固定化生物技術對抗生素及非類固醇類消炎止痛藥之生物降解與生物吸附研究

Bio-Degradation and Bio-Sorption of Antibiotics and Non-Steroidal Anti-Inflammatory Drugs by Immobilized Cell Bio-Process

余宗賢(Tsung-Hsien Yu)

指導教授 ： 林正芳

共同指導教授 ： 林郁真(Angela Yu-Chen Lin)

國立臺灣大學/工學院/環境工程學研究所/博士(2011年)

https://doi.org/10.6342/NTU.2011.10091

摘要

藥物和個人保健用品(pharmaceuticals and personal care products)不僅用以治療人類及動物的疾病，另亦用於畜牧養殖業及水產養殖業等，但藥物經食用後仍會以原型態及代謝型態隨著尿液及糞便排出，導致廢污水殘留藥物。目前廢污水需經由污水處理廠處理後才可排放，但傳統污水處理廠之設計並非針對藥物去除，故傳統污水處理廠無法有效地去除污水中之殘留藥物，且去除效能變異非常大(無去除~幾乎完全去除)。一般而言，藥物去除效率隨污泥停留時間(solid retention time)增加而提升，而固定化生物技術(immobilized cell bio-process)具有長污泥停留時間，且兼具好氧及厭氧程序可有效去除碳和氮。因此，共選定4種抗生素(sulfadimethoxine、sulfamethazine、sulfamethoxazole、trimethoprim)及4種非類醇類消炎止痛藥(acetaminophen、ibuprofen、naproxen、ketoprofen)等8種藥物為目標抗生素與止痛藥，並探討上流式固定化生物技術反應槽對於目標抗生素與止痛藥之處理效能，再藉由批次式實驗評估目標抗生素與止痛藥之主要去除機制及去除動力，及評估各目標抗生素與止痛藥之吸附及脫附特性。
上流式固定化生物反應槽對acetaminophen及ibuprofen之單位污泥吸附降解量介於0.5 ~ 12.3 µg/g-sludge/day (1 ~ 100 µg/L進流濃度)；ketoprofen及naproxen則為0.6 ~ 1.6 µg/g-sludge/day (5 ~ 15 µg/L進流濃度)；sulfadimethoxine、sulfamethazine及sulfamethoxazole為0.2 ~ 0.9 µg/g-sludge/day (2 ~ 10 µg/L進流濃度)；trimethoprim為0.1 µg/g-sludge/day (1 µg/L進流濃度)。
由批次實驗結果得知，目標抗生素與止痛藥之主要去除機制為生物降解作用(bio-degradation)及生物吸附作用(bio-sorption)，而揮發作用(volatilization)及水解作用(hydrolysis)均可忽略。依據生物降解及生物吸附可分成以下類型：acetaminophen可被歸類為易生物降解/易生物吸附之物質；sulfamethoxazole、sulfadimethoxine、ibuprofen及naproxen則被歸類為難生物吸附/易生物降解；sulfamethazine及ketoprofen則歸類為難生物吸附/難生物降解之物質；trimethoprim則為中等生物吸附/難生物降解之物質。
依據擬一階生物吸附降解反應速率常數(pseudo-first order bio-sorption-degradation rate constant)，acetaminophen及ibuprofen可歸類為容易生物吸附降解之物質，其次為sulfamethoxazole、sulfadimethoxine、naproxen及trimethoprim，而sulfamethazine及ketoprofen則為較難被生物吸附降解作用去除之物質。就90%去除時間(time required for 90% removal, t90)而言，以acetaminophen及ibuprofen之t90為最短，分別為2.1及2.6日；其次為sulfamethoxazole、sulfadimethoxine、trimethoprim及naproxen (7.2 ~ 14.3日)；而sulfamethazine及ketoprofen為最長，分別為39.7及44.0日。
由吸附脫附試驗結果，acetaminophen、sulfamethoxazole及sulfadimethoxine屬於易吸附/不易脫附物質；sulfamethazine、trimethoprim及naproxen歸類為中等吸附/易脫附物質；ibuprofen及naproxen屬於不易吸附/易脫附物質。

關鍵字

固定化生物處理 ； 抗生素 ； 非類固醇類消炎止痛藥 ； 生物降解 ； 生物吸附

並列摘要

Pharmaceuticals are widely used not only for curing human and animal diseases, but also in farming and aquaculture. Depending on the nature of the pharmaceuticals, parent compounds and metabolites of pharmaceuticals are excreted via urine and feces. Most of wastewater is typically treated by wastewater treatment plants (WWTPs). Since the existing domestic WWTPs are not specially designed for pharmaceuticals removal, their removal in WWTPs is often incomplete, and the degree of removal varied broadly from nearly complete to very little. In general, the removal of pharmaceuticals increases with the increase of solid retention time. Immobilized cell biological process is one of the biological treatment technologies with longer sludge retention time and combination of aerobic and anaerobic process that has excellent potential for carbon and nitrogen removal.
The aims of this study were to: 1) investigate treatability of eight selected pharmaceuticals (four antibiotics: sulfamethoxazole, sulfadimethoxine, sulfamethazine and trimethoprim and four non-steroidal anti-inflammatory drugs (NSAIDs): acetaminophen, ibuprofen, naproxen and ketoprofen) with various influent concentrations by up-flow immobilized cell bio-process at a constant operation, 2) evaluate potential elimination mechanism (bio-degradation, bio-sorption, hydrolysis and volatilization) and their kinetics using batch experiment, and 3) study sorption/desorption capacity and solid-liquid partitioning coefficient by batch experiment.
These removal efficiencies are good and steady even at high initial concentrations, removal rate ranging from 0.5 µg/g-sludge/day (at 5 µg/L) to 12.3 µg/g-sludge/day (at 100 µg/L) for acetaminophen and ibuprofen, 0.6 ~ 1.6 µg/g-sludge/day (at 5 ~ 15 µg/L) for ketoprofen and naproxen, 0.2 ~ 0.9 µg/g-sludge/day (at 2 ~ 10 µg/L) for sulfonamide antibiotics, and 0.1 µg/g-sludge/day (at 1 µg/L) for trimethoprim.
In the batch experiment, bio-degradation and bio-sorption were found to be the dominant elimination routes, while volatilization and hydrolysis can be ignored for all target pharmaceuticals. Based on the batch experiment results, acetaminophen was characterized by significant biodegradability and sorption, resulting in 100% removal in 8 days via sorption and > 25% removal by bio-degradation within 2 days. Sulfamethoxazole, sulfadimethoxine, ibuprofen and naproxen were fairly well biodegraded (> 40% removal) and hardly sorbed (< 40% removal) to the bio-carriers. Sulfamethazine and ketoprofen were slowly biodegraded and weakly sorbed, resulting in removal of 23% and 28% by bio-degradation and 20% and 18% by sorption. The fate of trimethoprim was characterized by low biodegradability (27%) and medium sorption (47%). Based on pseudo-first bio-sorption-degradation kinetic rate constants of target pharmaceuticals, acetaminophen and ibuprofen are readily bio-sorption-degradable substances, followed by sulfamethoxazole, sulfadimethoxine, naproxen and trimethoprim are slowly, while sulfamethazine and ketoprofen are hardly bio-sorption-degradable pharmaceuticals. Moreover, the time required for 90% removal (t90) via bio-sorption-degradation for acetaminophen and ibuprofen were 2.1 and 2.6 days, followed by sulfamethoxazole, sulfadimethoxine, trimethoprim and naproxen (7.2 ~ 14.3 days), while sulfamethazine and ketoprofen were persistent in immobilized cell system due to their longer t90 of 2.2 ~ 13.3 days.
In the sorption/desorption experiment, acetaminophen, sulfamethoxazole and sulfadimethoxine were characterized by strong sorption and weak desorption. A phenomenon of moderate sorption and well desorption was observed for sulfamethazine, trimethoprim and naproxen. Both ibuprofen and ketoprofen were weakly sorbed and strongly desorbed.

並列關鍵字

Immobilized cell biological process ； Antibiotics ； Non-steroidal anti-inflammatory drugs ； Bio-degradation ； Bio-sorption

參考文獻

Grady, C.P.L., Daigger, G.T., Lim, H.C., 1999. Biological wastewater treatment. Marcel Dekker, New York.

Abegglen, C., Joss, A., McArdell, C.S., Fink, G., Schlüsener, M.P., Ternes, T.A., Siegrist, H., 2009. The fate of selected micropollutants in a single-house MBR. Water Research 43, 2036-2046.

Alcock, R.E., Sweetman, A., Jones, K.C., 1999. Assessment of organic contaminant fate in waste water treatment plants I: Selected compounds and physicochemical properties. Chemosphere 38, 2247-2262.

Alexy, R., Kumpel, T., Kummerer, K., 2004. Assessment of degradation of 18 antibiotics in the Closed Bottle Test. Chemosphere 57, 505-512.

Batt, A.L., Kim, S., Aga, D.S., 2006. Enhanced biodegradation of iopromide and trimethoprim in nitrifying activated sludge. Environmental Science & Technology 40, 7367-7373.