Please use this identifier to cite or link to this item: http://hdl.handle.net/11455/90119
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dc.contributorYu-Min Tzouen_US
dc.contributor鄒裕民zh_TW
dc.contributor.authorChung-Tse Changen_US
dc.contributor.author張中澤zh_TW
dc.contributor.other土壤環境科學系所zh_TW
dc.date2015zh_TW
dc.date.accessioned2015-12-09T02:25:07Z-
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Applied Catalysis B-Environmental 17: 267-273. Kim, J.G., J.B. Dixon, C.C. Chusuei and Y.J. Deng. 2002. Oxidation of chromium(III) to (VI) by manganese oxides. Soil Science Society of America Journal 66: 306-315. Kotz, K.T., H. Yang, P.T. Snee, C.K. Payne and C.B. Harris. 2000. Femtosecond infrared studies of ligand rearrangement reactions: silyl hydride products from Group 6 carbonyls. Journal of Organometallic Chemistry 596: 183-192. Lee, K.P., C.E. Ulrich, R.G. Geil and H.J. Trochimowicz. 1989. Inhalation toxicity of chromium dioxide dust to rats after 2 years exposure. Science of the Total Environment 86: 83-108. Lennartson, A. 2014. The colours of chromium. Nature chemistry 6: 942. Libert, B. and V.R. Franceschi. 1987. Oxalate in crop plants. Journal of Agricultural and Food Chemistry 35: 926-938. Lim, M., K. Chiang and R. Amal. 2006. Photochemical synthesis of chlorine gas from iron(III) and chloride solution. Journal of Photochemistry and Photobiology a-Chemistry 183: 126-132. Lin, W.Y., C. Wei and K. Rajeshwar. 1993. Photocatalytic reduction and immobilization of hexavalent chromium at titanium-dioxide in aqueous basic media. Journal of the Electrochemical Society 140: 2477-2482. Linsebigler, A.L., G.Q. Lu and J.T. Yates. 1995. Photocatalysis on TiO2 surfaces - principles, mechanism, and selected results. Chemical Reviews 95: 735-758. Luis, A.L. 2001. Chromium-catalyzed Oxidations. University of Texas at Austin: pp. 13. Martinez, S.A., M.G. Rodriguez and C. Barrera. 2000. A kinetic model that describes removal of chromium VI from rinsing waters of the metal finishing industry by electrochemical processes. Water Science and Technology 42: 55-61. Martin, L.R., M.P. Easton, J.W. Foster and M.W. Hill. 1989. Oxidation of hydroxymethanesulfonic acid by Fenton's reagent. Atmospheric Environment 23: 563–568. Miller, W.L., D.W. King, J. Lin and D.R. Kester. 1995. Photochemical redox cycling of iron in coastal seawater. Marine Chemistry 50: 63-77. Mohan, D. and C.U. Pittman. 2006. Activated carbons and low cost adsorbents for remediation of tri- and hexavalent chromium from water. Journal of Hazardous Materials 137: 762-811. Nriagu, J.O. and E. Nieboer. 1988. Chromium in the natural and human environments. John Wiley & Sons, New York. Ogata, Y., K. Tomizawa and K. Takagi. 1981. Photo-oxidation of formic, acetic, and propianic acids with aqueous hydrogen-peroxide. Canadian Journal of Chemistry-Revue Canadienne De Chimie 59: 14-18. Papagianni, M. 2007. Advances in citric acid fermentation by Aspergillus niger: Biochemical aspects, membrane transport and modeling. Biotechnology Advances 25: 244-263. Patterson, R.R., S. Fendorf and M. Fendorf. 1997. Reduction of hexavalent chromium by amorphous iron sulfide. Environ. Sci. Technol. 31: 2039-2044. Prairie, M.R., L.R. Evans, B.M. Stange and S.L. Martinez. 1993. AN Investigation of TiO2 photocatalysis for the treatment of water contaminated with metals and organic -chemicals. Environ. Sci. Technol. 27: 1776-1782. Rai, D., B.M. Sass and D.A. Moore. 1987. Chromiun(III) hydrolysis constants and solubility of chromium hydrogenperoxide. Inorganic Chemistry 26: 345-349. Richard, F.C. and A.C.M. Bourg. 1991. Aqueous geochemistry of chromium - A review. Water Research 25: 807-816. Rush, J.D. and B.H.J. Bielski. 1985. Pulse radiolytic studies of the reactions of HO2/O2- with Fe(II)/Fe(III) ions. The reactivity of HO2/O2- with ferric ions and its irnpllcation on the occurrence of the Haber-Weiss reaction. The journal of physical chemistry A 89: 5062-5066. Sass, B.M. and D. Rai. 1987. Solubility of amorphous chromium(III)-Iron(III) hydroxide solid-solutions. Inorganic Chemistry 26: 2228-2232. Shriver, D.F., P.W. Adkins and C.H. Langford. 1994. Inorganic Chemistry, 2nd ed. Oxford University Press, Oxford. Spruit, D. and F.C.J.V. Neer. 1966. Penetration rate of Cr (III) and Cr (VI). Dermatologica 132: 179-182. Stanin, F.T. and M. Pirnie. 2004. The transport and fate of Cr(VI) in the environment. CHromium(VI) handbook. CRC Press: 186-190. Stepniewska, Z., K. Bucior and R.P. Bennicelli. 2004. The effects of MnO2 on sorption and oxidation of Cr(III) by soils. Geoderma 122: 291-296. Strobel, B.W. 2001. Influence of vegetation on low-molecular-weight carboxylic acids in soil solution - a review. Geoderma 99: 169-198. Szabo-Bardos, E., H. Czili and A. Horvath. 2003. Photocatalytic oxidation of oxalic acid enhanced by silver deposition on a TiO2 surface. Journal of Photochemistry and Photobiology a-Chemistry 154: 195-201. Tzou, Y.M., R.H. Loeppert and M.K. Wang. 2003. Light-catalyzed chromium(VI) reduction by organic compounds and soil minerals. Journal of Environmental Quality 32: 2076-2084. Tzou, Y.M., S.L. Wang and M.K. Wang. 2005. Fluorescent light induced Cr(VI) reduction by citrate in the presence of TiO2 and ferric ions. Colloids and Surfaces a-Physicochemical and Engineering Aspects 253: 15-22. USNAS Institute of Medicine, F.a.N.B. 2001. Dietary reference intakes for Vitamin A, Vitamin K, Arsenic, Boron, Chromium, Copper, Iodine, Iron, Manganese, Molybdenum, Nickel, Silicon, Vanadium, and Zinc. 207 - 211. Voelker, B.M. and B. Sulzberger. 1996. Effects of fulvic acid on Fe(II) oxidation by hydrogen peroxide. Environ. Sci. Technol. 30: 1106-1114. Winter, M. 2001. Webelements. Wittbrodt, P.R. and C.D. Palmer. 1995. Reduction of Cr(VI) in the presence of excess soil fulvic acid. Environ. Sci. Technol. 29: 255-263. Yoneyama, H., Y. Yamashita and H. Tamura. 1979. Heterogeneous photocatalytic reduction of dichromate on N-type semiconductor catalysts. Nature 282: 817-818. Yun, Y.S., D. Park, J.M. Park and B. Volesky. 2001. Biosorption of trivalent chromium on the brown seaweed biomass. Environ. Sci. Technol. 35: 4353-4358. Zhang, H. 2000. Light and Iron(III)-induced oxidation of chromium(III) in the presence of organic acids and manganese(II) in simulated atmospheric water. Atmospheric Environment 34: 1633-1640. Zhang, H. and R.J. Bartlett. 1999. Light-induced oxidation of aqueous chromium(III) in the presence of iron(III). Environ. Sci. Technol. 33: 588-594. Zhao, C., L.E. Arroyo-Mora, A.P. DeCaprio, V.K. Sharma, D.D. Dionysiou and K.E. O'Shea. 2014. Reductive and oxidative degradation of iopamidol, iodinated X-ray contrast media, by Fe(III)-oxalate under UV and visible light treatment. Water Research 67: 144-153.zh_TW
dc.identifier.urihttp://hdl.handle.net/11455/90119-
dc.description.abstractChromium is a commonly found pollutant in the soils/sediments and water bodies because it can be discharged intentionally or unintentionally from various industrial activities. Chromium exists in two major forms of Cr(III) and Cr(VI). The physicochemical properties and toxicities of Cr(VI) and Cr(III) are quite different. Cr(III) is a cation, exhibiting a lower mobility and toxicity than that of Cr(VI), and thus, the possible oxidation of Cr(III) to harmful Cr(VI) in a natural system had received much scientific concerns in the past decades. Photolysis of FeOH2+ is a well-known pathway occurred naturally which are capable of generating hydroxyl radicals (‧OH) for Cr(III) oxidation in an acidic solution. These reactions may be modified by the low molecular weight organic acid (LMWOA), because LMWOA distributes widely in the environment which may participate in the redox reactions. However, the role of LMWOA in regulating Fe species and subsequent Cr(III) photo-oxidation as influenced by pH remains unexplored. To evaluate precisely Cr transformation and fate, it is necessary to investigate the reactions of Fe(III) photolysis and Cr(III) photo-oxidation in detail when various LMWOAs are presented. Therefore, the objectives of this study are to evaluate systematically the effects of irradiation, pH and LMWOAs, including citric acid, oxalic acid and acetic acid, on the photo-oxidation of Cr(III) in the presence of Fe(III). Benzene was used as OH radical scavenger to investigate the reaction mechanisms of photo-oxidation of Cr(III) in the Fe(III)/organic system through the kinetic studies. Result showed that Cr(III) could be oxidized in the presence of Fe(III) at pH 2-4 under UV irradiation. At pH 3, Cr(III) photo-oxidation exhibited the highest efficiency because the proportion of FeOH2+, a major Fe species of generating OH radicals upon its photolysis, was greatest according to the calculations by a chemical equilibrium model of Visual MINTEQ. Phenol, formed by interacting benzene with OH radicals, it was confirmed that OH radicals were the major oxidants for Cr(III) in the acidic solution containing Fe(III). Although both phenol and Cr(VI) formations were attributed to the OH radical productions, the ratio of phenol/Cr(VI) did not maintain a constant value. The results demonstrated that some side reactions, such as Cr(VI) reduction by Fe(II), were involved in the Cr(III) photo-oxidation reactions. With the addition of 50-400 μM citrate and oxalate into a system with 400 μM Fe(III) at pH 3, 300 μM Cr(III) photo-oxidation was greatly inhibited, and thus, no discernible Cr(VI) were produced within 4 h reactions. Even if the OH radicals could still be produced through the photolysis of Fe(OH)2+ or Fe-organic complexes in the organic-containing systems, the rapid reduction of Cr(VI) by these two organic compounds may overwhelm Cr(III) photo-oxidation. Besides, a significant increase in Fe(II) productions, derived from the photolysis of Fe-organic complexes, were observed with the addition of the organic compounds. Rapid reduction of Cr(VI) by Fe(II) in an acidic solution may be the alternative reason inhibiting Cr(VI) productions. Dissolved oxygen (DO) was involved in photolysis of Fe-organic complexes, and thus, a decrease in DO concentrations was observed at the initial reaction time. However, with an accumulation of Fe(II), the interactions of O2●-, a photolytic product, with Fe(II) may release the O2 molecules and lead to an elevation of DO. Unlike the system with citrate and oxalate, Cr(III) photo-oxidation reactions was not inhibited completely in the acetate system. Because acetate would not complex with Fe(III), photolysis of Fe-organic complexes did not occur. Therefore, the OH radical productions were mainly from the photolysis of Fe(OH)2+, and thus, acetate may serve as a reductant when it was added into the irradiated Fe(III)/Cr(III) system. However, with the addition of higher concentrations of acetate (i.e., > 50 μM), the oxidative product of acetate, i.e., ●CH2CO2H, may react with Fe(II) and promote Fe(OH)2+ productions. Thus, the inhibition of Cr(VI) production was comparable lower when higher concentrations of acetate were added.en_US
dc.description.abstract環境中的鉻廣泛的存在於土壤以及自然水體中,其來源主要為工業廢棄物的排放。環境中的鉻通常以三價Cr(III)以及六價Cr(VI)兩種形態存在,其物理化學性質有明顯的差異。Cr(III)主要以陽離子型態存在,相對於以陰離子存在的Cr(VI)有較低的移動性以及毒性,因此近年來許多研究開始關注Cr(III)氧化成為Cr(VI)的潛勢探討。過去的研究發現三價鐵物種FeOH2+ 的光解可產生氫氧自由基(●OH),此一途徑被證實可以在酸性的環境下氧化Cr(III)。自然環境中廣泛存在的小分子量有機酸(LMWOA) 可與鐵離子錯合, 而此有機鐵錯合物在酸性的環境下, 可光解產生Fe(II)促進Cr(VI)的還原, 故三價鐵及有機鐵之光反應可控制環境中鉻物種的轉變, 但過去很少有研究系統性的探討此兩種光反應如何受到有機酸的影響而導致鉻物種的變化, 故本研究的目的為瞭解於Fe(III)的酸性系統中, UV光照、LMWOA(檸檬酸、草酸及醋酸)的添加, 以及初始LMWOA濃度對溶液中Cr(III)光氧化效率的影響,並透過氫氧自由基的定量以及溶液中氧氣的動力學變化,推測其反應的途徑。結果顯示,在暗反應的實驗中, 含鐵系統中不論有無LMWOA的添加皆不會產生●OH,因此也不會有Cr(VI)的生成。在無LMWOA系統中, 光照含400 μM Fe(III)與300 μM Cr(III)的酸性溶液後發現, Cr(III)的氧化效率與FeOH2+的物種分佈呈正相關,其中在pH 3的系統,Cr(VI)最高產量可達到4.3 μM;於pH 2和4下Cr(VI)產量約為 2.3 – 2.5 μM。Cr(VI)的高生成量伴隨著較低濃度Fe(II)的生成(<10 μM),相反地,於pH 2和4 系統內Fe(II)濃度在反應240分鐘內呈持續成長並符合零級反應(k=0.1029 μmol L-1 s-1), 且●OH的生成量沒有和Cr(VI)的生成量呈現固定的比值,此可能因Cr(VI)與Fe(II)於酸性環境中發生氧化還原反應所致。在有添加LMWOA的系統中,添加50–400 μM的檸檬酸和草酸於含鐵離子溶液中皆不會產生Cr(VI),但●OH的生成量會隨著此兩種有機酸濃度的提升而提高;醋酸的添加不會抑制Cr(III)的光氧化反應,且隨著醋酸濃度的提升, Cr(VI)及●OH的產量都會隨之提高, 由於草酸和檸檬酸對Fe(III)有較佳的錯和能力,故此二有機酸的存在除了直接抑制 ●OH直接由FeOH2+的光解產生外,大量由光解有機鐵還原生成的二價鐵亦會間接還原所生成的Cr(VI)。醋酸因與Fe(III)錯和能力低,故不會抑制FeOH2+的光解產生●OH,故有較高的Cr(VI)產生量, 此外, 以EPR檢測醋酸照光之產物發現, 其亦會產生●OH, 故可提升Cr(III)的氧化。zh_TW
dc.description.tableofcontentsCONTENTS 摘要 1 ABSTRACT 3 CONTENTS ............................................................................................. 6 FIGURES 9 TABLES 14 Chapter One: Introduction 15 1-1 Research origin and objectives 15 1-2 Research purposes 17 Chapter Two: Literature Reviews 18 2-1 Chromium 18 2-1-1 The properties of chromium 18 2-1-2 The species and the fate of chromium in the environment 18 2-1-3 Chromium (III) 21 2-1-4 Chromium (VI) 23 2-1-5 Hazard of chromium 26 2-1-6 Laws and regulations for Cr in Taiwan 28 2-1-7 Treatments of Cr-containing wastewaters 29 2-2 Photocatalytic reduction of Cr(VI) 31 2-2-1 Iron and organic compound roles in the photocatalytic system 34 2-3 Low molecular weight organic acids (LMWOAs) 37 2-3-1 The characteristics of citric acid, oxalic acid and acetic acid 38 2-3-1-1 Citric acid 38 2-3-1-2 Oxalic acid 38 2-3-1-3 Acetic acid 39 Chapter Three: Material and Methods 41 3-1 Reagents and Instruments 41 3-2 Kinetics experiment 43 3-2-1 Photo-oxidation of Cr(III) 43 3-2-2 Determination of Cr(VI) 46 3-2-3 Determination of Fe(II) 47 3-2-4 Determination of hydroxyl radicals 47 3-2-5 Determination of dissolved oxygen 48 Chapter Four: Result and Discussion 50 4-1 Effects of selected environmental factors on Cr(III) photo-oxidation as catalyzed by Fe(III) 50 4-1-1 Irradiation 50 4-1-2 pH effects 55 4-2 Effects of LMWOAs on Cr(III) photo-oxidation in the absence of Fe(III) 61 4-3 Effects of LMWOAs on Cr(III) photo-oxidation in the presence of Fe(III) 64 4-3-1 Effects of initial LMWOAs concentrations on Cr(III) photo-oxidation 69 4-3-1-1 Citric acid system 69 4-3-1-2 Oxalic acid system 78 4-3-1-3 Acetic acid system 85 4-3-2 Effects of initial Fe(III) concentrations on Cr(III) photo-oxidation 92 4-3-2-1 Citric acid system 92 4-3-2-2 Oxalic acid system 96 4-3-2-3 Acetic acid system 98 Chapter Five: Conclusion 100 References 102zh_TW
dc.language.isoen_USzh_TW
dc.rights同意授權瀏覽/列印電子全文服務,2018-08-17起公開。zh_TW
dc.subjectphotocatalyticen_US
dc.subjectFe(III)en_US
dc.subjectCr(III) photo-oxidationen_US
dc.subjectCr(VI)en_US
dc.subjectlow molecular weight organic acid (LMWOA)en_US
dc.subjecthydroxyl radicalen_US
dc.subject光催化zh_TW
dc.subject三價鐵zh_TW
dc.subject三價鉻光氧化zh_TW
dc.subject六價鉻zh_TW
dc.subject小分子量有機酸zh_TW
dc.subject氫氧自由基zh_TW
dc.titleEffects of low molecular organic acids (LMWOAs) on Cr(III) photo-oxidation in the presence of Fe(III)en_US
dc.title小分子量有機酸對三價鐵誘導三價鉻光氧化的影響zh_TW
dc.typeThesis and Dissertationen_US
dc.date.paperformatopenaccess2018-08-17zh_TW
dc.date.openaccess2018-08-17-
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item.openairetypeThesis and Dissertation-
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