This study aims efficient conversion of cotton stalks to cellulosic ethanol through ionic liquid pretreatment and enhanced enzymatic hydrolysis. Among several ionic liquids, EMIMAc exhibited the most striking impact on cotton stalks with respect to the changes in biomass structure and digestibility. Cotton stalks, which were subjected to EMIMAc pretreatment at 10% (w cotton stalks/w EMIMAc) of biomass loading and 150&deg / C for 30 minutes, were found to be 9 times more digestible than untreated cotton stalks. Besides, glucose and ethanol yields, which were based on the cellulose content of untreated cotton stalks, were found as 67% and 66%, respectively. These yields were insufficient regarding efficient conversion of the cellulosic portion of cotton stalks to glucose and ethanol which is linked to the superior solvation capability of EMIMAc towards biomass. In order to enhance aforementioned yields, EMIMAc pretreatment was conducted at 30% of biomass loading. Though lignin extracted was much lower, higher yields were obtained compared to the former case since 96% of cellulose was recovered upon EMIMAc pretreatment and reduced crystallinity was observed for pretreated biomass. Glucose yield was achieved as 84% even at a substrate loading of 15% (w/v). Additionally, 76% of ethanol yield and 3% (v/v) of ethanol titer were obtained upon fermentation. Accordingly, reduction in biomass crystallinity was satisfactory to improve enzymatic accessibility of the biomass. Besides, EMIMAc maintained its effectiveness as a pretreatment agent upon recycling since no change in terms of hydrolysis of pretreated samples was observed upon EMIMAc recycling for three times.

Anaerobic digestion of excess biological wastewater treatment sludge (WAS) from pulp mills has the potential to reduce disposal costs and to generate energy through biogas production. The organic matter in WAS is highly structured, which normally hinders biogas production. This study investigated three methods of pretreating WAS from two different pulp mills before anaerobic digestion to improve biogas yield and production rate. The three pretreatment methods tested were: i) thermal pretreatment at 170oC, ii) caustic pretreatment at 140oC and pH 12, and iii) sonication at 20 kHz and 1 W/mL. Thermal pretreatment proved to be the most effective, increasing biogas yield by 280% and 50% and increasing production rates 300-fold and 10-fold for the two samples, respectively. Caustic pretreatment showed similar results, but resulted in the formation of soluble non-biodegradable compounds. Sonication was the least effective pretreatment and did not substantially increase biogas yield, but increased biogas production rate.

Constructed wetlands are largely used for water treatment both in agricultural land and for treating water from municipal and industrial waste. These wetlands need to be managed in order to work properly. How to deal with the large amount of vegetation harvested in the wetlands has withdrawn a great concern. The application of using wetland biomass as the co-substrates in anaerobic digestion was studied in this project. Plant materials, mostly Phragmites australis (common reed) from three different wetlands were used as raw material to produce biogas. The methane production using reed material harvested from municipal wastewater, industrial wastewater and an agricultural wetland are 66, 106, 144 ml/g VS respectively, which were lower than the suggested number 180ml/g VS. The gas potential remains a lot to be improved such as harvesting at summer to reduce the lignin content and changing the co-digestion mixing level to adjust to the optimal C/N ratio. Chemical analyses were performed concerning the gas yield and the residue quality. The digested residues showed a low concentration of cadmium, providing a non-toxic possibility to be spread on farm land as fertilizers, and closing the nutrient circle from land into water and back to land again. Pretreatments in the biogas process are usually focusing on the reduction of the lignocellulosic content in the raw material. Assessment of costs and benefits is needed for using wetland reed in the biogas production and applying any pretreatment methods.

Algae is regarded as a good potential substrate for biogas production, due to high cells productivity, low cellulose and zero lignin content. Two parts were included in this study: first, cultivations of micro-algae (Chlorella sorokiniana and Tetraselmis suecica) at two different nitrate concentrations, also the effect of addition of CO2 on algae grow was investigated in this first part. Second, batch fermentations of the cultivated micro-algae as well as a powder Chlorella (obtained from Raw Food Shop) and a dry mix filamentous algae (collected in the pounds in the park at the back of the Tema-building and then dried) were performed. In this part also effects of thermo-lime pretreatment (room temperature, 80oC, 105oC and 120oC) on the algae biogas potentials was investigated. Both strains of micro-algae cultured at low nitrate gave more CH4 yield: 319 (±26) mL and 258 (±12) mL CH4 per added gVS was obtained during the degradation of Chlorella sorokiniana grown at 0.4mM-N and 2mM-N level, respectively. For Tetraselmis suecica 337 (±37) mL and 236 (±20) mL CH4 per added gVS was obtained at 2.4mM-N and 12mM-N level, respectively. Powder Chlorella gave the highest biogas production (719 ±53 mL/added gVS) and CH4 yields (392 ±14 mL/added gVS), followed by the dry filamentous algae (661 ±20 mL biogas and 295 ±9 mL CH4 per added gVS) and Tetraselmis suecica (12 mM-N; 584 ±7 mL biogas and 295 ±9 mL CH4 per added gVS). A negative effect of lime treatment at room temperature on CH4 yield of algal biomass was obtained. Lime treatment at 120oC showed the fastest degradation rate for Tetraselmis suecica and powder Chlorella during the initial 5 days of incubation. Chlorella sorokiniana and Tetraselmis suecica cultures flushed with biogas containing 70% and also CO2 enriched air (5% CO2) did not increase cells growth (measured as OD600) if compared to references grown under air. On the contrary, a clearly inhibition effect on the algal cells growth was observed in some cultures.

Verapamil is a commonly used medicine for the treatment of supraventricular arrhythmias, angina and hypertension. Recently, some newly developed applications of Verapamil, such as treating hypomania and chemotherapy for cancers, have been reported. Thus, monitoring the concentration of Verapamil accurately is very important. The major clinical analytical methods of Verapamil concentration determination are high performance liquid chromatography (HPLC) with UV or with fluorescence detector. However, these analytical methods have some disadvantages, like expensive instruments, complex operation, and time-consuming etc. The chemical structure and properties of Verapamil are very stable. The preliminary result of electrochemical analysis doesn¡¦t show any electrochemical activity. In this study, we developed an innovative ozone pre-treatment method to oxidize Verapamil to the smaller molecules and change its structure. Verapamil have excellent electrochemical activity after ozone pre-treatment. The spectroscopy and mass spectrometry show the changes of Verapamil structure. The products of Verapamil treated with ozone are also predicted by mass spectrometry. The gold nanoelectrode ensemble electrodes (GNEE) are used as working electrode for its good catalytic activity of electrochemical reaction, high sensitivity and high selectivity. The overall experimental framework of this study is microchip with GNEE working electrode accompanied by cyclic voltammetry, an electrochemical analytical instrument. Compared with traditional analytical methods, the system has some advantages such as small size, micro sample volume, easy operation, rapid detection and low cost. The limit concentration of Verapamil solution for stable detection in the system is 10 ng/mL. A linear dynamic range with a high correlation factor from 10 ng/mL to 100 £gg/mL was obtained. For the analysis of serum sample, Verapamil present excellent electrochemical activity at 1 ng/mL. A linear dynamic range with a high correlation factor from 1 ng/mL to 100 £gg/mLwas obtained. According to the results, our system for clinical Verapmil concentration analysis has the feasibility of the practical application.

In this study, bio-hydrogen generation potential of sugar-beet processing wastes (sugar-beet processing wastewater and beet-pulp) through dark fermentation was investigated. For this purpose, four different experimental set-ups were used. In the first set-up, sugar-beet processing wastewater was used along with four different cultures to investigate the effect of culture type on bio-hydrogen production. In addition, unseeded reactor was prepared to investigate bio-hydrogen production potential of indigenous microorganisms. The highest bio-hydrogen production yield (87.7 mL H2/g COD) was observed in the unseeded reactor. In the second set-up, beet-pulp was compared with sugar-beet processing wastewater in terms of bio-hydrogen generation potentials at an initial COD level of 4.5 g/L. In the third set-up, bio-hydrogen productivities of only beet-pulp and co-digestion of beet-pulp and sugar-beet processing wastewater at high COD values were investigated. The results of third set-up revealed that the reactor fed by 20 g/L COD beet-pulp provided the highest bio-hydrogen production yield (95.6 mL H2 /g COD). Finally, in the fourth set-up, the effects of five different pretreatment methods on solubilization of beet-pulp were investigated. Then, three out of five pretreatment methods were chosen to compare the corresponding bio-hydrogen productivities. Maximum bio-hydrogen production yield (115.6 mL H2/g COD) was observed in reactor which contained alkaline pretreated beet-pulp. Based on the results obtained in this study, it is postulated that, bio-hydrogen production from sugar-beet processing wastes by dark fermentation can not only enable waste minimization but also contribute to sustainability via valuable bio-based product formation from wastes, namely bio-hydrogen.

Lignocellulosic biomass is under extensive investigation as a bioethanol and bio-based materials feedstock. However, the complex structural and chemical mechanisms of lignocellulosic plant, which cause resistance to deconstruction during saccharification, require a pretreatment process. In this study, raw materials (corn bran, wheat bran and wheat straw) were selected because of their production and consumption in Turkey and also their accessibilities to be used as bioethanol source. Microfluidization pretreatment (high-pressure fluidization), which stands as a new approach for nano-cellulosic fibers production, was studied at 500 bar and 2000 bar to observe the qualitative and quantitative modifications in enzymatic hydrolysis depending on its effects on lignocellulosic structure. Optimum cellulase concentrations were determined for microfluidized samples as 4.5 U/g dry biomass for wheat bran, corn bran and 6.0 U/g dry biomass for wheat straw samples for the first 150 min interval. Effective usage of solid loads were found as 5.0 %, 2.5 %, and 7.5 % (dw/v) for wheat bran, wheat straw and corn bran, respectively. X-ray diffraction and SEM results of the microfluidized samples have indicated that the pretreatment has increased crystallinity index of all the samples and resulted in a scattered structure. Comparisons with other methods (softening, dilute-acid and lime pretreatments) have shown that microfluidization is advantageous over others by reducing the time required for enzymatic hydrolysis and thus can be a promising alternative pretreatment.

Wastewaters resulted from anthropogenic influence can encompass a wide range of potential contaminants and concentrations. There are numerous procedures that can be used to clear out wastewaters depending on the type and extent of contamination, however / disposal of pollutants from wastewaters in industrial scale is a difficult and costly problem. In this study, the use of ion exchange theory utilizing natural Turkish clinoptilolite zeolite from G&ouml / rdes-Manisa as ion exchange resins in down-flow column mode is investigated. The clinoptilolite with particle size range of 0.25-0.50 mm is used in the removal of lead Pb2+ and ammonium NH4+ ions from aqueous solutions. The aim of the study is to set up the conditions under which clinoptilolite may be used in an economical and efficient approach in the removal process. Experiments were divided into two sets: binary studies, and ternary studies, and the effects of conditioning clinoptilolite with NaCl solution, flow rate, and initial concentration of the solutions on the removal behavior were investigated. In binary studies, results showed that increasing the loading volumetric flow rate resulted in decreasing the breakthrough capacity and the column efficiency, while the total capacity remained constant. The maximum total capacity was determined as 1.16 meq/g of zeolite for NH4+, and 1.1 meq/g of zeolite for Pb2+ and these values were close to each other and to the sodium content of Na-form of pretreated clinoptilolite (1.16 meq/g of zeolite). In addition, by decreasing the initial contaminant concentration, an increase in breakthrough capacity and column efficiency was observed. In ternary studies, the results showed that the removal of Pb2+ and NH4+ ions are dependent on the flow rate, in which at moderately low flow rate, a higher ion exchange capacity is yielded. That was explained as at higher flow rates, the retention time was insufficient for the ion exchange process to take place completely between clinoptilolite and lead and ammonium ions. Thus, a competition between Pb2+ and NH4+ ions for the exchange sites on clinoptilolite was observed and this competition was in favor of lead ions. Consequently, it was observed that the clinoptilolite zeolite has affinity for both Pb2+ and NH4+ ions. However, the affinity of clinoptilolite for lead ions is higher than that for ammonium ions. Therefore, the cations selectivity for clinoptilolite according to their affinity is determined as the following sequence: NH4+ &gt / Pb2+ &gt / Na+.

There is an increasing trend in the world for using renewable sources of fuels and chemicals due to the continuous depletion of fossil fuel reserves besides the environmental issues related with the exploitation of these resources. Lignocellulosic biomass is seen as the most promising candidate to be used instead of fossil sources because of its availability, relatively low price and less competition with food and feed crops. In this study, corn cobs, a lignocellulosic agricultural waste, were subjected to alkaline pretreatment for the co-production of glucose and hemicellulose based films with a multi-product approach in order to diversify the product range and to increase the revenues of the process. The pretreatment applied to lignocellulosic agricultural waste has a significant impact on the quantities and properties of the products that can be produced from the lignocellulosic feedstock upon pretreatment. Within the context of this study, the parameters utilized during the alkaline pretreatment of corn cobs were investigated in terms of their effect on the amount of glucose obtained through the enzymatic v hydrolysis of the cellulosic portion and on the mechanical properties of the films obtained through the solvent casting of the hemicellulosic portion of corn cob. The pretreatment parameters including the alkaline type and concentration, addition and type of boron compound as well as the duration of pretreatment, were optimized with respect to the amounts and the properties of the products. Following the pretreatments conducted with 24 % KOH and 1% NaBH4, which were the initial pretreatment parameters in the study, a glucose yield of 22 % and a tensile energy to break of 2.1 MJ/m3 were obtained. Upon the optimization of the pretreatment procedure, the optimum pretreatment conditions were determined as 5 % NaOH, 1 % NaBH4 and 3 hours and a glucose yield of approximately 31% and a tensile energy to break of around 1.7 MJ/m3 were obtained.

In this work, the steady-state performance of zeolite-based (Cu-ZSM-5) and vanadium-based honeycomb monolith catalysts was investigated in the selective catalytic reduction process (SCR) for NO removal using NH3. The aim was to delineate the effect of various parameters including pretreatment of the catalyst sample with H2, NH3-to-NO ratio, inlet oxygen concentration, and space velocity. The concentrations of the species (e.g. NO, NH3, and others) were determined using a Fourier Transform Infrared (FTIR) spectrometer. The temperature was varied from ambient (25 C) to 500 C. The investigation showed that all of the above parameters (except pre-treatment with H2) significantly affected the peak NO reduction, the temperature at which peak NO reduction occurred, and residual ammonia left at higher temperatures (also known as 'NH3 slip'). Depending upon the particular values of the parameters, a peak NO reduction of around 90% was obtained for both the catalysts. However, an accompanied generation of N2O and NO2 species was observed as well, being much higher for the vanadium-based catalyst than for the Cu-ZSM-5 catalyst. For both catalysts, the peak NO reduction decreased with an increase in space velocity, and did not change significantly with an increase in oxygen concentration. The temperatures at which peak NO reduction and complete NH3 removal occurred increased with an increase in space velocity but decreased with an increase in oxygen concentration. The presence of more ammonia at the inlet (i.e. higher NH3-to-NO ratio) improved the peak NO reduction but simultaneously resulted in an increase in residual ammonia. Pretreatment of the catalyst sample with H2 (performed only for the Cu-ZSM-5 catalyst) did not produce any perceivable difference in any of the results for the conditions of these experiments.