Sevde ÜSTÜN ODABAŞI, Bareera MARYAM, Hanife BÜYÜKGÜNGÖR

Diklofenak İlaç Kalıntısının UV ve UV/ H2O2 Yöntemleri ile Gideriminin Karşılaştırılması

Dünya nüfusunun hızlı artışına paralel olarak ilaç tüketimi artış göstermektedir. İlaçlar kullanıldıktan sonra bir kısmı vücut tarafından metabolize edilirken kalan kısmı ise vücuttan idrar yoluyla atılmaktadır. Atıksu arıtma tesislerine ulaşan bu ilaçlar biyolojik yöntemlerle arıtılamamakta ve oradan alıcı ortamlara deşarj edilmektedir. Bu nedenle ilaç kalıntılarının giderimlerinde yüksek verimine sahip olan ileri oksidasyon yöntemleri kullanılmaktadır. Çalışmada analjezik, antipiretik ve antiromatizmal etkiye sahip olan non-sterodial anti-inflamatuar (NSAİ) ilaç grubuna giren diklofenak ilacından oluşturulan sentetik suyun UV ve UV/H2O2 yöntemleri ile giderim verimleri karşılaştırılmıştır. Bu çalışmada ilaç derişimleri LCMS/MS cihazı kullanılarak ölçülmüştür. Çalışma sonucunda diklofenağın UV prosesi ile giderimi %90 verim ile gerçekleşirken UV/H2O2 prosesi ile giderim verimi ise %100 bulunmuştur. Bu sonuçlara göre hidrojen peroksit ilavesinin ilaç kalıntılarının gideriminde daha etkili olduğu görülmüştür. Çalışma sonucunda UV ve UV/H2O2 prosesleri ile diklofenağın mineralizasyonu ile ilgili kinetik çalışmaları yapılmış ve her iki proses içinde birinci dereceden reaksiyon hız sabitleri belirlenmiştir.

Anahtar Kelimeler:

Diklofenak, İlaçlar, LCMS/MS, UV, UV/ H2O2

Comparison of Removal of Diclofenac Pharmaceutical Residue by UV and UV/ H2O2

Along with the rapid growth of the world population, drug consumption is also increasing. In case of all the drugs, some part of it is metabolized by the body after its consumption, while the rest is excreted via urine. These drugs reaching the wastewater treatment plants cannot be treated by biological methods and are discharged to the receiving environment. For this reason, advanced oxidation methods with high removal efficiency are used for drug residues removal. In the study, removal efficiencies of diclofenac drug, which belong to the non-steroidal anti-inflammatory (NSAID) drug group and has analgesic, antipyretic and antirheumatic effect, were determined using UV and UV/ H2O2 methods from synthetic water. Drug concentrations were measured using LCMS / MS instrument. And it was found that, the removal of diclofenac by UV process was 90% and the recovery by real UV / H2O2 process was 100%. These results show that hydrogen peroxide addition is more effective in the removal of drug residues. In the scope of study, the kinetic studies on the mineralization of diclofenac with UV and UV / H2O2 processes were also carried out and first order kinetic was determined for both of the processes.

Keywords:

Diclofenac, Pharmaceuticals, LCMS/MS, UV, UV/H2O2,

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Al-Rifai J.H., Gabelish C.L., Schäfer A.I. (2007). Occurrence of Pharmaceutically Active and Non-Steroidal Estrogenic Compounds in Three Different Wastewater Recycling Schemes in Australia, Chemosphere, 69(5), 803-815.
Basavaraju M.M. (2012). Degradation Kinetics of Diclofenac in Water by Fenton’s Oxidation, Journal of Sustainable Energy and Environment, 3,173-176.
Behera S.K., Kim H.W., Oh J.E., Park H.S. (2011). Occurrence and Removal of Antibiotics, Hormones and Several Other Pharmaceuticals in Wastewater Treatment Plants of the Largest Industrial City of Korea, Science of Total Environment, 409,4351-4360.
Ben Abdelmelek S., Greaves J., Ishida K.P., Cooper W.J., Song W. (2011). Removal of Pharmaceutical and Personal Care Products from Reverse Osmosis Retentate Using Advanced Oxidation Processes, Environmental Science and Technology, 45(8), 3665-3671.
Bo L., Feng L., Fu J., Li P., Zhang Y. (2015). The Fate of Typical Pharmaceuticals in Wastewater Treatment Plants of Xi’an City in China, Journal of Environmental Chemical Engineering, 3, 2203-2211.
Buser H.R., Poiger T., Muller M. (1998). Occurrence and Fate of the Pharmaceutical Drug Diclofenac in Surface Waters: Rapid Photo-Degradation in A Lake, Environmental Science and Technology, 32, 3449-3456.
Crittendena, J.C., Hu S., Hand D.W., Gren S.A. (1999). A Kinetic Model for H2O2/UV Process in a Completely Mixed Batch Reactor, Water Research, 33, 2315-2328.
Çatalkaya E.Ç., Bali U., Şengül F. (2004). Fenol‟ün Fotokimyasal Yöntemlerle Parçalanması ve Mineralizasyonu, Su Kirlenmesi ve Kontrolü Dergisi, 14(3), 31-41.
Epold I., Dulova N., Trapido M. (2012). Degradation of Diclofenac in Aqueous Solution by Homogeneous and Heterogeneous Photolysis, Journal of Environmental Engineering and Ecological Science, http://dx.doi.org/10.7243/2050-1323-1-3.
Heberer T. (2002). Occurrence, fate, and removal of pharmaceutical residues in the aquatic environment: A Review of Recent Research Data, Toxicology Letters, 131 (1/2), 5–17.
Ikehata K, Naghashkar N.J, Gamal El-Din M. (2006). Degradation of Aqueous Pharmaceuticals by Ozonation and Advanced Oxidation Processes: A review, Ozone Science and Engineering, 28, 353-414.
Jiang J.O., Zhou Z., Sharma V.K. (2013). Occurrence, Transportation, Monitoring and Treatment of Emerging Micro-Pollutants in Waste Water-A Review From Global Views, Microchemical Journal, 110, 292-300.
Kabak H. (2008). Kullanılan Bazı Tıbbi İlaçların Canlı Aktif Çamur Biyokütlesi Tarafından Adsorplanma Özelliğinin İncelenmesi. Doktora Tezi, Çukurova Üniversitesi, Adana, Türkiye.
Kanat İ.H. (2011). Yaygın Kullanılan Bazı Ağrı Kesici ve Veteriner İlaçlarının Koagülasyon ile Giderim Verimlerinin İncelenmesi. Yüksek Lisans Tezi, Çukurova Üniversitesi, Adana, Türkiye.
Kim I., Yamashita N., Tanaka H. (2009a). Photodegradation of Pharmaceuticals and Personal Care Products during UV and UV/H2O2 Treatments, Chemosphere, 77, 518-524.
Kim I., Yamashita N., Tanaka H. (2009b). Performance of UV and UV/H2O2 Processes for the Removal of Pharmaceuticals Detected in Secondary Effluent of a Sewage Treatment Plant in Japan, Journal of Hazardous Materials, 166, 1134-1140.
Kim S.D., Chou J.W., Kim I.S., Vanderford B.J., Snyder S.A. (2007). Occurrence and Removal of Pharmaceuticals and Endocrine Disruptors in South Korean Surface, Drinking, and Waste Water, Water Research, 4,1013-1021.
Klavarioti M., Mantzavinos D., Kassinos D. (2009). Removal of Residual Pharmaceuticals from Aqueous Systems by Advanced Oxidation Processes, Environment International, 35 (2), 402-417.
Kolpin D.W., Furlong E.T., Meyer M.T., Thurman E.M., Zaug S.D., Barber L.B., Buxton H.T. (2002). Pharmaceuticals, Hormones, and Other Organic Wastewater Contaminants in U.S. Streams, 1999-2000: A National Reconnaissance, Environmental Science and Technology, 36(6), 1202-1211.
Kümmerer K. (2001). Drugs in the Environment-. Emissions of Drugs, Diagnostic Acids and Disinfectants into Wastewater by Hospitals in Relation to Other Sources-A Review, Chemosphere, 45, 957-969.
Landsdrop D., Vree T.B., Hanssen T.J., Guelen P.M.J. (1990). Pharmacokinetics of Rectal Diclofenac and Its Hydroxyl Metabolites in Man”. International Journal of Clinical Pharmacology, Therapy, and Toxicology, 28(7), 298-302.
Liu N., Zheng M., Sijak S., Tang L., Xu G., Wu M. (2015). Aquatic Photolysis of Carbamazepine by UV/H2O2 and UV/Fe(II) Processes, Research on Chemical Intermediates, 41, 7015-7028.
Naddeo V., Belgiorno V., Ricco D., Kassinos D. (2009). Degradation of Diclofenac during Sonolysis, Ozonation and Their Simultaneous Application, Ultrasonics Sonochemistry, 16, 790-794.
Nghiem L.D., Schäfer A.I., Elimelech M. (2005). Pharmaceutical Retention Mechanisms by Nanofiltration Membranes, Environmental Science and Technology, 39 (19), 7698–7705.
Peker İ. (2007). Çevre Mühendisliğinde Temel İşlemler, Birsen Yayınevi, İstanbul, Türkiye.
Perez-Estrada L.A., Malato S., Gernjak W., Aguera A., Thurman E.M., Ferrer I., Fernandez-Alba A.R. (2005). Photo-Fenton Degradation of Diclofenac: Identification of Main Intermediates and Degradation Pathway, Environmental Science and Technology, 39, 8300-8306.
Romero V., González O., Bayarri B., Marco P., Giménez J., Esplugas S. (2015). Performance of Different Advanced Oxidation Technologies for the Abatement of the Beta-Blocker Metoprolol, Catalysis Today, 240, 86-92.
Santos J.L., Aparicio I., Callejón M., Alonso E. (2009). Occurrence of Pharmaceutically Active Compounds During 1-Year Period in Wastewater from Four Wastewater Treatment Plants in Seville (Spain), Journal of Hazardous Materials, 164, 1506-1516.
Scheurell M., Franke S., Shah R.M., Hühnerfuss H. (2009). Occurrence of Diclofenac and Its Metabolites in Surface Water and Effluent Samples from Karachi, Pakistan. Chemosphere, 77(6), 870-876.
Shraim A., Diab A., Alsuhaimi A., Niazy E., Metwally M., Amad M., Sioud, Dawoud A. (2017). Analysis of Some Pharmaceuticals in Municipal Wastewater of Almadinah Almunawarah, Arabian Journal of Chemistry, 10, 719-729.
Sönmez G. (2015). İleri Oksidasyon Prosesleri ile Bazı İlaç Kalıntılarının Giderimi. Doktora Tezi, Aksaray Üniversitesi, Aksaray, Türkiye.
Sönmez G., Işık M. (2017). Removal of Caffeine and Paracetamol Pharmaceutical Residues by UV and UV-H2O2, Sigma Journal of Engineering and Natural Sciences, 8(3), 235-244.
Stülten D., Zülke S., Lamshöft M., Spiteller M. (2008). Occurrence of Diclofenac and Selected Metabolities in Sewage Effluents, Science of the Total Environment, 405(1-3), 310-316.
Sun Q., Lv M., Hu A., Yang X., Yu C.P. (2014). Seasonal Variation in the Occurrence and Removal of Pharmaceuticals and Personal Care Products in a Wastewater Treatment Plant in Xiamen, China, Journal of Hazardous Materials, 277, 69-75.
Ternes T.A. (1998). Occurence of drugs in German Sewage Treatment Plants and Rivers, Water Research, 32, 3245-3260.
Tchobonoglous G., Burton F.L., Stensel H.D., Metcalf-Eddy. (2003).Wastewater Engineering Treatment and Reuse, 4th Edition, McGraw-Hill, Newyork, USA.
The New York Times. Drugs Are in the Water. Does It Matter? URL (Erişim Tarihi: 06.03.2018) http://www.nytimes.com/2007/04/03/science/earth/03water.html.
Üstün Odabaşı S., Büyükgüngör H. (2017). Removal of Diclofenac in Drinking Water with Fenton Process, European Water, 58, 41-46.
Verliefde A.R.D., Heijman S.G.J., Cornelissen E.R., Amy G., Van der Bruggen B., van Dijk J.C. (2007). Influence of Electrostatic İnteractions on the Rejection with NF and Assessment of The Removal Efficiency During NF/GAC Treatment of Pharmaceutically Active Compounds in Surface Water, Water Research, 41(15), 3227–3240.
Vogna D., Marotta R., Napolitano A., Andreozzi R., D’Ischia M. (2004). Advanced Oxidation of Pharmaceutical Drug Diclofenac with UV/H2O2 and Ozone, Water Research, 38, 414-422.
von Gunten U. (2003). Ozonation of Drinking Water: Part II. Disinfection and By-product Formation in Presence of Bromide, Iodide or Chlorine, Water Research, 37(7), 1469-1487.
Yangali-Quintanilla V., Sadmani A., McConville M., Kennedy M., Amy G. (2010). A QSAR Model for Predicting Rejection of Emerging Contaminants (Pharmaceuticals, Endocrine Disruptors) by Nanofiltration Membranes, Water Research, 44(2), 373-384.
Yu H., Nie E., Xu J., Yan S., Cooper J.W., Song W. (2013). Degradation of Diclofenac by Advanced Oxidation and Reduction Processes: Kinetic Studies, Degradation Pathways and Toxicity Assessments, Water Research, 47, 1909-1918.
Zhou S., Xia Y., Li T., Shi Z., Zhu S. (2016). Degradation of Carbamazepine by UV/Chlorine Advanced Oxidation Process and Formation of Disinfection By-Products, Environmental Science and Pollution Research, 23, 16448-16455.