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The use of treated wastewater for agricultural irrigation, is a common practice in several countries as it has several benefits, such as decreasing pressure on freshwater sources and reduced nutrient loads to receiving waters. However, wastewater treatment plants (WWTP) are not always able to remove all the contaminants present, thus representing a significant risk for environmental contamination. Soil contamination by wastewater may potentially promote contaminants uptake and accumulation by plants and derived products which consequently can affect human health. Pathogens and heavy metals are traditionally the main concern, however contaminants of emerging concern (CECs), and particularly pharmaceutical and personal care products (PPCPs), are gaining scientific and public attention. In the present dissertation, the electrokinetic (EK) process was applied as a remediation technology to an agricultural soil contaminated with a mixture of PPCPs. To better understand the remediation mechanisms involved, different assays were developed to discriminate biotic, abiotic and EK contributions, alone and coupled, to the degradation of the PPCPs. As environmental factors may affect the remediation processes, trials with and without irrigation and at different temperatures were also conducted (18 and 24 ºC). As contaminants, 10 commonly environmentally occurring PPCPs were selected for the study: 17β-estradiol (E2), sulfamethoxazole (SMX), bisphenol A (BPA), ibuprofen (IBU), 17α-ethinylestradiol (EE2), oxybenzone (OXY), triclosan (TCS), diclofenac (DCF), caffeine (CAF) and carbamazepine (CBZ). These compounds represent the major PPCPs classes and attain diverse physicochemical properties. All experiments were carried out in a lab scale microcosm using a 12h ON/OFF current mode at 20 mA for 4 days (in duplicates). The best remediation results were attained when EK process was applied in biotic conditions at 24ºC and combined with a daily irrigation (EK-Biotic-24-W); these conditions allowed to remove approximately 37% of the total mass on PPCPs in the soil. By eliminating the microbiological contribution to the degradation processes (sterilized soil; abiotic setting) in the same EK conditions (EK-Abiotic-24-W) a decrease in the removal by 7% was observed. The abiotic removal mechanisms only contributed to a total mass decay of 6%, whereas the biotic mechanism removed 20% (at 24ºC). The PPCPs more recalcitrant to degradation were CBZ, OXY and TCS. Oppositely E2, SMX e BPA displayed to be more biodegradable. Such results are compatible with previous tests, which suggest that usage of EK in combination with bioremediation vastly improves the efficiency over that of EK remediation alone in removing pollutants from soil. The EK process showed to be an effective option for the remediation of PPCPs in clay soils, which may enhance the degradation of contaminants by two main remediation mechanisms: (i) electrochemical induced degradation and (ii) bioremediation.

(SOE2/P5/F0505) UIDB/04085/2020 UIDB/04612/2020 UIDP/04612/2020 SFRH/BPD/114660/2016 CEECIND/04210/2017) This study analyses the electrokinetic (EK) contribution to the removal from a clay soil of a mixture of 10 different contaminants of emerging concern (CECs; 17β-estradiol, E2; sulfamethoxazole, SMX; bisphenol A, BPA; ibuprofen, IBU; 17α-ethinylestradiol, EE2; oxybenzone, OXY; diclofenac, DCF; triclosan, TCS; caffeine, CAF; carbamazepine, CBZ). After 4 days, the CECs natural attenuation was between 0% (CBZ) and 90% (E2) yet increasing with the application of EK (20 mA, 12 h ON/OFF) to 14% (CBZ) and 100% (E2). When EK was applied, the CECs more recalcitrant to biodegradation (i.e. ≤ 13% biotic decay) mostly underwent electro-chemical induced degradation (OXY, DCF, TCS, CAF, CBZ). Daily irrigation enhanced the rates of the electro-oxidation -osmosis and -migration, increasing the CECs decay. After 8 days of EK treatment, the CECs decay increased, surpassing the decay lag phase of some compounds (OXY, TCS, and CBZ). Yet after 16 days, most CECs showed similar removals with and without EK, with EK only acting positively on SMX, OXY, TCS and CBZ (ca. +10%). Our results support that EK application can improve the removal of CECs from soil, however, under the conditions tested, 16-day treatment lead to pH alterations that decreased the bioremediation efficiency and inhibited electro-degradation near the cathode. proof epub_ahead_of_print

Applying manganese(IV)- or iron(III)-(hydr)oxides to remove pharmaceuticals from water could be attractive, due to the capacity of these metal oxides to remove pharmaceuticals and be regenerated. As pharmaceutical removal under anaerobic conditions is foreseen, Mn(IV) or Fe(III) regeneration under anaerobic conditions, or with minimum oxygen dosage, is preferred. In this study, batch experiments are performed to investigate (1) Mn(IV) and Fe(III) regeneration from Mn(II) and Fe(II); (2) the pharmaceutical removal during biological Mn(IV) and Fe(III) regeneration; and (3) anaerobic abiotic pharmaceutical removal with different Mn(IV) or Fe(III) species. Results show that biological re-oxidation of reduced Mn(II) to Mn(IV) occurs under oxygen-limiting conditions. Biological re-oxidation of Fe(II) to Fe(III) is obtained with nitrate under anaerobic conditions. Both bio-regenerated Mn(IV)-oxides and Fe(III)-hydroxides are amorphous. The pharmaceutical removal is insignificant by Mn(II)- or Fe(II)-oxidizing bacteria during regeneration. Finally, pharmaceutical removal is investigated with various Mn(IV) and Fe(III) sources. Anaerobic abiotic removal using Mn(IV) produced from drinking water treatment plants results in 23% metoprolol and 44% propranolol removal, similar to chemically synthesized Mn(IV). In contrast, Fe(III) from drinking water treatment plants outperformed chemically or biologically synthesized Fe(III); Fe (III) from drinking water treatment can remove 31–43% of propranolol via anaerobic abiotic process. In addition, one of the Fe(III)-based sorbents tested, FerroSorp®RW, can also remove propranolol (20–25%). Biological regeneration of Mn(IV) and Fe(III) from the reduced species Mn(II) and Fe(II) could be more effective in terms of cost and treatment efficiency.

TEZ8260 Tez (Doktora) -- Çukurova Üniversitesi, Adana, 2010. Kaynakça (s. 181-196) var. xix, 203 s. : res. (bzs. rnk.), çizelge ; 29 cm. Adsorption is the important part of abiotic removal for many chemicals during the biological treatment. In this study, the adsorption properties of the activated sludge (0.5 g and 1.0 g) on pharmaceuticals that are ranitidine, acetyl salicylic acid (ASA), erythromycin, ivermectin, gentamicin sulfate and metamizol sodium have been investigated. The results of the equilibrium experiments have been applied Langmuir, Freundlich and Tempkin models and data fitted better to Freundlich isotherm model compared to the others models for all pharmaceuticals except eritromicin. The kinetics of the adsorption were also investigated and it was found that the adsorption rates were best described by the pseudo second order model. The pseudo isotherms of all adsorption processes were also studied with using pseudo second order constants and it was concluded that the pseudo Freundlich isotherms described live activated sludge-ranitidine (0.5 g-1.0 g), live activated sludge-ASA (0.5 g), live activated sludge -gentamisin sülfat (0.5 g) and live activated sludge-metamizol sodyum (0.5 g) processes better than the real isotherms, but real Freundlich isotherms described the others processes better than the pseudo isotherms. The Gibbs free energies of all pharmaceuticals have been calculated. Sorption coefficient, Kd , which describes the solid liquid partitioning charecteristics of a compound in sorption mechanism were also calculated for each pharmaceutical. Adsorpsiyon, biyolojik arıtım süresince çok sayıda kimyasal madde için abiyotik giderimin önemli bir parçasıdır. Bu çalışmada, canlı aktif çamurun (0.5 g ve 1.0 g) ranitidin, asetil salisilik asit (ASA), eritromisin, ivermektin, gentamisin sülfat ve metamizol sodyumu adsorplama kabiliyeti incelenmiştir. Yapılan denge deneylerinden elde edilen sonuçlar Langmuir, Freundlich ve Temkin izoterm modellerine uygulanmış ve eritromisin dışında her bir ilacın aktif çamur tarafından adsorpsiyonunun Freundlich izotermine daha iyi uyum sağlamakta olduğu görülmüştür. Her bir ilacın canlı aktif çamur tarafından adsorplanma kinetikleri incelenmiş ve adsorpsiyon hızlarının yalancı ikinci dereceden hız modeline uyduğu bulunmuştur. Yalancı ikinci dereceden hız denkleminden ve katsayılarından yola çıkarak hesaplanan yalancı izotermler ile gerçek izotermler karşılaştırıldığında canlı aktif çamur-ranitidin (0.5 g-1.0 g), canlı aktif çamur-ASA (0.5 g), canlı aktif çamurgentamisin sülfat (0.5 g) ve canlı aktif çamur-metamizol sodyum (0.5 g) sistemleri için en iyi izoterm modelinin yalancı Freundlich İzoterm modeli, diğer sistemler içinse en uygun izotermin gerçek Freundlich izotermi olduğu görülmüştür. Bütün sistemler için Gibbs serbest enerji değerleri de hesaplanmıştır. Çalışmada ayrıca deneysel olarak elde edilen değerler adsorpsiyon katsayılarının (Kd) hesaplanmasında da kullanılarak canlı aktif çamurun ilaçları adsorplama özellikleri değerlendirilmiştir. Bu çalışma Ç.Ü. Bilimsel Araştırma Projeleri Birimi tarafından desteklenmiştir. Proje No: MMF2008D1.

TEZ7145 Tez (Yüksek Lisans) -- Çukurova Üniversitesi, Adana, 2009. Kaynakça (s.76-85) var. viii, 86 s. : res. ; 29 cm. In this study adsorption properties of two pharmaceuticals Diclofenac (analgesic) and Ranitidine (antihistamine) by live activated sludge was investigated. Concentrations of activated sludge as an adsorbent were 1 and 2 g for Diclofenac and 0,25 g for Ranitidine. The results obtained from equilibrium experiments were applied to Langmuir and Freundlich models and according to this isoterms, adsorption of both ranitidine (R=0,9951, Kf=0,1388, n=0,9286) and diclofenac (for 1 g, R=0,975 Kf=0,0382., n=0,5513, for 2 g, R=0,9843 Kf=1,062., n=0,9169) by active sludge is well described with Freundlich isoterm model. It has seen that adsorption rate of both medicines fit to pseudo second order model. Gibbs free energy values were also calculated for both pharmaceuticals. Bu çalışmada canlı aktif çamurun iki adet ilacı Diklofenak (ağrıkesici) ve Ranitidin'i (mide ilacı) adsorplama kabiliyeti incelenmiştir. Adsorban olarak kullanılan aktif çamur Diklofenak için 1 ve 2 g, Ranitidin için ise 0,25 g olacak şekilde kullanılmıştır. Yapılan denge deneylerinde elde edilen sonuçlar Langmuir ve Freundlich izoterm modellerine uygulanmış ve buna göre hem ranitidin'in (R=0,9951, Kf=0,1388, n=0,9286) hemde diklofenak'ın (1 g Adsorban için R=0,975 Kf=0,0382., n=0,5513, 2 g için R=0,9843 Kf=1,062., n=0,9169) aktif çamur tarafından adsorpsiyonunun Freundlich izotermine daha iyi uyum göstermekte olduğu görülmüştür. Her iki ilacında adsorpsiyon hızlarının yalancı ikinci dereceden hız modeline uyduğu görülmüştür. Her iki ilaç için ayrıca Gibbs serbest enerji değerleri de hesaplanmıştır. Bu çalışma Ç.Ü. Bilimsel Araştırma Projeleri Birimi Tarafından Desteklenmiştir. Proje No:MMF2008YL2

TEZ7105 Tez (Doktora) -- Çukurova Üniversitesi, Adana, 2008. Kaynakça (s.122-136) var. xii, 138 s. : res. ; 29 cm. In this study, the removal properties of several anti-inflammatory pharmaceuticals such as diclofenac, paracetamol, ibuprofen and naproxen through the adsorption by live activated sludge were investigated in a batch system. Each pharmaceutical was found to be adsorbed by the live activated sludge at various rates. It was found that the adsorption took place substantially at the first 20 to 40 minutes of the contact time and reached steady-state within 80 minutes for all pharmaceuticals tested. Removal rates varied between 40-79% for all pharmaceuticals examined. Results obtained from the equilibrium experiments have been applied to both Langmuir and Freundlich isotherm models and data fitted beter to Freundlich isotherm model compared to Langmuir model for all pharmaceuticals. The kinetics of the adsorption were also investigated and it was found that the adsorption rates were best described by the pseudo second order model. Sorption coefficient, Kd, which describes the solid liqiud partitioning charecteristics of a compound in sorption mechanism were also calculated for each pharmaceutical. Bu çalışmada, ağrı kesici grubundan olan tıbbi ilaçlardan diklofenak, parasetamol, ibuprofen ve naproksenin kesikli sitemde canlı aktif çamur tarafından adsorpsiyonla giderim özellikleri incelenmiştir. Her bir ilacın canlı aktif çamur tarafından belirli oranlarda adsorplandığı ve adsorpsiyon işleminin büyük oranda ilk 20-40 dakika içerisinde gerçekleştiği ve tüm ilaçlar içinde, 80 dakika içerisinde dengeye ulaşıldığı tespit edilmiştir. Giderim verimi ilaç türüne bağlı olarak %40-79 arasında değişim göstermektedir. Yapılan denge deneylerinde elde edilen sonuçlar Langmuir ve Freundlich izoterm modellerine uygulanmış ve her bir ilacın aktif çamur tarafından adsorpsiyonunun Freundlich izotermine daha iyi uyum gösterdiği görülmüştür. Her bir ilacın canlı aktif çamur tarafından adsorplanma kinetikleri incelenmiş ve adsorpsiyon hızlarının yalancı ikinci dereceden hız modeline uyduğu bulunmuştur. Çalışmada ayrıca deneysel olarak elde edilen değerler adsorpsiyon katsayılarının (Kd) hesaplanmasında da kullanılarak canlı aktif çamurun ilaçları adsorplama özellikleri değerlendirilmiştir. Bu çalışma Ç.Ü. Bilimsel Araştırma Projeleri Birimi Tarafından Desteklenmiştir. Proje No:MMF2006D9

TEZ6275 Tez (Yüksek Lisans) -- Çukurova Üniversitesi, Adana, 2007. Kaynakça (s.64-78) var. ix, 79 s. ; 29 cm. Bu çalışmada canlı aktif çamurun iki anti-inflammatuar ilaç olan Parasetamol ve Diklofenak'ı adsorplama kabiliyeti incelenmiştir. Temel adsorpsiyon çalışmaları parasetomol ve diklofenak'ın canlı aktif çamur tarafından adsorplandığını göstermiştir. Giderim verimi parasetamol için %53-69 ve diklofenak için bu değer %36-86 arasında değişmektedir.Yapılan denge deneylerinden elde edilen sonuçlar Langmuir ve Freundlich izoterm modellerine uygulanmış ve buna göre hem parasetamol (R=0.9987, Kf=2.5118, n=3.0998) ve hem de diklofenak'ın (R=0.9877, Kf=0.8692, n=2.6781) aktif çamur tarafından adsorpsiyonu Freundlich izotermine uyum gösterdiği görülmüştür. Bu iki ilacın canlı aktif çamur tarafından adsorplanma kinetikleri de incelenmiş olup, bu amaçla birinci derece, ikinci derece ve yalancı ikinci derece modellere uygunluğu incelenmiştir. Parasetamol ve Diklofenak'ın adsorpsiyon hızlarının yalancı ikinci dereceden hız modeline uyduğu bulunmuştur. Her iki ilacın ayrıca Gibbs serbest enerji değerleri de hesaplanmış olup, parasetamol için ?G0=-0.8123 kJ/mol ve diklofenak için ?G0=1.3718 kJ/mol değerleri In this study, the adsorption properties of the activated sludge on two antiinflammatory pharmaceuticals that are paracetamol and diclofenac have been investigated. Basic adsorption studies indicated that the paracetamol and diclofenac were adsorped by activated sludge. The removal efficiency for paracetamol changes between 53-69% and for diclofenac changes 36-86%. The results of the equilibrium experiments have been applied on Langmuir and Freundlich isotherm models and according to those results, both of adsorption of paracetamol by activated sludge (R=0.9987, Kf=2.5118, n=3.0998) and adsorption of diclofenac by activated sludge (R=0.9877, Kf=0.8692, n=2.6781) were fitted to Freundlich isotherm model. The kinetics of the adsorption were also investigated and for this purpose three kinetic models namely first order lagergren model, the second order model and a pseudo second order models have been investigated. It was found out that kinetics of both adsorption processes was best described by pseudo-second order model. The Gibbs free energies of both pharmaceuticals have been calculated and it was found out that for paracetamol ?G0=-0.8123 kJ/mol and for diclofenac ?G0=1.3718 kJ/mol. Bu çalışma Ç.Ü. Bilimsel Araştırma Projeleri Birimi Tarafından Desteklenmiştir. Proje No

ÖZYÜKSEK L SANS TEZREAKT F BOYAR MADDELER N CANLI AKT F ÇAMUR B YOKÜTLESTARAFINDAN ADSORPLANAB LME ÖZELL KLER N N NCELENMESFatma Elçin ERKURTÇUKUROVA ÜN VERS TESFEN B L MLER ENST TÜSÜÇEVRE MÜHEND SL Ğ ANAB L M DALIDanışman: Doç. Dr. Mesut BAŞIBÜYÜKYıl : 2006 Sayfa : 57Jüri : Doç. Dr. Mesut BAŞIBÜYÜKProf. Dr. Ahmet YÜCEERProf. Dr. lyas DEHRBu çalışmada canlı aktif çamurun iki reaktif boyar madde Reactive Black 5ve Cibacron Yellow HR'yi adsorplama kabiliyeti incelenmiştir. Reactive Black 5 veCibacron Yellow HR boyar maddelerinin aktif çamur tarafından maksimumadsorplanma kapasiteleri sırasıyla 26.04 mg/G ve 4.66 mg/g'dır. Aynı zamanda buboyar maddelerin canlı aktif çamur biyokütlesi tarafından adsorplanma kinetiği deincelenmiştir. Her iki boyar maddenin de aktif çamurla adsorpsiyonunun yalancıikinci dereceden hız modeline uyduğu görülmüştür. Hem RB5 boyar maddesininhem de CBYHR boyar maddesinin (-1.2 ve -1.48 kJ/mol) aktif çamurlaadsorpsiyonunun Gibbs serbest enerjileri negatif olarak bulunmuştur. Bu değerinnegatif olması, adsorpsiyonun kendiliğinden gerçekleştiğini göstermektedirAnahtar Kelimeler : Abiyotik Giderim, Reaktif Boyar Madde, Kinetik, zoterm ABSTRACTM.Sc. THESISINVESTIGATION OF ADSORPTION CHARACTERISTICS OF SOMEREACTIVE DYESTUFF BY LIVE ACTIVATED SLUDGE BIOMASSFatma Elçin ERKURTÇUKUROVA UNIVERSITYINSTITUTE OF NATURAL AND APPLIED SCIENCESDEPARTMENT OF ENVIRONMENTAL ENGINEERINGAssoc.Prof.Dr. Mesut BAŞIBÜYÜKSupervisor:2006 Pages :57Year :Assoc.Prof.Dr. Mesut BAŞIBÜYÜKJury :Prof. Dr. Ahmet YÜCEERProf. Dr. lyas DEHRIn this study, the adsorption capacities of Reactive Black 5 and CibacronYellow HR by activated sludge were investigated. The maximum adsorptioncapacities of these dyes by activated sludge were found 26.4 mg/g and 4.66 mg/g.The kinetics of sorption have been analyzed by three kinetics models, the first orderlagergren model, the second order model and a pseudo second order model. Kineticsof both adsorption processes was best described by pseudo-second order model. Thethermodynamic caculations showed that Gibbs fre energies of both processes (RB5,G= -1.2kJ/mol; CBYHR, G= -1.48kJ/mol) have negative values indicating thespontaneous nature of the processes.Key Words : Abiotic Removal, Reactive Dyes, Kinetic, Isotherm 57