6+ to Cr3+ and decrease the skin absorption of Cr6+ can also be considered.

中文摘要………………………………………………………………I
Abstract………………………………………………………………II
誌謝……………………………………………………………………IV
目錄……………………………………………………………………V
表目錄…………………………………………………………………VII
圖目錄…………………………………………………………………IX
一、緒論………………………………………………………………1
1-1 前言………………………………………………………………1
1-2 文獻探討…………………………………………………………1
二、研究動機及目的…………………………………………………11
三、研究材料與方法…………………………………………………12
3-1 採樣策略…………………………………………12
3-1-1 流程圖………………………………………12
3-1-2 勞工選取……………………………………12
3-2 材料及藥品………………………………………13
3-2-1 採樣材料……………………………………13
3-2-2 使用藥品……………………………………13
3-2-3 分析儀器及條件……………………………14
3-3 樣本的採集………………………………………17
3-4 樣本儲存、運送與分析…………………………19
3-5 各種樣品前處理方法……………………………20
3-6 品質控制…………………………………………21
3-6-1 採樣泵浦……………………………………21
3-6-2 空白值………………………………………21
3-6-3 標準品檢量線………………………………21
3-6-4 儀器偵測下限與回收率……………………22
3-6-5 血液冰存實驗………………………………24
3-6-6 分析準確性…………………………………25
3-6-7 儀器再現性…………………………………25
3-6-8 資料分析……………………………………25
四、結果與討論………………………………………………………26
4-1 工作項目介紹……………………………………26
4-2 勞工人口學資料…………………………………28
4-3 空氣樣本的濃度分析結果………………………30
4-4 皮膚樣本的濃度分析結果………………………30
4-5 尿液樣本的濃度分析結果………………………31
4-6 血漿與紅血球樣本的濃度分析結果……………32
4-7 皮膚體表面積估算………………………………33
4-8 皮膚樣本統計分析………………………………35
4-9 尿液樣本統計分析………………………………39
4-10 皮膚樣本與尿液樣本之相關性探討……………44
4-11 皮膚樣本、尿液樣本與問卷項目之相關性探討49
4-12 血液樣本相關討論………………………………53
4-13 皮膚症狀檢驗結果………………………………54
五、結論………………………………………………………………56
六、建議………………………………………………………………57
七、研究限制…………………………………………………………58
八、參考文獻…………………………………………………………59
附件一、泥水業勞工訪談問卷………………………………………66

Anderson RA. Bryden NA. Polansky MM. Serum chromium of human subjects: effects of chromium supplementation and glucose. American Journal of Clinical Nutrition 1985; 41(3): 571-577.
Angerer J. Amin W. Heinrich-Ramm R et al. Occupational chronic exposure to metals. I. Chromium exposure of stainless steel welders—biological monitoring. International archives of occupational and environmental health 1987; 59(5): 503-512.
Avnstorp C. Follow-up of workers from the prefabricated concrete industry after the addition of ferrous sulphate to Danish cement. Contact Dermatitis 1989a; 20(5): 365-371.
Avnstorp C. Prevalence of cement eczema in Denmark before and since addition of ferrous sulfate to Danish cement. Acta dermato-venereologica 1989b; 69(2): 151-155.
Avnstorp C. Cement Eczema. An Epidemiological Intervention Study. Acta dermato-venereologica. Supplementum 1992; 179: 1-22.
American Conference of Governmental Industrial Hygienists (ACGIH), TLVs?? and BEIs?? Based on the Documentation of the Threshold Limit Values for Chemical Substances and Physical Agents & Biological Exposure Indices, Cincinnati, OH 2006; 20, 92-93, 97.
Barceloux DG. Chromium. Clinical Toxicology 1999; 37(2): 173-194.
Baruthio F. Toxic effects of chromium and its compounds. Biological Trace Element Research 1992; 32: 145-153.
Belsito DV: Immunological aspects. In Adams RM. editor, Occupational skin disease, 3rd edition. W.B. Saunders company 1999; 28-34.
Brune D. Aitio A. Nordberg G et al. Normal concentrations of chromium in serum and urine—a TRACY project. Scandinavian Journal of Work, Environment & Health 1993; 19 suppl 1: 39-44.
Burrows D: Adverse chromate reactions on the skin. In Burrows D. editor, Chromium: metabolism and toxicity. Boca Raton, CRC Press, Inc. 1983; 137-163.
Corbett GE. Finley BL. Paustenbach DJ. Kerger BD. Systemic uptake of chromium in human volunteers following dermal contact with hexavalent chromium(22 mg/L). Journal of Exposure Analysis and Environmental Epidemiology 1997; 7(2): 179-189.
Cronin E. Edinburgh: Churchill Livingstone. Contact dermatitis 1980; 297.
De Flora S. Camoirano A. Bagnasco M et al. Estimates of the chromium(VI) reducing
capacity in human body compartments as a mechanism for attenuating its potential toxicity and carcinogenicity. Carcinogenesis 1997; 18(3): 531-537.
Finley BL. Kerger BD. Katona MW et al. Human ingestion of chromium (VI) in drinking
water: pharmacokinetics following repeated exposure. Toxicology and applied pharmacology 1997; 142(1): 151-159.
Fullerton A. Gammelgaard B. Avnstorp C. Menne T. Chromium content in human skin after in vitro application of ordinary cement and ferrous-sulphate-reduced cement. Contact Dermatitis 1993; 29(3): 133-137.
Fendorf SE. Surface reactions of chromium in soils and waters. Geoderma 1995; 67: 55-71.
Fowler JF. Kauffman CL. Marks JG et al. An environmental hazard assessment of low-level dermal exposure to hexavalent chromium in solution among chromium-sensitized volunteers. Journal of Occupational and Environmental Medicine 1999; 41(3): 150-160.
Gambelunghe A. Piccinini R. Ambrogi M et al. Primary DNA damage in chrome-plating workers. Toxicology 2003; 188(2-3): 187-195.
Gargas ML. Norton RL. Harris MA et al. Urinary excretion of chromium following ingestion of chromite-ore processing residues in humans: implications for biomonitoring. Risk Analysis 1994; 14(6): 1019-1024.
Guo YL. Wang BJ. Wang JC et al. Skin diseases in cement workers in Southern Taiwan. Contact Dermatitis 1999; 40(1): 1-7.
Goh CL. Gan SL. Change in cement manufacturing process, a cause for decline in chromate allergy? Contact Dermatitis 1996; 34(1): 51-54.
Gammelgaard B. Fullerton A. Avnstorp C et al. Permeation of chromium salts through human skin in vitro. Contact Dermatitis 1992; 27(5): 302-310.
Hayes RB. The carcinogenicity of metals in humans. Cancer Causes Control 1997; 8(3): 371-385. Review.
Herold DA. Fitzgerald RL: Chromium. In Seiler HG. Sigel A. Sigel H. editors, Handbook on metals in clinical and analytical chemistry. Marcel Dekker, Inc. 1994; 321-332.
Hersting K. Adelmann M. Determination of the chromium-VI content of cement, Implementation of TRGS613: first experiments. Staub Reinhaltungder Luft 1994; 54: 409-413.
Iyengar V. Woittiez J. Trace elements in human clinical specimens: evaluation of literature data to identify reference values. Clinical Chemistry 1988; 34(3): 474-481.
Jeejeebhoy KN. The role of chromium in nutrition and therapeutics and as a potential toxin. Nutrition Reviews 1999; 57(11): 329-335.
Kasperek K. Iyengar GV. Kiem J et al. Elemental composition of platelets. Part III. Determination of Ag, Au, Cd, Co, Cr, Cs, Mo, Rb, Sb, and Se in normal human platelets by neutron activation analysis. Clinical Chemistry 1979; 25(5): 711-715.
Kent C. Survey of toxic substances in basics of toxicology. John Wiley & Sons, Inc. 1998; 177-228.
Kerger BD. Paustenbach DJ. Corbett GE et al. Absorption and elimination of trivalent and hexavalent chromium in humans following ingestion of a bolus dose in drinking water. Toxicology and Applied Pharmacology 1996; 141(1): 145-158.
Kerger BD. Finley BL. Corbett GE et al. Ingestion of chromium(VI) in drinking water by human volunteers: absorption, distrobution, and excretion of single and repeated doses. Journal of Toxicology and Environmental Health 1997; 50(1): 67-95.
Kiilunen M. Järvisalo J. Mäkitie O. Aitio A. Analysis, storage stability and reference values for urinary chromium and nickel. International Archives of Occupational and Environmental Health 1987; 59(1): 43-50.
Kristiansen J. Christensen JM. Iversen BS. 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(2): 147-160.
Langard S. Chromium, in metals in the environment. Waldron HA. editor, Academic Press London 1980; 111.
Lewalter J. Korallus U. Harzdorf C. Weidemann H. Chromium bond detection in isolated erythrocytes: a new principle of biological monitoring of exposure to hexavalent chromium. International Archives of Occupational and Environmental Health 1985; 55(4): 305-318.
Mertz W. Review Article. Chromium research from a distance:from 1959 to 1980. Journal of the American College of Nutrition 1998; 17(6): 544-547.
Miksche LW. Lewalter J. Health surveillance and biological effect monitoring for chromium-exposed workers. Regulatory Toxicology and Pharmacology 1997; 26(1): S94–99.
Morris BW. Kemp GJ. Chromium in plasma and urine as measured by electrothermal atomic absorption spectroscopy. Clinical Chemistry 1985; 31(1): 171-172.
Occupational Safety and Health Administration, 29 CFR Parts 1910, 1915 et al., Occupational Exposure to Hexavalent Chromium. Final rule Federal Register 2006; 71(39).
Ottenwaelder H. Wiegand HJ. Bolt HM. Uptake of 51Cr(VI) by human erythrocytes: evidence for a carrier-mediated transport mechanism. The Science of the Total Environment 1988; 71(3): 561-566.
Paschal DC. Ting BG. Morrow JC et al. Trace metals in urine of United States residents: reference range concentrations. Environmental Research 1998; 76(1): 53-59.
Paustenbach DJ. Panko JM. Fredrick MM et al. Urinary chromium as a biological marker of environmental exposure: what are the limitations? Regulatory Toxicology and Pharmacology 1997; 26: S23–S34.
Pellerin C. Booker SM. Reflections on hexavalent chromium: health hazards of an industrial heavyweight. Environmental Health Perspectives 2000; 108(9): 402-407.
Pilliere F. Levy F. Renier A et al. Induction of DNA-repair synthesis(UDS)in rat pleural mesothelial cells by urine of subjects exposed to genotoxic agents. Journal of Toxicology-Clinical Toxicology 1992; 30(2): 223-238.
Polak L: Immunology of chromium. In Burrows D. editor, Chromium: metabolism and toxicity. Boca Raton, CRC Press, Inc. 1983; 54-55.
Romaguera C. Grimalt F. Vilaplana J. Carreras E. Formulation of a barrier cream against chromate. Contact Dermatitis 1985; 13(2): 49-52.
Rustemeyer T. van Hoogstraten IMW. von Blomberg BME. Scheper RJ: Mechanisms in allergic contact dermatitis. In Frosch PJ. Menné T. Lepoittevin J-P. editors, Contact dermatitis, 4th edition. Springer Berlin Heidelberg New York 2006; 11-33.
See SW. Balasubramanian R. Risk assessment of exposure to indoor aerosols associated with Chinese cooking. Environmental research 2006; 102(2): 197-204.
Smith CJ. Livingston SD. Doolittle DJ. An international literature survey of “IARC Group I carcinogens” reported in mainstream cigarette smoke. Food and chemical toxicology 1997; 35(10-11): 1107-1130. Review.
Travis JO. Susan C. Steven RP. Complexities of chromium carcinogenesis: role of cellular response, repair and recovery mechanisms. Mutation Research 2003; 533(1-2): 3-36. Review.
Trumbo P. Yates AA. Schlicker S. Poos M. Dietary reference intakes: vitamin A, vitamin K, arsenic, boron, chromium, copper, iodine, iron, manganese, molybdenum, nickel, silicon, vanadium, and zinc. Journal of the American Dietetic Association 2001; 101(3): 294-301.
Tsalev DL. Zaprianov ZK. Atomic absorption spectrometry in occupational and environmental health practice. Vol.1. Analytical Aspects and Health Significance. CRC Press, Boca Raton, Florida USA 1985; 113.
Turk K. Rietschel RL. Effect of processing cement to concrete on hexavalent chromium levels. Contact Dermatitis 1993; 28(4): 209-211.
Van Lierde V. Chéry CC. Roche N et al. In vitro permeation of chromium species through porcine and human skin as determined by capillary electrophoresis-inductively coupled plasma-sector field mass spectrometry. Analytical and Bioanalytical Chemistry 2006; 384(2): 378-384.
Versieck J. Hoste J. Barbier F et al. Determination of chromium and cobalt in human serum by neutron activation analysis. Clinical Chemistry 1978; 24(2): 303-308.
Vincent JB. Recent advances in the nutritional biochemistry of trivalent chromium. Proceedings of the Nutrition Society 2004; 63(1): 41-47.
White MA. Sabbioni E. Trace element reference values in tissues from inhabitants of the
European Union. X. A study of 13 elements in blood and urine of a United Kingdom population. The Science of the Total Environment 1998; 216(3): 253-270.
Wiegand HJ. Ottenwaelder H. Bolt HM. Recent advances in biological monitoring of hexavalent chromium compounds. The Science of the Total Environment 1988; 71(3): 309-315.
Zielhuis RL. Exposure limits to metals for the general population, Proc. Int. Conf. Heavy Metals in the Environment, CEC-WHO Amsterdam 1981; 429.
行政院勞工委員會，勞工作業環境空氣中有害物容許濃度標準，2003。
郭育良、李玉雲、王伯智、陳艷菁、高惠冠，1994；職業性皮膚病之盛行率調查建立全國職業性皮膚病之監控系統初報，勞工安全衛生研究所研究報告 IOSH83-M221。
葉文裕、施鴻志、楊瑞鍾、鄭蓉瑛、陳春萬、鍾弘，1995；工作環境安全衛生狀況調查報告-受僱者認知調查，勞工安全衛生研究所研究報告IOSH84-H302。
潘致弘、謝俊明、石東生，1995；水泥中之總鉻與可抽出性六價鉻之定量分析，勞工安全衛生研究季刊，第三卷第四期 第81-92頁。
黃經，1996；實用內外科護理-下冊(三版)，p1539，華杏出版股份有限公司，台北市。
謝俊明，1996；勞工鉻暴露生物偵測標準參考方法之建立，勞工安全衛生研究所研究報告 IOSH85-A308。
謝俊明，1997；國產水泥中鉻、鈷、鎳定量分析研究，勞工安全衛生研究所研究報告IOSH85-A312。
郭憲文、李信謀、賴俊雄，1998；影響六價鉻環境採樣分析之因素，勞工安全衛生研究季刊，第六卷第一期 第69-78頁。
謝俊明，1998；添加硫酸亞鐵降低國產水泥中六價鉻含量研究，勞工安全衛生研究所研究報告 IOSH87-A318。
陳志郎、蔡朋枝、郭育良、蘇麗芳，2000；鉻電鍍勞工含六價鉻之可吸入性氣膠暴露與生物偵測，勞工安全衛生研究季刊，第八卷第二期 第145-158頁。
賴美淑、姚克明、余惠君，2000；檳榔嚼塊的化學致癌性暨其防制：現況與未來，p3，財團法人國家衛生研究院，台北市。
趙德彰(譯者)，2003；圖解生理學，p39、p57，原書著者：中野昭一、吉岡利忠、田中越郎，長年出版社，高雄市。
李宜娟，2003；以職場勞工與動物實驗探討鉻(VI/III)暴露下尿中鉻之排除情形與動力學，國立成功大學環境醫學研究所碩士論文。
林雅崙，2006；泥水業員工皮膚鉻暴露與經皮水分喪失值對鉻暴露生物指標值之影響，長榮大學職業安全與衛生研究所碩士論文。
郝俠遂，2007；水泥，科學發展409期，p60-p65。
台灣人體體型銀行，2008年2月20日；http://3d.cgu.edu.tw/DesktopDefault.aspx。