以電化學法去除水中多重藥物之研究

Removal of multiple pharmaceuticals from water by electrochemical methods

黃永凌(Yung-Ling Huang)

指導教授 ： 胡景堯

臺北醫學大學/公共衛生暨營養學院/公共衛生學系暨研究所/碩士(2014年)

摘要

摘要
近二十年來，全世界藥品的使用量日漸增加，個人藥品和護理用品（PPCPs）也在世界各地的廢水、地表水、地下水…等水體中，發現濃度範圍約為ng/L ~ug/L的藥物殘留，成為一種新興污染物。因為用藥種類繁多，傳統污水處理廠並不能有效去除水中的藥品，並已經從排放的污水裡檢測出有藥品殘留，尤其是醫院廢水；若將其直接排放至環境可能會導致潛在的環境風險。電化學法已經被用於處理許多污染物，其複雜的機制可以處理醫院廢水中複雜的污染物。本研究以電化學法去除在醫院廢水中被檢測出頻率較高的三種藥物（六個品項）：β-受體阻滯劑 - 阿替洛爾 (Atenolol)；非類固醇消炎止痛藥 - 乙醯氨酚 (Acetaminophen)、雙氯芬酸 (Diclofenac)、布洛芬 (Ibuprofen)、酮洛芬 (Ketoprofen)；磺胺類抗生素 - 磺胺甲噁唑（Sulfamethoxazole），作為去除之目標藥品。本研究所使用之電化學法中，主要以電解氧化法和電化學混凝浮除法去除目標藥品。兩種方法之間的主要差異為所採用的電極板材料不同所致；反應系統使用鋁和不鏽鋼作為犧牲性電極板，以石墨作為非犧牲性電極板。
結果顯示，在單一藥品環境之下，疏水性較強的藥品比較容易在電混凝浮除法中被去除；而除了布洛芬 (Ibuprofen)和酮洛芬 (Ketoprofen)之外，大部份的藥品可以在電化學氧化過程當中被有效去除。在多重藥品系統中，發現經由電解氧化的反應後，水中解離程度較大的藥品，以電解氧化法處理後有較佳的藥品去除率。將此反應方法應用在醫院實廠廢水的模擬實驗之下，結果顯示所有藥品的去除率與合成廢水相似；且醫院廢水的進流水與放流水相比，進流水中有較佳的藥品去除率，因為此醫院污水處理流程在將廢水放流前，會添加含有三氯異氰酸之氯錠消毒，故水體中有氯錠分解後殘留的鈣離子影響導電效果所致。
最後，使用HPLC-DAD和UPLC - Q – TOF-MS來鑑定的氧化產物，發現經過電解氧化處理，雙氯芬酸(Diclofenac)與次氯酸反應後，會被附著一個氯離子而產生一新副產物；乙醯氨酚(Acetaminophen)則會聚合為二聚體分子。故本方法可以被應用到醫院廢水廠中二級前處理的部分，以利生物礦化殘留藥品之效果，增加實際的藥品去除率。

關鍵字

電化學法 ； 電解氧化法 ； 電化學混凝浮除法 ； 醫院廢水 ； 乙醯氨酚 ； 雙氯芬酸 ； 布洛芬 ； 酮洛芬 ； 磺胺類抗生素 ； 磺胺甲噁唑 ； 阿替洛爾 ； 極致液相層析 - 四極桿飛行時間質譜儀 ； 高效能液相層析儀

並列摘要

Abstract
During the last two decades, the amount of drug-using increase constantly in the world. Pharmaceuticals and personal care products (PPCPs) have been detected as emerging contaminants of the novel concern in the aquatic environment. Due to the variety of pharmaceutical compounds are used in the whole medical treatment, and the traditional urban sewage water treatment plants can not remove the pharmaceuticals completely, some of these compounds can be detected in the wastewater, especially in the hospital wastewater. The direct discharge of these effluents into sewerage system, therefore, may lead to a potential risk to the environment. Electro-chemical process has been used to treat many kinds of pollutants and its complex mechanism may be also useful to treat the complex pollutants in hospital wastewater or effluents.
The chosen pharmaceuticals in this research are acetaminophen, diclofenac, ibuprofen, ketoprofen, sulfamethoxazole and atenolol, which are often detected in the hospital effluent wastewater. There are two kinds of electrochemical processes were used in this research, electro-oxidation and electrocoagulation-flotation. The difference between the two reactions is caused by the different material of the electrodes they used. Aluminum and stainless steel are used as the sacrificial electrodes for electrocoagulation-flotation process and graphite is used for electro-oxidation process.
The results show that as single pharmaceutical in the water only hydrophobic pharmaceuticals can be removed by electrocoagulation-flotation process; while the most of the pharmaceuticals (except ibuprofen and ketoprofen) can be effectively removed by electro-oxidation process. In multiple- pharmaceuticals system, it can be found that the dissociated pharmaceuticals were more effectively removed than the neutral compounds in electro-oxidation process. The results of hospital waste water shows the removal efficiencies of all pharmaceuticals were similar to those in synthetic wastewater. The removal rate of pharmaceuticals, however, was better in the influent water than that in the effluent water because the residual calcium ions from the usage of trichloroisocyanuric acid tablets in the effluent.
Finally, HPLC-DAD and UPLC-Q-TOF-MS was used to identify oxidation products, which finds that after electro-oxidation, diclofenac is attached of one chlorine by hypochlorite and a dimer polymer of acetaminophen was produced. These results are useful in using for the pre-treatment of secondary water treatment; thus, the biodegradation of the pharmaceuticals can be better and more efficacy.

並列關鍵字

Electrochemical reaction ； electro-oxidation ； electrocoagulation-flotation ； hospital wastewater ； Acetaminophen ； Diclofenac ； Ibuprofen ； Ketoprofen ； Sulfamethoxazole ； Atenolol ； Ultra-Performance Liquid Chromatography Quadrupole Time of Flight Mass Spectrometry (UPLC-Q-TOF-MS) ； High performance liquid chromatography (HPLC)

參考文獻

文獻探討

1. Moldovan, Z., Occurrences of pharmaceutical and personal care products as micropollutants in rivers from Romania. Chemosphere, 2006. 64(11): p. 1808-1817.

2. Sim, W.J., et al., Evaluation of pharmaceuticals and personal care products with emphasis on anthelmintics in human sanitary waste, sewage, hospital wastewater, livestock wastewater and receiving water. J Hazard Mater, 2013. 248-249: p. 219-27.

3. Lin, A.Y. and Y.T. Tsai, Occurrence of pharmaceuticals in Taiwan's surface waters: impact of waste streams from hospitals and pharmaceutical production facilities. Sci Total Environ, 2009. 407(12): p. 3793-802.

4. Mompelat, S., B. Le Bot, and O. Thomas, Occurrence and fate of pharmaceutical products and by-products, from resource to drinking water. Environment International, 2009. 35(5): p. 803-814.