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研究生:高玉安
研究生(外文):Kao Yu-An
論文名稱:靛藍法測氨之鹽度效應的剖析和pH校正及試劑配方改良之研究
論文名稱(外文):Diagnosis of the Salinity Effect for the Determination of Ammonia by Indophenol-Blue Method and the Improvement of Ammonia Measurement by pH Adjustment and Reagents
指導教授:陳瑤湖陳瑤湖引用關係
指導教授(外文):CHIEN YEW-HU
學位類別:碩士
校院名稱:國立海洋大學
系所名稱:水產養殖學系
學門:農業科學學門
學類:漁業學類
論文種類:學術論文
論文出版年:1999
畢業學年度:87
語文別:中文
論文頁數:77
中文關鍵詞:靛藍法海水分析鹽度效應淡水分析化學分析
外文關鍵詞:ammoniaindophenol blueseawater determinationammonia and salinityammonia and pHfreshwater determination
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水中氨氮的測定對養殖池水質管理非常重要,因水產動物有80% ~ 90%以上含氮廢物均是以氨氮形式排泄,而氨氮是造成魚類死亡的主要原因之一。靛藍法 ( indophenol blue ) 是目前水中氨氮測定方法中最廣被接受及使用者,此法係根據Berthelot 反應( Berthelot, 1859 ),其原理為:在鹼性環境 ( pH > 9.8 ) 及在sodium nitroprusside的催化下,氨經次氯酸氧化成氯化物後再與酚反應形成靛藍色的Indophenol化合物,此外為防止因高pH而產生金屬沉澱,故於反應中亦加入檸檬酸鈉來螯合這些金屬。
然而靛藍法因反應慢,呈色不穩定,且易受溫度、pH及鹽度干擾,常導致測定結果的準確度及精確度無法掌握。過去雖有不少學者提出改善修正的方法,但均侷限於自然水域的測定,對於應用在養殖上的測定問題卻少有探討及解決。養殖上氨氮測定的特色為:試水的鹽度變化可涵蓋整個海、淡水範圍,及氨氮的濃度高且範圍大。據經驗顯示,靛藍法因在海、淡水中的反應速率及吸光係數大不相同,因而在比較不同鹽度的水中氨濃度時,其結果常因鹽度及pH干擾及因稀釋的誤差而不易判讀,此問題在快速自動分析 ( 通常為不完全反應下之測定 ) 更因加上呈色反應慢之限制而更顯嚴重。
為有系統地探討靛藍法在養殖上的測定問題及謀求改善,本研究因此以Strickland and Parsons ( 1972 ) 法 ( SP法 ) 為基礎依序分三個部份進行。
第一部份實驗:比較海水及淡水在不同最終pH條件下對靛藍法吸收光譜的影響。以其經海、淡水實驗後最佳吸收波長及吸光值的主要因素是最終pH而非鹽度,且海、淡水均適用的最佳吸收波長為630nm,最佳pH為10.5。同時,由本實驗亦可發現海水中的鹽度干擾實際上是因反應的最終pH不同所造成的,且經由最佳模式化結果,顯示當pH在9.8~10.5時吸光係數與最終pH有良好的二次模式關係(R2>98%),似可用來校正SP法測定結果因最終pH不同而造成的差異 ( 數學模式修正法 )。
第二部分:比較靛藍法在不同海水比例下的NaOH滴定曲線及緩衝容量,以探討海水鹽度對最終pH的影響,並求出不同海水比例在最佳pH下所需的NaOH最佳添加量。由結果顯示,NaOH滴定曲線隨海水比例不同而異,經比對結果與理論滴定曲線並無顯著差異。因此顯然可知,海水比例不同會影響靛藍法的最終pH,更確定鹽度干擾效應來自於最終pH不同。且由本實驗滴定曲線所求得之NaOH最佳添加量,似可用於試劑的調整以抵銷所謂的〝鹽度干擾〞的問題( 試劑修正法 )。
第三部份:以標準曲線及實際樣品比較SP法、數學模式修正法及試劑修正法對6種不同比例海水樣品的測定效果。由標準曲線結果顯示:海水比例會影響SP法的標準曲線斜率,對試劑修正法及數學模式修正法的標準曲線則無影響。經由養殖池實際樣品測定的驗證結果顯示:SP法的最終pH值隨鹽度增加而減少,試劑修正法的最終pH則不受鹽度影響而定數在10.5左右,數學模式修正法的最終pH值則固定在10.5。另經卡方試驗結果顯示數學模式修正法確實與試劑修正法的符合性較高。
由本研究結果可確實證明靛藍法測氨的鹽度干擾問題事實上是因反應最終pH不同所造成的。同時,亦可得知靛藍法最佳吸收波長為630nm,最佳pH為10.5。因此,若能如本研究的試劑修正法依試水滴定曲線調整試劑NaOH用量,將最終pH定數在10.5左右,即可去除鹽度干擾,進而得到不受海水或淡水影響的測定結果,且對高濃度試水的測定而言,亦不會因稀釋造成鹽度改變而帶來誤差。
第一章 前言 1
第二章 比較海水及淡水在不同最終pH條件下對靛藍法吸收光譜的影響 3
摘要 3
1.前言 4
2.材料與方法 6
3.結果 8
4.討論 10
第三章 比較靛藍法在不同海水比例下的NaOH滴定曲線及緩衝容量 12
摘要 12
1.前言 13
2.材料與方法 15
2.1實驗上的滴定曲線及緩衝容量 15
2.1.1試劑材料準備 15
2.2理論上的滴定曲線及緩衝容量 17
2.2.1理論上滴定弱酸模擬流程 17
2.2.2理論上的滴定曲線公式 18
2.3更改試劑於不同比例海水之配方及測氨步驟 23
2.3.1 NaOH的添加量 22
2.4卡方測驗之符合性測驗 23
3.結果 24
4.討論 26
第四章 以SP法、數學模式修正法、以及試劑修正法比較不同
鹽度之不同水源之氨濃度 31
摘要 31
1.前言 32
2.材料與方法 34
3.結果 39
4.討論 43
第五章 總結 46
參考文獻 47
表 53
圖 62
個人簡歷 77
參考文獻
1.Aminot, A., Kirwood, D. S. and Kerouel, R., 1997. Determination of ammonia in seawater by the indophenol-blue method: Evaluation of the ICES NVTS I/C 5 questionnaire. Marine Chemistry 56 pp 59-75.
2.Benesch, R. and Mangelsdorf, P., 1972. Eine Methode zur colorimetrischen bestimmung von ammoniak in meerwasser. Helgolander wissenschgftliche Meeresuntersuchungen 23, pp 365-375.
3.Berthelot, M., 1859. Rep. Chem. Appl. 1.282-284.
Bower, C. E. and T. Holm-Hansen, 1980. Asalicylate-hypochlorite method for determination ammonia in sea water. Can. J. Fish. Aquat. Sci. 37:794-798.
4.Brzezinski, Mark A., 1987. Colorimetric determination of nanomolor concentrations of ammonia in seawater using solvent extraction. Marine Chemistry. Vol. 20, No.3, pp 277-288.
5.Colt, J. E. and D. A. Armstrong, 1981. Nitrogen toxicity to crustaceans, fish and molluscs. Proceedings of the Bio-Engineering symposium for fish culture in Allen, L. J. and E. C. Kimmey eds. Fish Culture Sction, Northeast Society of Conservation Engineers, pp 34-47.
6.Colt, J. and G. Tchobanoglous, 1978. Chronic exposure of channel catfish, Ictalurus pumctatus, to ammonia:Effect on growth and survival, Aquaculture, 15:353-372.
7.Downing, K. M. and J. C. Merkens, 1955. Dissolved oxygen concentration on the toxicity of un-ionized ammonia to rainbow trout (Salmo gairdnerii Richardson). Ann. Appl. Biol., 43:243-246.
8.Emmet, R. T., 1968. Direct spectrophotometric analysis of ammonia in natural water by the phenol-hypochlorite reaction. Nav. Ship. Res. Develop. Cent., Rep. 2570.
9.Folkard, A. R., 1978. Automatic analysis of sea water nutrients. Fisheries Technical Report No. 446. Ministry of Agriculture, Fisheries and Food, Lowestoft, pp 23.
10.Fromm, P. O. and Gillette, J. R., 1968. Effect ammonia on blood ammonia and nitrogen excrection of rainbow trout (salmo gairdneri). Comp. Biochem Physiol, 26:887-896.
11.Gardiner, J., 1973. Chloroisocyanurates in the treatment of swimming pool water. Wat. Res., 7(6)823-833.
12.Grasshoff, K., 1976. The automated determination of ammonia In: K. Grasshoff (Editor). Method of Seawater Analsis. Verlag Chemie Weinheim, pp 276-278.
13.Grasshoff, K. and Johannsen, H., 1972. A new sensitive and direct methods for the automatic determination of ammonia in sea water. J. Cons. Int. Explor. Mer. 34(3): 516-521.
14.Hampson, B. L., 1977. The analysis of ammonia in polluted sea water. Water Research. Vol. 11. No3. Pp305-308.
15.Hansen, H. P. and Grasshoff, K., 1983. Automated determination of ammonia. In: K. Grasshoff. M. Ehrhardt and F. Kremling (Editors), Methods of Seawater Analysis. Verlag Chemie, Weinheim, 2nd., pp363-365.
16.Harwood, J. E. and Huyser, D. J., 1970.Some aspects of the phenol-hypochlorite reaction as applied to ammonia analysis. Water Research. Vol. 4. pp501-515.
17.Head, P.C., 1971. An automated phenolhypochoorite method for the determination of ammonia in sea water. Deep sea Research
18, pp 531-532.
18.Huang, M. Y., Shyu C. Z., Lu M. Y., 1996. A comparison on the ammonia-N and nitrite-N in aquaculture system determined by different methods. J. Fish. Soc. Taiwan, 23(4):307-321.
19.Ivancic, I. And Degobbis, D., 1983. An optimal procedure for ammonia analysis in natural waters by the indophenol blue mathod. Water Res. Voi.18, No.9. pp 1143-1147.
20.Koroleff, F., 1969. Direct determination of ammonia in natural waters as indophenol blue. ICES C. M. 1969/C: 9, Hydrol. Commun., pp 4.
21.Koroleff, F., 1970. Direct determination of ammonia in natural waters as indophenol blue. In: ICES, Information on Techniques and Methods for Seawater Analysis, An Interlaboratory Report, 3: 19-22.
22.Krom, M. D., 1980. Spectrophotometric determination of ammonia: a study of a modified Berthlot reaction using salicylate and dichloroisocyanurate. Analyst 105, pp 305-316.
23.Le corre, P. and Treguer, P., 1978. Dosage de l’ammonium dans l’eau demer: comparison entre deux methods d’analyse automatique. Journal du Conseil International pour l’Exploration dela Mar. 38. pp 147-153.
24.Liddicoat M. I., Tibbits S. and Butler E. I., 1975. The determination of ammonia in water. Limnol Oceanogr, 19:131-132.
25.Loder, T. C. and Glibert, P. M., 1976. Blank and salinity corrections for automated nutribution UNH-SG-JR-101. To Technicon International Congress, December. pp 13-15.
26.Lubochinsky, B. and Zalta, J. P., 1954. Colormetric micro-determination of total nitrogen. Bull. Soc. Chim. Biol. 36, 1363-1366.
27.Mantoure, R. F. C. and Woddward, E. M. S., 1983. Optimization of the indophenol blue method water. Estuaeine Coastul andshelf Science. 17, pp 219-224.
28.Merkens, J. C. and K. M. Downing, 1957. The effect of tension of dissolved oxygen on the toxicity of un-ionized ammonia to several species of fish. Ann. Appl., Biol., 45:521-527.
29.Milne, M. D., B. H. Scribner and M. A. Craford, 1958. Non-ionic diffusion and excretion of weak acids and bases. Am. J. Med., 24:709-729.
30.Nimura, Y., 1973. A direct estimation of microgram amounts of ammonia in water without salt-error. Bull. Jap. Scient. Fish., 39: 1315-1324.
31.Patton, C. J. and Crouch, S. R., 1977. Spectrophotometric and kinetics investigation of the Berthelot reaction for the determination of ammonia. Anal. Chem., 49(3): 464-469.
32.Pym, R. V. E. and Milham, P. J., 1976. Selectivity of reaction among chlorine, ammonia, and salicylte for determination of ammonia. Analytical Chemistry., 48, 1413-1415.
33.Riley, J. P., 1975. The analytical chemistry of sea water. In chemical Oceanography (Rilet, J. P. and Skirrow, G., eds.) Vol. 3 . and editio, Academic Press, Comdon, pp 193-477.
34.Robinette, H. R., 1976. Effect of selected sublethal levels of ammonia om the growth of chan nel catfish (Ictalurus punctatus). Prog, Fish-Cult., 38:26-29.
35.Roskam, R. T. and De Langen, D., 1964. Asimple colorimetric method for the determination of ammonia in seawater. Anal. Chim. Acta. 30: 56-59.
36.Ruffier, P. J., Boyle, W. C., and Kleinschmidt, J., 1981. Short-term acute bioassays to evaluate ammonia toxicity and effluent standards. J. Water Pollution Control Fed., 53:367-377
37.Russo, R. C., 1985. Ammonia, nitrite, and nitrate. In Fundamentals of aquatic toxicology (G. M. Rand and S. R. Pctrocelli, eds.). Hemisphere, New York, pp455-471
38.Sagi, T., 1966. Determination of ammonia in sea water by the indophenol method and its application to coastal and off-shore water. Oceanogr. Mag., 18:43-51.
39.Sasaki, K. and Sawada, Y., 1980. Determination of ammonia in an estuary. Bulletin of the Japanese Society of Scientific Fisheries 46, 319-321.
40.Scheiner, D., 1976. Determination of ammonia in Kjeldahl nitrogen by indophenol method. Water. Research, 10:31-36.
41.Sillen, L. G., 1961. Thephysical chemistry of sea water, oceanography publication. Amer. Ass. Adv. Sci., No. 67. pp 549-581.
42.Slawyk, G. and Maclsaac, J. J., 1972. A comparison of two automated ammonium method in a region of coastal upwelling. Deep-Sea Res., 19:521-524
43.Smith, C. E. and Piper, R. G., 1975. Losion associated with chronic exposure to ammonia. In: The pathology of Fishes. (W.E. Ribelin and G. Migaki, eds.) 497-514. Vniv. Wis. Press, Madison.
Soderberg, R. W., McGee, M. V., Grizzle, J. M., and Boyd, C. E., 1984. Comparative histology of rinbow trout and channel catfish grown in intensive static water aquaculture. Progr. Fish. Cult., 46:195-199.
44.Solorzano L., 1969. Determation of ammonia in natural water by the phenolhypochlorite method. Limnol. Oceanogr, 14: 799-801.
Spotte, S., 1979. Fish and Invertebrate. Culture. Water management in closed systems, 2nd edn, Wiley-Interscience, New York, pp.114.
45.Strickland, J. D. H. and Parsons, T. R., 1972. A practical handbook of seawater analysis. Fisheries Research Board of Canada, pp 82-89.
46.Tabate, K., 1962. Suisa dobutsh nioyobosu ammonia no dokusei to pH, tunsan to no kakei (Toxicity of ammonia to aquatic animals with reference to effect of ph and carbon dioxide). Tokaiku Suisan Kenkyusho Knkyu Hokool 34:67-74. (In Japanese).
47.Verdouw, H., van Echteld C. J. A. and Dekkers M. J., 1978. Ammonia determination based on indophenol formation with sodium salicylate. Water Research, 12: 399-402.
48.Zadorojny, C., Saxton, S. and Finger, R., 1973. Spectrophotometric determination of ammonia. Journal Water Pollution Control Federation. Vol. 45, No.5, pp 905-912.
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