河川底泥中壬基苯酚與腐植化物質相互反應及δ-MnO2對壬基苯酚之氧化降解作用

Oxidative degradation of nonylphenol in river sediments by δ-MnO2 and interactions of nonylphenol with humic substances

蔡佩蓉(Pey-Rong Tsai)

指導教授 ： 張簡水紋 ； 王敏昭

朝陽科技大學/理工學院/環境工程與管理系/碩士(2012年)

摘要

壬基苯酚(nonylphenol, NP)結構式與雌性激素類似，具有高潛勢之生物內分泌干擾物質，被稱為環境荷爾蒙。壬基苯酚屬於疏水性(hydrophobicity)有機微污染物(log Kow = 4.48)，易與底泥中腐植化物質(humic substance, HS)產生鍵結，尤其是水溶性腐植酸(humic acid, HA)。本研究添加壬基苯酚(NP)以及添加0.02%乙基汞柳酸鈉(sodium ethylmercurthiosalicyclate, thimerosal)殺菌劑之河川底泥懸浮液，利用0.1 M HCl 及0.1 M NaOH調節其pH值為4.00，6.00及8.00，再分別添加腐植酸及黃酸(fulvic acid, FA)。於室溫下測定反應系統中壬基苯酚與腐植酸或黃酸的鍵結反應。另外，以自行研發設計且獲專利之氣體吸收及釋放反應瓶，於室溫(25℃)、滅菌及常壓下，於河川底泥中壬基苯酚有無添加腐植酸或黃酸經由δ-MnO2之氧化及礦化作用（mineralization）。研究指出添加δ-MnO2可促進壬基苯酚降解釋出CO2 。然而，添加腐植化物質會降低δ-MnO2對壬基苯酚 礦化釋出CO2，但是對壬基苯酚降解反而上升。以傅立葉轉換紅外線光譜儀(FT-IR)分析壬基苯酚與腐植化物質相互反應後，壬基苯酚之苯環結構產生結合轉移為其他產物。這明確指出底泥中腐植化物質會以非生物性緩慢破壞壬基苯酚，經添加δ-MnO2加速氧化及礦化壬基苯酚之苯環結構釋出CO2及其他產物， 減少壬基苯酚對環境潛在之危害。進而，以動力學及等溫吸附模式在不同pH值下，底泥中壬基苯酚和腐植化物質符合Dubinin–Radushkevich和Temkin之等溫吸附模式，以二階動力學反應為主。本實驗之數據及參數，可作為規劃整治河川底泥中壬基苯酚污染之方針。

關鍵字

二氧化錳 ； 礦化作用 ； 腐植酸 ； 黃酸 ； 壬基苯酚 ； 底泥

並列摘要

Nonylphenol (NP) is a degraded product of nonylphenol polyethoxylate (NPnEO) mode surfactants which accounted for 80% of the non-ionized detergent used. It is widely proliferated in the streams and creeks of country because of illegal dumping into effluent waters of NPnEO surfactants. Since the structure of NP is similar to estrogen, NP possesses the ability to mimic natural hormones by interaction with estrogen receptors. It has been confirmed that, once NP runs into human body, it will decrease male sperm count and interfere normal metabolism. It will also reduce immunity, interfere physiology, and cause breast and testicular cancer when exposures at NP-contaminated environment in a long time. Nonylphenol would also reduce and inhibit estrogen efficacy in animals and zooplankton.
Manganese oxides are involved in many environmentally important minerals because they are strongly oxidizing and can affect the fate and transport of metals and organic compounds through oxidative/reductive reactions. Birnessite (its synthetic analogue is δ-MnO2) is an abundant naturally occurring mixed valence oxide. Natural organic matter (NOM) is ubiquitous in the environment and can be involved in the interaction between contaminants. Aquatic humicsubstances have a greater sorption capacity for nonylphenol. This work focuses primarily on the oxidation of nonylphenol in river sediments by δ-MnO2 (birnessite) and interaction with humic substances. The results showed that addition of δ-MnO2 to nonylphenol was mineralized and release CO2. However, addition of humic substances to nonylphenol in the presence of δ-MnO2 will reduce the decarboxylation and increase the nonylphenol degradation. Therefore, δ-MnO2 had good decomposition effects on nonyphenol in the presence of humic substances. Nonylphenol and humic substances interactions were analyses by FT-IR. The kinetics studies of adsorption isotherm at different pH values, of NP and HA in sediments was described by Dubinin-Radushkevich and Temkin adsorption isotherm models, and mainly pseudo-second -order kinetics.

並列關鍵字

δ-MnO2 ； Mineralization ； Fulvic acid ； Humic acid ； Nonylphenol ； Sediment

參考文獻

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