Search results for: Langmuir adsorption isotherm

Authors: Abhishek Sraw, Amit Sobti, Yamini Pandey, R. K. Wanchoo, Amrit Pal Toor

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Monocrotophos (MCP) is a widely used pesticide in India, which belong to an extremely toxic organophosphorus family, is persistent in nature and its toxicity is widely reported in all environmental segments in the country. Advanced Oxidation Process (AOP) is a promising solution to the problem of water pollution. TiO₂ is being widely used as a photocatalyst because of its many advantages, but it has a large band gap, due to which it is modified using metal and nonmetal dopant to make it active under sunlight and visible light. The use of nanosized powdered catalysts makes the recovery process extremely complicated. Hence the aim is to use low cost, easily available, eco-friendly clay material in form of bead as the support for the immobilization of catalyst, to solve the problem of post-separation of suspended catalyst from treated water. A recirculation type photocatalytic reactor (RTPR), using ultraviolet light emitting source (blue black lamp) was designed which work effectively for both suspended catalysts and catalyst coated clay beads. The bare, TiO₂ and W-TiO₂ coated clay beads were characterized by scanning electron microscopy (SEM), electron dispersive spectroscopy (EDS) and N₂ adsorption–desorption measurements techniques (BET) for their structural, textural and electronic properties. The study involved variation of different parameters like light conditions, recirculation rate, light intensity and initial MCP concentration under UV and sunlight for the degradation of MCP. The degradation and mineralization studies of the insecticide solution were performed using UV-Visible spectrophotometer, and COD vario-photometer and GC-MS analysis respectively. The main focus of the work lies in checking the recyclability of the immobilized TiO₂ over clay beads in the developed RTPR up to 30 continuous cycles without reactivation of catalyst. The results demonstrated the economic feasibility of the utilization of developed RTPR for the efficient purification of pesticide polluted water. The prepared TiO₂ clay beads delivered 75.78% degradation of MCP under UV light with negligible catalyst loss. Application of W-TiO₂ coated clay beads filled RTPR for the degradation of MCP under sunlight, however, shows 32% higher degradation of MCP than the same system based on undoped TiO₂. The COD measurements of TiO₂ coated beads led to 73.75% COD reduction while W-TiO₂ resulted in 87.89% COD reduction. The GC-MS analysis confirms the efficient breakdown of complex MCP molecules into simpler hydrocarbons. This supports the promising application of clay beads as a support for the photocatalyst and proves its eco-friendly nature, excellent recyclability, catalyst holding capacity, and economic viability.

Keywords: immobilized clay beads, monocrotophos, recirculation type photocatalytic reactor, TiO₂

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Authors: Priyanka Mondal, Santosh K. Sarkar

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The present study investigated the spatiotemporal distribution and ecological risk assessment of trace elements of surface sediments (top 0 - 5 cm; grain size ≤ 0.63 µm) in relevance to sediment quality characteristics along the Ganges River Estuary, India. Sediment samples were collected during ebb tide from intertidal regions covering seven sampling sites of diverse environmental stresses. The elements were analyzed with the help of ICPAES. This positive, mixohaline, macro-tidal estuary has global significance contributing ecological and economic services. Presence of fine-clayey particle (47.03%) enhances the adsorption as well as transportation of trace elements. There is a remarkable inter-metallic variation (mg kg-1 dry weight) in the distribution pattern in the following manner: Al (31801± 15943) > Fe (23337± 7584) > Mn (461±147) > S(381±235) > Zn(54 ±18) > V(43 ±14) > Cr(39 ±15) > As (34±15) > Cu(27 ±11) > Ni (24 ±9) > Se (17 ±8) > Co(11 ±3) > Mo(10 ± 2) > Hg(0.02 ±0.01). An overall trend of enrichment of majority of trace elements was very much pronounced at the site Lot 8, ~ 35km upstream of the estuarine mouth. In contrast, the minimum concentration was recorded at site Gangasagar, mouth of the estuary, with high energy profile. The prevalent variations in trace element distribution are being liable for a set of cumulative factors such as hydrodynamic conditions, sediment dispersion pattern and textural variations as well as non-homogenous input of contaminants from point and non-point sources. In order to gain insight into the trace elements distribution, accumulation, and their pollution status, geoaccumulation index (Igeo) and enrichment factor (EF) were used. The Igeo indicated that surface sediments were moderately polluted with As (0.60) and Mo (1.30) and strongly contaminated with Se (4.0). The EF indicated severe pollution of Se (53.82) and significant pollution of As (4.05) and Mo (6.0) and indicated the influx of As, Mo and Se in sediments from anthropogenic sources (such as industrial and municipal sewage, atmospheric deposition, agricultural run-off, etc.). The significant role of the megacity Calcutta in relevance to the untreated sewage discharge, atmospheric inputs and other anthropogenic activities is worthwhile to mention. The ecological risk for different trace elements was evaluated using sediment quality guidelines, effects range low (ERL), and effect range median (ERM). The concentration of As, Cu and Ni at 100%, 43% and 86% of the sampling sites has exceeded the ERL value while none of the element concentration exceeded ERM. The potential ecological risk index values revealed that As at 14.3% of the sampling sites would pose relatively moderate risk to benthic organisms. The effective role of finer clay particles for trace element distribution was revealed by multivariate analysis. The authors strongly recommend regular monitoring emphasizing on accurate appraisal of the potential risk of trace elements for effective and sustainable management of this estuarine environment.

Keywords: pollution assessment, sediment contamination, sediment quality, trace elements

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Authors: Stefania Fortino, Petr Hradil, Timo Avikainen

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Timber bridges have an excellent environmental performance, are economical, relatively easy to build and can have a long service life. However, the durability of these bridges is the main problem because of their exposure to outdoor climate conditions. The moisture content accumulated in wood for long periods, in combination with certain temperatures, may cause conditions suitable for timber decay. In addition, moisture content variations affect the structural integrity, serviceability and loading capacity of timber bridges. Therefore, the monitoring of the moisture content in wood is important for the durability of the material but also for the whole superstructure. The measurements obtained by the usual sensor-based techniques provide hygro-thermal data only in specific locations of the wood components. In this context, the monitoring can be assisted by numerical modelling to get more information on the hygro-thermal response of the bridges. This work presents a hygro-thermal model based on a multi-phase moisture transport theory to predict the distribution of moisture content, relative humidity and temperature in wood. Below the fibre saturation point, the multi-phase theory simulates three phenomena in cellular wood during moisture transfer, i.e., the diffusion of water vapour in the pores, the sorption of bound water and the diffusion of bound water in the cell walls. In the multi-phase model, the two water phases are separated, and the coupling between them is defined through a sorption rate. Furthermore, an average between the temperature-dependent adsorption and desorption isotherms is used. In previous works by some of the authors, this approach was found very suitable to study the moisture transport in uncoated and coated stress-laminated timber decks. Compared to previous works, the hygro-thermal fluxes on the external surfaces include the influence of the absorbed solar radiation during the time and consequently, the temperatures on the surfaces exposed to the sun are higher. This affects the whole hygro-thermal response of the timber component. The multi-phase model, implemented in a user subroutine of Abaqus FEM code, provides the distribution of the moisture content, the temperature and the relative humidity in a volume of the timber deck. As a case study, the hygro-thermal data in wood are collected from the ongoing monitoring of the stress-laminated timber deck of Tapiola Bridge in Finland, based on integrated humidity-temperature sensors and the numerical results are found in good agreement with the measurements. The proposed model, used to assist the monitoring, can contribute to reducing the maintenance costs of bridges, as well as the cost of instrumentation, and increase safety.

Keywords: moisture content, multi-phase models, solar radiation, timber decks, FEM

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Authors: Carlos A. C. G. Neto, Natan C. G. Silva, Thais O. Costa, Luciana R. B. Goncalves, Maria v. P. Rocha

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Galactosidases are enzymes responsible for catalyzing lactose hydrolysis reactions and also favoring transgalactosylation reactions for the production of prebiotics, among which lactulose stands out. These enzymes, when immobilized, can have some enzymatic characteristics substantially improved, and the coating of supports with multifunctional polymers in immobilization processes is a promising alternative in order to extend the useful life of the biocatalysts, for example, the coating with polyethyleneimine (PEI). PEI is a flexible polymer that suits the structure of the enzyme, giving greater stability, especially for multimeric enzymes such as β-galactosidases and also protects it from environmental variations, for example, pH and temperature. In addition, it can substantially improve the immobilization parameters and also the efficiency of enzymatic reactions. In this context, the aim of the present work was first to develop biocatalysts of β-galactosidase from Kluyveromyces lactis immobilized on PEI coated agarose, determining the immobilization parameters, its operational and thermal stability, and then to apply it in the hydrolysis of lactose and synthesis of lactulose, using whey as a substrate. This immobilization strategy was chosen in order to improve the catalytic efficiency of the enzyme in the transgalactosylation reaction for the production of prebiotics, and there are few studies with β-galactosidase from this strain. The immobilization of β-galactosidase in agarose previously functionalized with 48% (w/v) glycidol and then coated with 10% (w/v) PEI solution was evaluated using an enzymatic load of 10 mg/g of protein. Subsequently, the hydrolysis and transgalactosylation reactions were conducted at 50 °C, 120 RPM for 20 minutes, using whey (66.7 g/L of lactose) supplemented with 133.3 g/L fructose at a ratio of 1:2 (lactose/fructose). Operational stability studies were performed in the same conditions for 10 cycles. Thermal stabilities of biocatalysts were conducted at 50 ºC in 50 mM phosphate buffer, pH 6.6, with 0.1 mM MnCl2. The biocatalysts whose supports were coated were named AGA_GLY_PEI_GAL, and those that were not coated were named AGA_GLY_GAL. The coating of the support with PEI considerably improved immobilization yield (2.6-fold), the biocatalyst activity (1.4-fold), and efficiency (2.2-fold). The biocatalyst AGA_GLY_PEI_GAL was better than AGA_GLY_GAL in hydrolysis and transgalactosylation reactions, converting 88.92% of lactose at 5 min of reaction and obtaining a residual concentration of 5.24 g/L. Besides that, it was produced 13.90 g/L lactulose in the same time interval. AGA_GLY_PEI_GAL biocatalyst was stable during the 10 cycles evaluated, converting approximately 80% of lactose and producing 10.95 g/L of lactulose even after the tenth cycle. However, the thermal stability of AGA_GLY_GAL biocatalyst was superior, with a half-life time 5 times higher, probably because the enzyme was immobilized by covalent bonding, which is stronger than adsorption (AGA_GLY_PEI_GAL). Therefore, the strategy of coating the supports with PEI has proven to be effective for the immobilization of β-galactosidase from K. lactis, considerably improving the immobilization parameters, as well as the enzyme, catalyzed reactions. In addition, the use of whey as a raw material for lactulose production has proved to be an industrially advantageous alternative.

Keywords: β-galactosidase, immobilization, lactulose, polyethylenimine, whey

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Authors: G. C. Santini, C. Potrich, L. Lunelli, L. Vanzetti, S. Marasso, M. Cocuzza, C. Pederzolli

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The relevance of circulating miRNAs as non-invasive biomarkers for several pathologies is nowadays undoubtedly clear, as they have been found to have both diagnostic and prognostic value able to add fundamental information to patients’ clinical picture. The availability of these data, however, relies on a time-consuming process spanning from the sample collection and processing to the data analysis. In light of this, strategies which are able to ease this procedure are in high demand and considerable effort have been made in developing Lab-on-a-chip (LOC) devices able to speed up and standardise the bench work. In this context, a very promising polydimethylsiloxane (PDMS)-based microdevice which integrates the processing of the biological sample, i.e. purification of extracellular miRNAs, and reverse transcription was previously developed in our lab. In this study, we aimed at the improvement of the miRNA extraction performances of this micro device by increasing the ability of its surface to absorb extracellular miRNAs from biological samples. For this purpose, we focused on the modulation of two properties of the material: roughness and charge. PDMS surface roughness was modulated by casting with several templates (terminated with silicon oxide coated by a thin anti-adhesion aluminum layer), followed by a panel of curing conditions. Atomic force microscopy (AFM) was employed to estimate changes at the nanometric scale. To introduce modifications in surface charge we functionalized PDMS with different mixes of positively charged 3-aminopropyltrimethoxysilanes (APTMS) and neutral poly(ethylene glycol) silane (PEG). The surface chemical composition was characterized by X-ray photoelectron spectroscopy (XPS) and the number of exposed primary amines was quantified with the reagent sulfosuccinimidyl-4-o-(4,4-dimethoxytrityl) butyrate (s-SDTB). As our final end point, the adsorption rate of all these different conditions was assessed by fluorescence microscopy by incubating a synthetic fluorescently-labeled miRNA. Our preliminary analysis identified casting on thermally grown silicon oxide, followed by a curing step at 85°C for 1 hour, as the most efficient technique to obtain a PDMS surface roughness in the nanometric scaleable to trap miRNA. In addition, functionalisation with 0.1% APTMS and 0.9% PEG was found to be a necessary step to significantly increase the amount of microRNA adsorbed on the surface, therefore, available for further steps as on-chip reverse transcription. These findings show a substantial improvement in the extraction efficiency of our PDMS microdevice, ultimately leading to an important step forward in the development of an innovative, easy-to-use and integrated system for the direct purification of less abundant circulating microRNAs.

Keywords: circulating miRNAs, diagnostics, Lab-on-a-chip, polydimethylsiloxane (PDMS)

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Authors: Ahmed Tawfik

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Oxidation of 1,4 dioxane produces metabolites by-products involving glycolaldehyde and acids that have geno- and cytotoxicity impact on microbial degradation. Thereby, the incorporation of algae with bacteria in the treatment system would eliminate and overcome the accumulation of metabolites that are utilized as a carbon source for the build-up of biomass. Therefore, the aim of the present study is to assess the potential of algae/bacteria-based membrane bioreactor (AB-MBR) for biodegradation of 1,4 dioxane-rich wastewater at a high imposed loading rate. Three identical reactors, i.e., AB-MBR1, AB-MBR2, and AB-MBR3, were operated in parallel at 1,4 dioxane loading rates of 641.7, 320.9, and 160.4 mg/L. d., and HRTs of 6.0, 12 and 24 h. respectively. The AB-MBR1 achieved 1,4 dioxane removal rate of 263.7 mg/L.d., where the residual value in the treated effluent amounted to 94.4±22.9 mg/L. Reducing the 1,4 dioxane loading rate (LR) to 320.9 mg/L.d in the AB-MBR2 maximized the removal rate efficiency of 265.9 mg/L.d., with a removal efficiency of 82.8±3.2%. The minimum value of 1,4 dioxane of 17.3±1.8 mg/L in the treated effluent of AB-MBR3 was obtained at an HRT of 24.0 h and loading rate of 160.4 mg/L.d. The mechanism of 1,4 dioxane degradation in AB-MBR was a combination of volatilization (8.03±0.6%), UV oxidation (14.1±0.9%), microbial biodegradation (49.1±3.9%) and absorption/uptake and assimilation by algae (28.8±2.%). Further, the Thioclava, Afipia, and Mycobacterium genera oxidized and produced the required enzymes for hydrolysis and cleavage of the dioxane ring into 2-hydroxy-1,4 dioxane. Moreover, the fungi, i.e., Basidiomycota and Cryptomycota, played a big role in the degradation of the 1,4 dioxane into 2-hydroxy-1,4 dioxane. Xanthobacter and Mesorhizobium were involved in the metabolism process by secreting alcohol dehydrogenase (ADH), aldehyde dehydrogenase (ALDH), and glycolate oxidase. Bacteria and fungi produced dehydrogenase (DH) for the transformation of 2-hydroxy-1,4 dioxane into 2-hydroxy-ethoxyacetaldehyde. The latter is converted into Ethylene glycol by Aldehyde hydrogenase (ALDH). Ethylene glycol is oxidized into acids using Alcohol hydrogenase (ADH). The Diatomea, Chlorophyta, and Streptophyta utilize the metabolites for biomass assimilation and produce the required oxygen for further oxidation of the dioxane and its metabolites by-products of bacteria and fungi. The major portion of metabolites (ethylene glycol, glycolic acid, and oxalic acid were removed due to uptake and absorption by algae (43±4.3%), followed by adsorption (18.4±0.9%). The volatilization and UV oxidation contribution for the degradation of metabolites were 8.7±0.7% and 12.3±0.8%, respectively. The capabilities of genera Defluviimonas, Thioclava, Luteolibacter, and Afipia. The genera of Defluviimonas, Thioclava, Luteolibacter, and Mycobacterium were grown under a high 1,4 dioxane LR of 641.7 mg/L.d. The Chlorophyta (4.1-43.6%), Streptophyta (2.5-21.7%), and Diatomea (0.8-1.4%) phyla were dominant for degradation of 1,4 dioxane. The results of this study strongly demonstrated that the bioremediation and bioaugmentation process can safely remove 1,4 dioxane from industrial wastewater while minimizing environmental concerns and reducing economic costs.

Keywords: wastewater, membrane bioreactor, bacterial community, algal community

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Authors: Nikolai A. Khlebnikov, Vladimir N. Krasilnikov, Evgenii V. Polyakov, Anastasia A. Maltceva

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Carbon materials with advanced surfaces are widely used both in modern industry and in environmental protection. The physical-chemical nature of these materials is determined by the morphology of primary atomic and molecular carbon structures, which are the basis for synthesizing the following materials: zero-dimensional (fullerenes), one-dimensional (fiber, tubes), two-dimensional (graphene) carbon nanostructures, three-dimensional (multi-layer graphene, graphite, foams) with unique physical-chemical and functional properties. Experience shows that the microscopic morphological level is the basis for the creation of the next mesoscopic morphological level. The dependence of the morphology on the chemical way and process prehistory (crystallization, colloids formation, liquid crystal state and other) is the peculiarity of the last called level. These factors determine the consumer properties of carbon materials, such as specific surface area, porosity, chemical resistance in corrosive environments, catalytic and adsorption activities. Based on the developed ideology of thin precursor synthesis, the authors discuss one of the approaches of the porosity control of carbon-containing materials with a given aggregates morphology. The low-temperature thermolysis of precursors in a gas environment of a given composition is the basis of the above-mentioned idea. The processes of carbothermic precursor synthesis of two different compounds: tungsten carbide WC:nC and zinc oxide ZnO:nC containing an impurity phase in the form of free carbon were selected as subjects of the research. In the first case, the transition metal (tungsten) forming carbides was the object of the synthesis. In the second case, there was selected zinc that does not form carbides. The synthesis of both kinds of transition metals compounds was conducted by the method of precursor carbothermic synthesis from the organic solution. ZnO:nC composites were obtained by thermolysis of succinate Zn(OO(CH2)2OO), formate glycolate Zn(HCOO)(OCH2CH2O)1/2, glycerolate Zn(OCH2CHOCH2OH), and tartrate Zn(OOCCH(OH)CH(OH)COO). WC:nC composite was synthesized from ammonium paratungstate and glycerol. In all cases, carbon structures that are specific for diamond- like carbon forms appeared on the surface of WC and ZnO particles after the heat treatment. Tungsten carbide and zinc oxide were removed from the composites by selective chemical dissolution preserving the amorphous carbon phase. This work presents the results of investigating WC:nC and ZnO:nC composites and carbon nanopowders with tubular, tape, plate and onion morphologies of aggregates that are separated by chemical dissolution of WC and ZnO from the composites by the following methods: SEM, TEM, XPA, Raman spectroscopy, and BET. The connection between the carbon morphology under the conditions of synthesis and chemical nature of the precursor and the possibility of regulation of the morphology with the specific surface area up to 1700-2000 m2/g of carbon-structured materials are discussed.

Keywords: carbon morphology, composite materials, precursor synthesis, tungsten carbide, zinc oxide

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Authors: Elvis Medina, Alejandro Karelovic, Romel Jiménez

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Catalytic ammonia decomposition represents an attractive alternative due to its high H₂ content (17.8% w/w), a product stream free of COₓ, among others; however, challenges need to be addressed for its consolidation as an H₂ chemical storage technology, especially, those focused on the synthesis of efficient bimetallic catalytic systems, as an alternative to the price and scarcity of ruthenium, the most active catalyst reported. In this sense, from the perspective of rational catalyst design, adjusting the main catalytic activity descriptor, a screening of supported catalysts with different compositional settings of cobalt-molybdenum metals is presented to evaluate their effect on the catalytic decomposition rate of ammonia. Subsequently, a kinetic study on the supported monometallic Co and Mo catalysts, as well as on the bimetallic CoMo catalyst with the highest activity is shown. The synthesis of catalysts supported on γ-alumina was carried out using the Charge Enhanced Dry Impregnation (CEDI) method, all with a 5% w/w loading metal. Seeking to maintain uniform dispersion, the catalysts were oxidized and activated (In-situ activation) using a flow of anhydrous air and hydrogen, respectively, under the same conditions: 40 ml min⁻¹ and 5 °C min⁻¹ from room temperature to 600 °C. Catalytic tests were carried out in a fixed-bed reactor, confirming the absence of transport limitations, as well as an Approach to equilibrium (< 1 x 10⁻⁴). The reaction rate on all catalysts was measured between 400 and 500 ºC at 53.09 kPa NH3. The synergy theoretically (DFT) reported for bimetallic catalysts was confirmed experimentally. Specifically, it was observed that the catalyst composed mainly of 75 mol% cobalt proved to be the most active in the experiments, followed by the monometallic cobalt and molybdenum catalysts, in this order of activity as referred to in the literature. A kinetic study was performed at 10.13 – 101.32 kPa NH3 and at four equidistant temperatures between 437 and 475 °C the data were adjusted to an LHHW-type model, which considered the desorption of nitrogen atoms from the active phase surface as the rate determining step (RDS). The regression analysis were carried out under an integral regime, using a minimization algorithm based on SLSQP. The physical meaning of the parameters adjusted in the kinetic model, such as the RDS rate constant (k₅) and the lumped adsorption constant of the quasi-equilibrated steps (α) was confirmed through their Arrhenius and Van't Hoff-type behavior (R² > 0.98), respectively. From an energetic perspective, the activation energy for cobalt, cobalt-molybdenum, and molybdenum was 115.2, 106.8, and 177.5 kJ mol⁻¹, respectively. With this evidence and considering the volcano shape described by the ammonia decomposition rate in relation to the metal composition ratio, the synergistic behavior of the system is clearly observed. However, since characterizations by XRD and TEM were inconclusive, the formation of intermetallic compounds should be still verified using HRTEM-EDS. From this point onwards, our objective is to incorporate parameters into the kinetic expressions that consider both compositional and structural elements and explore how these can maximize or influence H₂ production.

Keywords: CEDI, hydrogen carrier, LHHW, RDS

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Authors: Aleksander Ejsmont, Stefan Wuttke, Joanna Goscianska

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Gaining control over particle shape, size and crystallinity is an ongoing challenge for many materials. Especially metalorganic frameworks (MOFs) are recently widely studied. Besides their remarkable porosity and interesting topologies, morphology has proven to be a significant feature. It can affect the further material application. Thus seeking new approaches that enable MOF morphology modulation is important. MOFs are reticular structures, where building blocks are made up of organic linkers and metallic nodes. The most common strategy of ensuring metal source is using salts, which usually exhibit high solubility and hinder morphology control. However, there has been a growing interest in using metal oxides as structure-directing agents towards MOFs due to their very low solubility and shape preservation. Metal oxides can be treated as a metal reservoir during MOF synthesis. Up to now, reports in which receiving MOFs from metal oxides mostly present ZnO conversion to ZIF-8. However, there are other oxides, for instance, Co₃O₄, which often is overlooked due to their structural stability and insolubility in aqueous solutions. Cobalt-based materials are famed for catalytic activity. Therefore the development of their efficient synthesis is worth attention. In the presented work, an optimized Co₃O₄transition to Co-MOFviaa solvothermal approach was proposed. The starting point of the research was the synthesis of Co₃O₄ flower petals and needles under hydrothermal conditions using different cobalt salts (e.g., cobalt(II) chloride and cobalt(II) nitrate), in the presence of urea, and hexadecyltrimethylammonium bromide (CTAB) surfactant as a capping agent. After receiving cobalt hydroxide, the calcination process was performed at various temperatures (300–500 °C). Then cobalt oxides as a source of cobalt cations were subjected to reaction with trimesic acid in solvothermal environment and temperature of 120 °C leading to Co-MOF fabrication. The solution maintained in the system was a mixture of water, dimethylformamide, and ethanol, with the addition of strong acids (HF and HNO₃). To establish how solvents affect metal oxide conversion, several different solvent ratios were also applied. The materials received were characterized with analytical techniques, including X-ray powder diffraction, energy dispersive spectroscopy,low-temperature nitrogen adsorption/desorption, scanning, and transmission electron microscopy. It was confirmed that the synthetic routes have led to the formation of Co₃O₄ and Co-based MOF varied in shape and size of particles. The diffractograms showed receiving crystalline phase for Co₃O₄, and also for Co-MOF. The Co₃O₄ obtained from nitrates and with using low-temperature calcination resulted in smaller particles. The study indicated that cobalt oxide particles of different size influence the efficiency of conversion and morphology of Co-MOF. The highest conversion was achieved using metal oxides with small crystallites.

Keywords: Co-MOF, solvothermal synthesis, morphology control, core-shell

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Authors: Anna Krukowska, Tomasz Klimczuk, Adriana Zaleska-Medynska

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Photoactive materials have attracted attention due to their potential application in the degradation of environmental pollutants to non-hazardous compounds in an eco-friendly route. Among semiconductor photocatalysts, tantalates such as potassium tantalate (KTaO3) is one of the excellent functional photomaterial. However, tantalates-based materials are less active under visible-light irradiation, the enhancement in photoactivity could be improved with the modification of opto-eletronic properties of KTaO3 by doping rare earth metal (Er) and further photodeposition of noble metal nanoparticles (Pt). Inclusion of rare earth element in orthorhombic structure of tantalate can generate one high-energy photon by absorbing two or more incident low-energy photons, which convert visible-light and infrared-light into the ultraviolet-light to satisfy the requirement of KTaO3 photocatalysts. On the other hand, depositions of noble metal nanoparticles on the surface of semiconductor strongly absorb visible-light due to their surface plasmon resonance, in which their conducting electrons undergo a collective oscillation induced by electric field of visible-light. Furthermore, the high dispersion of Pt nanoparticles, which will be obtained by photodeposition process is additional important factor to improve the photocatalytic activity. The present work is aimed to study the effect of photocatalytic process of the prepared Er-doped KTaO3 and further incorporation of Pt nanoparticles by photodeposition. Moreover, the research is also studied correlations between photocatalytic activity and physico-chemical properties of obtained Pt/Er-KTaO3 samples. The Er-doped KTaO3 microcomposites were synthesized by a hydrothermal method. Then photodeposition method was used for Pt loading over Er-KTaO3. The structural and optical properties of Pt/Er-KTaO3 photocatalytic were characterized using scanning electron microscope (SEM), X-ray diffraction (XRD), volumetric adsorption method (BET), UV-Vis absorption measurement, Raman spectroscopy and luminescence spectroscopy. The photocatalytic properties of Pt/Er-KTaO3 microcomposites were investigated by degradation of phenol in aqueous phase as model pollutant under visible and ultraviolet-light irradiation. Results of this work show that all the prepared photocatalysis exhibit low BET surface area, although doping of the bare KTaO3 with rare earth element (Er) presents a slight increase in this value. The crystalline structure of Pt/Er-KTaO3 powders exhibited nearly identical positions for the main peak at about 22,8o and the XRD pattern could be assigned to an orthorhombic distorted perovskite structure. The Raman spectra of obtained semiconductors confirmed demonstrating perovskite-like structure. The optical absorption spectra of Pt nanoparticles exhibited plasmon absorption band for main peaks at about 216 and 264 nm. The addition of Pt nanoparticles increased photoactivity compared to Er-KTaO3 and pure KTaO3. Summary optical properties of KTaO3 change with its doping Er-element and further photodeposition of Pt nanoparticles.

Keywords: heterogeneous photocatalytic, KTaO3 photocatalysts, Er3+ ion doping, Pt photodeposition

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Authors: Ramzi Farra, Detre Teschner, Marc Willinger, Robert Schlögl

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Introduction: The conventional approach of characterizing solid catalysts under static conditions, i.e., before and after reaction, does not provide sufficient knowledge on the physicochemical processes occurring under dynamic conditions at the molecular level. Hence, the necessity of improving new in situ characterizing techniques with the potential of being used under real catalytic reaction conditions is highly desirable. In situ Prompt Gamma Activation Analysis (PGAA) is a rapidly developing chemical analytical technique that enables us experimentally to assess the coverage of surface species under catalytic turnover and correlate these with the reactivity. The catalytic HCl oxidation (Deacon reaction) over bulk ceria will serve as our example. Furthermore, the in situ Transmission Electron Microscopy is a powerful technique that can contribute to the study of atmosphere and temperature induced morphological or compositional changes of a catalyst at atomic resolution. The application of such techniques (PGAA and TEM) will pave the way to a greater and deeper understanding of the dynamic nature of active catalysts. Experimental/Methodology: In situ Prompt Gamma Activation Analysis (PGAA) experiments were carried out to determine the Cl uptake and the degree of surface chlorination under reaction conditions by varying p(O2), p(HCl), p(Cl2), and the reaction temperature. The abundance and dynamic evolution of OH groups on working catalyst under various steady-state conditions were studied by means of in situ FTIR with a specially designed homemade transmission cell. For real in situ TEM we use a commercial in situ holder with a home built gas feeding system and gas analytics. Conclusions: Two complimentary in situ techniques, namely in situ PGAA and in situ FTIR were utilities to investigate the surface coverage of the two most abundant species (Cl and OH). The OH density and Cl uptake were followed under multiple steady-state conditions as a function of p(O2), p(HCl), p(Cl2), and temperature. These experiments have shown that, the OH density positively correlates with the reactivity whereas Cl negatively. The p(HCl) experiments give rise to increased activity accompanied by Cl-coverage increase (opposite trend to p(O2) and T). Cl2 strongly inhibits the reaction, but no measurable increase of the Cl uptake was found. After considering all previous observations we conclude that only a minority of the available adsorption sites contribute to the reactivity. In addition, the mechanism of the catalysed reaction was proposed. The chlorine-oxygen competition for the available active sites renders re-oxidation as the rate-determining step of the catalysed reaction. Further investigations using in situ TEM are planned and will be conducted in the near future. Such experiments allow us to monitor active catalysts at the atomic scale under the most realistic conditions of temperature and pressure. The talk will shed a light on the potential and limitations of in situ PGAA and in situ TEM in the study of catalyst dynamics.

Keywords: CeO2, deacon process, in situ PGAA, in situ TEM, in situ FTIR

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Authors: Siba Soren, Purnendu Parhi

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Today, the world is facing a severe challenge due to depletion of traditional fossil fuels. Scientists across the globe are working for a solution that involves a dramatic shift to practical and environmentally sustainable energy sources. High-capacity energy systems, such as metal-air batteries, fuel cells, are highly desirable to meet the urgent requirement of sustainable energies. Among the fuel cells, Direct methanol fuel cells (DMFCs) are recognized as an ideal power source for mobile applications and have received considerable attention in recent past. In this advanced electrochemical energy conversion technologies, Oxygen Reduction Reaction (ORR) is of utmost importance. However, the poor kinetics of cathodic ORR in DMFCs significantly hampers their possibilities of commercialization. The oxygen is reduced in alkaline medium either through a 4-electron (equation i) or a 2-electron (equation ii) reduction pathway at the cathode ((i) O₂ + 2H₂O + 4e⁻ → 4OH⁻, (ii) O₂ + H₂O + 2e⁻ → OH⁻ + HO₂⁻ ). Due to sluggish ORR kinetics the ability to control the reduction of molecular oxygen electrocatalytically is still limited. The electrocatalytic ORR starts with adsorption of O₂ on the electrode surface followed by O–O bond activation/cleavage and oxide removal. The reaction further involves transfer of 4 electrons and 4 protons. The sluggish kinetics of ORR, on the one hand, demands high loading of precious metal-containing catalysts (e.g., Pt), which unfavorably increases the cost of these electrochemical energy conversion devices. Therefore, synthesis of active electrocatalyst with an increase in ORR performance is need of the hour. In the recent literature, there are many reports on transition metal oxide (TMO) based ORR catalysts for their high activity TMOs are also having drawbacks like low electrical conductivity, which seriously affects the electron transfer process during ORR. It was found that 2D graphene layer is having high electrical conductivity, large surface area, and excellent chemical stability, appeared to be an ultimate choice as support material to enhance the catalytic performance of bare metal oxide. g-C₃N₄ is also another candidate that has been used by the researcher for improving the ORR performance of metal oxides. This material provides more active reaction sites than other N containing carbon materials. Rare earth oxide like CeO₂ is also a good candidate for studying the ORR activity as the metal oxide not only possess unique electronic properties but also possess catalytically active sites. Here we will discuss the ORR performance (in alkaline medium) of N-rGO/C₃N₄ supported nano Cerium Oxides hybrid synthesized by microwave assisted Solvothermal method. These materials exhibit superior electrochemical stability and methanol tolerance capability to that of commercial Pt/C.

Keywords: oxygen reduction reaction, electrocatalyst, cerium oxide, graphene

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Authors: Damien Rinsant, Eugen Andreiadis, Michael Carboni, Daniel Meyer

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Different types of materials have been developed for the solid/liquid uranium extraction processes, such as functionalized organic polymers, hybrid silica or inorganic adsorbents. In general, these materials exhibit a moderate affinity for uranyl ions and poor selectivity against impurities like iron, vanadium or molybdenum. Moreover, the structural organization deficiency of these materials generates ion diffusion issues inside the material. Therefore, the aim of our study is to developed efficient and organized materials, stable in the acid media encountered in uranium extraction processes. Metal organic frameworks (MOFs) are hybrid crystalline materials consisting of an inorganic part (cluster or metal ions) and tailored organic linkers connected via coordination bonds. These hierarchical materials have exceptional surface area, thermal stability and a large variety of tunable structures. However, due to the reversibility of constitutive coordination bonds, MOFs have moderate stability in strongly complexing or acidic media. Only few of them are known to be stable in aqueous media and only one example is described in strong acidic media. However, these conditions are very often encountered in the environmental pollution remediation of mine wastewaters. To tackle the challenge of developing MOFs adapted for uranium extraction from acid mine waters, we have investigated the stability of several materials. To ensure a good stability we have synthetized and characterized different materials based on highly coordinated metal clusters, such as LnOFs and Zirconium based materials. Among the latter, the UiO family shows a great stability in sulfuric acid media even in the presence of 1.4 M sodium sulfate at pH 2. However, the stability in phosphoric media is reduced due to the high affinity between zirconium and phosphate ligand. Based on these results, we have developed a tertiary amine functionalized MOF denoted UiO-68-NMe2 particularly adapted for the extraction of anionic uranyl (VI) sulfate complexes mainly present in the acid mine solutions. The adsorption capacity of the material has been determined upon varying total sulfate concentration, contact time and uranium concentration. The extraction tests put in evidence different phenomena due to the complexity of the extraction media and the interaction between the MOF and sulfate anion. Finally, the extraction mechanisms and the interaction between uranyl and the MOF structure have been investigated. The functionalized material UiO-68-NMe2 has been characterized in the presence and absence of uranium by FT-IR, UV and Raman techniques. Moreover, the stability of the protonated amino functionalized MOF has been evaluated. The synthesis, characterization and evaluation of this type of hybrid material, particularly adapted for uranium extraction in sulfuric acid media by an anionic exchange mechanism, paved the way for the development of metal organic frameworks functionalized by different other chelating motifs, such as bifunctional ligands showing an enhanced affinity and selectivity for uranium in acid and complexing media. Work in this direction is currently in progress.

Keywords: extraction, MOF, ligand, uranium

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Authors: Mayoorika Shukla, Pramila Jakhar, Tejendra Dixit, I. A. Palani, Vipul Singh

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Biosensors are analytical devices with wide range of applications in biological, chemical, environmental and clinical analysis. It comprises of bio-recognition layer which has biomolecules (enzymes, antibodies, DNA, etc.) immobilized over it for detection of analyte and transducer which converts the biological signal into the electrical signal. The performance of biosensor primarily the depends on the bio-recognition layer and therefore it has to be chosen wisely. In this regard, nanostructures of metal oxides such as ZnO, SnO2, V2O5, and TiO2, etc. have been explored extensively as bio-recognition layer. Recently, ZnO has the attracted attention of researchers due to its unique properties like high iso-electric point, biocompatibility, stability, high electron mobility and high electron binding energy, etc. Although there have been many reports on usage of ZnO as bio-recognition layer but to the authors’ knowledge, none has ever observed correlation between optical properties like defect suppression and biosensing capability of the sensor. Here, ZnO nanorods (ZNR) have been synthesized by a low cost, simple and low-temperature hydrothermal growth process, over Platinum (Pt) coated glass substrate. The ZNR have been synthesized in two steps viz. initially a seed layer was coated over substrate (Pt coated glass) followed by immersion of it into nutrient solution of Zinc nitrate and Hexamethylenetetramine (HMTA) with in situ addition of KMnO4. The addition of KMnO4 was observed to have a profound effect over the growth rate anisotropy of ZnO nanostructures. Clustered and powdery growth of ZnO was observed without addition of KMnO4, although by addition of it during the growth, uniform and crystalline ZNR were found to be grown over the substrate. Moreover, the same has resulted in suppression of defects as observed by Normalized Photoluminescence (PL) spectra since KMnO4 is a strong oxidizing agent which provides an oxygen rich growth environment. Further, to explore the correlation between defect suppression and biosensing capability of the ZNR Glucose oxidase (Gox) was immobilized over it, using physical adsorption technique followed by drop casting of nafion. Here the main objective of the work was to analyze effect of defect suppression over biosensing capability, and therefore Gox has been chosen as model enzyme, and electrochemical amperometric glucose detection was performed. The incorporation of KMnO4 during growth has resulted in variation of optical and charge transfer properties of ZNR which in turn were observed to have deep impact on biosensor figure of merits. The sensitivity of biosensor was found to increase by 12-18 times, due to variations introduced by addition of KMnO4 during growth. The amperometric detection of glucose in continuously stirred buffer solution was performed. Interestingly, defect suppression has been observed to contribute towards the improvement of biosensor performance. The detailed mechanism of growth of ZNR along with the overall influence of defect suppression on the sensing capabilities of the resulting enzymatic electrochemical biosensor and different figure of merits of the biosensor (Glass/Pt/ZNR/Gox/Nafion) will be discussed during the conference.

Keywords: biosensors, defects, KMnO4, ZnO nanorods

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Authors: Valentina V. Goftman, Vladislav A. Pankratov, Alexey V. Markin, Tangi Aubert, Zeger Hens, Sarah De Saeger, Irina Yu. Goryacheva

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The most important requirements for biochemical applicability of quantum dots (QDs) are: 1) the surface cap should render intact or improved optical properties; 2) mono-dispersion and good stability in aqueous phase in a wide range of pH and ionic strength values; 3) presence of functional groups, available for bioconjugation; 4) minimal impact from the environment on the QDs’ properties and, vice versa, minimal influence of the QDs’ components on the environment; and 5) stability against chemical/biochemical/physical influence. The latter is especially important for in vitro and in vivo applications. For example, some physical intracellular delivery strategies (e.g., electroporation) imply a rapid high-voltage electric field impulse in order to temporarily generate hydrophilic pores in the cell plasma membrane, necessary for the passive transportation of QDs into the cell. In this regard, it is interesting to investigate how different capping layers, which can provide high stability and sufficient fluorescent properties of QDs in a water solution, behave under these abnormal conditions. In this contribution, hydrophobic core-shell CdSe/CdS/CdZnS/ZnS QDs (λem=600 nm), produced by means of the Successive Ion Layer Adsorption and Reaction (SILAR) technique, were transferred to a water solution using two of the most commonly used methods: (i) encapsulation in an amphiphilic brush polymer based on poly(maleic anhydride-alt-1-octadecene) (PMAO) modified with polyethylene glycol (PEG) chains and (ii) silica covering. Polymer encapsulation preserves the initial ligands on the QDs’ surface owing to the hydrophobic attraction between the hydrophobic groups of the amphiphilic molecules and the surface hydrophobic groups of the QDs. This covering process allows maintaining the initial fluorescent properties, but it leads to a considerable increase of the QDs’ size. However, covering with a silica shell, by means of the reverse microemulsion method, allows maintaining both size and fluorescent properties of the initial QDs. The obtained water solutions of polymer covered and silica-coated QDs in three different concentrations were exposed to a low-voltage electric field for a short time and the fluorescent properties were investigated. It is shown that the PMAO-PEG polymer acquires some additional charges in the presence of the electric field, which causes repulsion between the polymer and the QDs’ surface. This process destroys the homogeneity of the whole amphiphilic shell and it dramatically decreases the fluorescent properties (dropping to 10% from its initial value) because of the direct contact of the QDs with the strongly oxidative environment (water). In contrast, a silica shell possesses dielectric properties which allow retaining 90% of its initial fluorescence intensity, even after a longer electric impact. Thus, silica shells are clearly a preferable covering for bio-application of QDs, because – besides the high uniform morphology, controlled size and biocompatibility – it allows protecting QDs from oxidation, even under the influence of an electric field.

Keywords: electric field, polymer coating, quantum dots, silica covering, stability

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Authors: E. A. Krasikov

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As the service life of an operating nuclear power plant (NPP) increases, the potential misunderstanding of the degradation of aging components must receive more attention. Integrity assurance analysis contributes to the effective maintenance of adequate plant safety margins. In essence, the reactor pressure vessel (RPV) is the key structural component determining the NPP lifetime. Environmentally induced cracking in the stainless steel corrosion-preventing cladding of RPV’s has been recognized to be one of the technical problems in the maintenance and development of light-water reactors. Extensive cracking leading to failure of the cladding was found after 13000 net hours of operation in JPDR (Japan Power Demonstration Reactor). Some of the cracks have reached the base metal and further penetrated into the RPV in the form of localized corrosion. Failures of reactor internal components in both boiling water reactors and pressurized water reactors have increased after the accumulation of relatively high neutron fluences (5´1020 cm–2, E>0,5MeV). Therefore, in the case of cladding failure, the problem arises of hydrogen (as a corrosion product) embrittlement of irradiated RPV steel because of exposure to the coolant. At present when notable progress in plasma physics has been obtained practical energy utilization from fusion reactors (FR) is determined by the state of material science problems. The last includes not only the routine problems of nuclear engineering but also a number of entirely new problems connected with extreme conditions of materials operation – irradiation environment, hydrogenation, thermocycling, etc. Limiting data suggest that the combined effect of these factors is more severe than any one of them alone. To clarify the possible influence of the in-service synergistic phenomena on the FR structural materials properties we have studied hydrogen-irradiated steel interaction including alternating hydrogenation and heat treatment (annealing). Available information indicates that the life of the first wall could be expanded by means of periodic in-place annealing. The effects of neutron fluence and irradiation temperature on steel/hydrogen interactions (adsorption, desorption, diffusion, mechanical properties at different loading velocities, post-irradiation annealing) were studied. Experiments clearly reveal that the higher the neutron fluence and the lower the irradiation temperature, the more hydrogen-radiation defects occur, with corresponding effects on the steel mechanical properties. Hydrogen accumulation analyses and thermal desorption investigations were performed to prove the evidence of hydrogen trapping at irradiation defects. Extremely high susceptibility to hydrogen embrittlement was observed with specimens which had been irradiated at relatively low temperature. However, the susceptibility decreases with increasing irradiation temperature. To evaluate methods for the RPV’s residual lifetime evaluation and prediction, more work should be done on the irradiated metal–hydrogen interaction in order to monitor more reliably the status of irradiated materials.

Keywords: hydrogen, radiation, stability, structural steel

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Authors: Marius Sebastian Secula, Andreea Vajda, Benoit Cagnon, Ioan Mamaliga

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One of the most important classes of pollutants is represented by dyes. The synthetic character and complex molecular structure make them more stable and difficult to be biodegraded in water. The treatment of wastewaters containing dyes in order to separate/degrade dyes is of major importance. Various techniques have been employed to remove and/or degrade dyes in water. Advanced oxidation processes (AOPs) are known as among the most efficient ones towards dye degradation. The aim of this work is to investigate the efficiency of a cheap Iron-impregnated activated carbon Fenton-like catalyst in order to degrade organic compounds in aqueous solutions. In the presented study an anionic dye, Indigo Carmine, is considered as a model pollutant. Various AOPs are evaluated for the degradation of Indigo Carmine to establish the effect of the prepared catalyst. It was found that the Iron(II)-embedded activated carbon composite enhances significantly the degradation process of Indigo Carmine. Using the wet impregnation procedure, 5 g of L27 AC material were contacted with Fe(II) solutions of FeSO4 precursor at a theoretical iron content in the resulted composite of 1 %. The L27 AC was impregnated for 3h at 45°C, then filtered, washed several times with water and ethanol and dried at 55 °C for 24 h. Thermogravimetric analysis, Fourier transform infrared, X-ray diffraction, and transmission electron microscopy were employed to investigate the structural, textural, and micromorphology of the catalyst. Total iron content in the obtained composites and iron leakage were determined by spectrophotometric method using phenantroline. Photo-catalytic tests were performed using an UV - Consulting Peschl Laboratory Reactor System. UV light irradiation tests were carried out to determine the performance of the prepared Iron-impregnated composite towards the degradation of Indigo Carmine in aqueous solution using different conditions (17 W UV lamps, with and without in-situ generation of O3; different concentrations of H2O2, different initial concentrations of Indigo Carmine, different values of pH, different doses of NH4-OH enhancer). The photocatalytic tests were performed after the adsorption equilibrium has been established. The obtained results emphasize an enhancement of Indigo Carmine degradation in case of the heterogeneous photo-Fenton process conducted with an O3 generating UV lamp in the presence of hydrogen peroxide. The investigated process obeys the pseudo-first order kinetics. The photo-Fenton degradation of IC was tested at different values of initial concentration. The obtained results emphasize an enhancement of Indigo Carmine degradation in case of the heterogeneous photo-Fenton process conducted with an O3 generating UV lamp in the presence of hydrogen peroxide. Acknowledgments: This work was supported by a grant of the Romanian National Authority for Scientific Research and Innovation, CNCS - UEFISCDI, project number PN-II-RU-TE-2014-4-0405.

Keywords: photodegradation, heterogeneous Fenton, anionic dye, carbonaceous composite, screening factorial design

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Authors: Gabriela Wyszogrodzka, Przemyslaw Dorozynski, Barbara Gil, Maciej Strzempek, Bartosz Marszalek, Piotr Kulinowski, Wladyslaw Piotr Weglarz, Elzbieta Menaszek

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MOFs (Metal-Organic Frameworks) belong to a new group of porous materials with a hybrid organic-inorganic construction. Their structure is a network consisting of metal cations or clusters (acting as metallic centers, nodes) and the organic linkers between nodes. The interest in MOFs is primarily associated with the use of their well-developed surface and large porous. Possibility to build MOFs of biocompatible components let to use them as potential drug carriers. Furthermore, forming MOFs structure from cations possessing paramagnetic properties (e.g. iron cations) allows to use them as MRI (Magnetic Resonance Imaging) contrast agents. The concept of formation of particles that combine the ability to transfer active substance with imaging properties has been called theranostic (from words combination therapy and diagnostics). By building MOF structure from iron cations it is possible to use them as theranostic agents and monitoring the distribution of the active substance after administration in real time. In the study iron-MOF: Fe-MIL-101-NH2 was chosen, consisting of iron cluster in nodes of the structure and amino-terephthalic acid as a linker. The aim of the study was to investigate the possibility of applying Fe-MIL-101-NH2 as inhalable theranostic particulate system for the first-line anti-tuberculosis antibiotic – isoniazid. The drug content incorporated into Fe-MIL-101-NH2 was evaluated by dissolution study using spectrophotometric method. Results showed isoniazid encapsulation efficiency – ca. 12.5% wt. Possibility of Fe-MIL-101-NH2 application as the MRI contrast agent was demonstrated by magnetic resonance tomography. FeMIL-101-NH2 effectively shortening T1 and T2 relaxation times (increasing R1 and R2 relaxation rates) linearly with the concentrations of suspended material. Images obtained using multi-echo magnetic resonance imaging sequence revealed possibility to use FeMIL-101-NH2 as positive and negative contrasts depending on applied repetition time. MOFs micronization via ultrasound was evaluated by XRD, nitrogen adsorption, FTIR, SEM imaging and did not influence their crystal shape and size. Ultrasonication let to break the aggregates and achieve very homogeneously looking SEM images. MOFs cytotoxicity was evaluated in in vitro test with a highly sensitive resazurin based reagent PrestoBlue™ on L929 fibroblast cell line. After 24h no inhibition of cell proliferation was observed. All results proved potential possibility of application of ironMOFs as an isoniazid carrier and as MRI contrast agent in inhalatory treatment of tuberculosis. Acknowledgments: Authors gratefully acknowledge the National Science Center Poland for providing financial support, grant no 2014/15/B/ST5/04498.

Keywords: imaging agents, metal-organic frameworks, theranostics, tuberculosis

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Authors: Pola Goldberg Oppenheimer, Stephan Hofmann, Sumeet Mahajan

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Owing to its fingerprint molecular specificity and high sensitivity, surface-enhanced Raman scattering (SERS) is an established analytical tool for chemical and biological sensing capable of single-molecule detection. A strong Raman signal can be generated from SERS-active platforms given the analyte is within the enhanced plasmon field generated near a noble-metal nanostructured substrate. The key requirement for generating strong plasmon resonances to provide this electromagnetic enhancement is an appropriate metal surface roughness. Controlling nanoscale features for generating these regions of high electromagnetic enhancement, the so-called SERS ‘hot-spots’, is still a challenge. Significant advances have been made in SERS research, with wide-ranging techniques to generate substrates with tunable size and shape of the nanoscale roughness features. Nevertheless, the development and application of SERS has been inhibited by the irreproducibility and complexity of fabrication routes. The ability to generate straightforward, cost-effective, multiplex-able and addressable SERS substrates with high enhancements is of profound interest for miniaturised sensing devices. Carbon nanotubes (CNTs) have been concurrently, a topic of extensive research however, their applications for plasmonics has been only recently beginning to gain interest. CNTs can provide low-cost, large-active-area patternable substrates which, coupled with appropriate functionalization capable to provide advanced SERS-platforms. Herein, advanced methods to generate CNT-based SERS active detection platforms will be discussed. First, a novel electrohydrodynamic (EHD) lithographic technique will be introduced for patterning CNT-polymer composites, providing a straightforward, single-step approach for generating high-fidelity sub-micron-sized nanocomposite structures within which anisotropic CNTs are vertically aligned. The created structures are readily fine-tuned, which is an important requirement for optimizing SERS to obtain the highest enhancements with each of the EHD-CNTs individual structural units functioning as an isolated sensor. Further, gold-functionalized VACNTFs are fabricated as SERS micro-platforms. The dependence on the VACNTs’ diameters and density play an important role in the Raman signal strength, thus highlighting the importance of structural parameters, previously overlooked in designing and fabricating optimized CNTs-based SERS nanoprobes. VACNTs forests patterned into predesigned pillar structures are further utilized for multiplex detection of bio-analytes. Since CNTs exhibit electrical conductivity and unique adsorption properties, these are further harnessed in the development of novel chemical and bio-sensing platforms.

Keywords: carbon nanotubes (CNTs), EHD patterning, SERS, vertically aligned carbon nanotube forests (VACNTF)

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Authors: J. Roberto Lopez, Hened Saade, Graciela Morales, Javier Enriquez, Raul G. Lopez

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Implementation of systems based on nanostructures for drug delivery applications have taken relevance in recent studies focused on biomedical applications. Although there are several nanostructures as drugs carriers, the use of polymeric nanoparticles (PNP) has been widely studied for this purpose, however, the main issue for these nanostructures is the size control below 50 nm with a narrow distribution size, due to they must go through different physiological barriers and avoid to be filtered by kidneys (< 10 nm) or the spleen (> 100 nm). Thus, considering these and other factors, it can be mentioned that drug-loaded nanostructures with sizes varying between 10 and 50 nm are preferred in the development and study of PNP/drugs systems. In this sense, the Semicontinuous Heterophase Polymerization (SHP) offers the possibility to obtain PNP in the desired size range. Considering the above explained, methacrylic copolymer nanoparticles were obtained under SHP. The reactions were carried out in a jacketed glass reactor with the required quantities of water, ammonium persulfate as initiator, sodium dodecyl sulfate/sodium dioctyl sulfosuccinate as surfactants, methyl methacrylate and methacrylic acid as monomers with molar ratio of 2/1, respectively. The monomer solution was dosed dropwise during reaction at 70 °C with a mechanical stirring of 650 rpm. Nanoparticles of poly(methyl methacrylate-co-methacrylic acid) were loaded with acetylsalicylic acid (ASA, aspirin) by a chemical adsorption technique. The purified latex was put in contact with a solution of ASA in dichloromethane (DCM) at 0.1, 0.2, 0.4 or 0.6 wt-%, at 35°C during 12 hours. According to the boiling point of DCM, as well as DCM and water densities, the loading process is completed when the whole DCM is evaporated. The hydrodynamic diameter was measured after polymerization by quasi-elastic light scattering and transmission electron microscopy, before and after loading procedures with ASA. The quantitative and qualitative analyses of PNP loaded with ASA were measured by infrared spectroscopy, differential scattering calorimetry and thermogravimetric analysis. Also, the molar mass distributions of polymers were determined in a gel permeation chromatograph apparatus. The load capacity and efficiency were determined by gravimetric analysis. The hydrodynamic diameter results for methacrylic PNP without ASA showed a narrow distribution with an average particle size around 10 nm and a composition methyl methacrylate/methacrylic acid molar ratio equal to 2/1, same composition of Eudragit S100, which is a commercial compound widely used as excipient. Moreover, the latex was stabilized in a relative high solids content (around 11 %), a monomer conversion almost 95 % and a number molecular weight around 400 Kg/mol. The average particle size in the PNP/aspirin systems fluctuated between 18 and 24 nm depending on the initial percentage of aspirin in the loading process, being the drug content as high as 24 % with an efficiency loading of 36 %. These average sizes results have not been reported in the literature, thus, the methacrylic nanoparticles here reported are capable to be loaded with a considerable amount of ASA and be used as a drug carrier.

Keywords: aspirin, biocompatibility, biodegradable, Eudragit S100, methacrylic nanoparticles

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Authors: Natalia Lukasik, Ewa Wagner-Wysiecka

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Development of selective, fast-responsive, and economical sensors for diverse ions detection and determination is one of the most extensively studied areas due to its importance in the field of clinical, environmental and industrial analysis. Among chemical sensors, vast popularity has gained ionophore-based optical sensors, where the generated analytical signal is a consequence of the molecular recognition of ion by the ionophore. Change of color occurring during host-guest interactions allows for quantitative analysis and for 'naked-eye' detection without the need of using sophisticated equipment. An example of application of such sensors is colorimetric detection of iron(III) cations. Iron as one of the most significant trace elements plays roles in many biochemical processes. For these reasons, the development of reliable, fast, and selective methods of iron ions determination is highly demanded. Taking all mentioned above into account a chromogenic amide derivative of 3,4-dihydroxybenzoic acid was synthesized, and its ability to iron(III) recognition was tested. To the best of authors knowledge (according to chemical abstracts) the obtained ligand has not been described in the literature so far. The catechol moiety was introduced to the ligand structure in order to mimic the action of naturally occurring siderophores-iron(III)-selective receptors. The ligand–ion interactions were studied using spectroscopic methods: UV-Vis spectrophotometry and infrared spectroscopy. The spectrophotometric measurements revealed that the amide exhibits affinity to iron(III) in dimethyl sulfoxide and fully aqueous solution, what is manifested by the change of color from yellow to green. Incorporation of the tested amide into a polymeric matrix (cellulose triacetate) ensured effective recognition of iron(III) at pH 3 with the detection limit 1.58×10⁻⁵ M. For the obtained sensor material parameters like linear response range, response time, selectivity, and possibility of regeneration were determined. In order to evaluate the effect of the size of the sensing material on iron(III) detection nanospheres (in the form of nanoemulsion) containing the tested amide were also prepared. According to DLS (dynamic light scattering) measurements, the size of the nanospheres is 308.02 ± 0.67 nm. Work parameters of the nanospheres were determined and compared with cellulose triacetate-based material. Additionally, for fast, qualitative experiments the test strips were prepared by adsorption of the amide solution on a glass microfiber material. Visual limit of detection of iron(III) at pH 3 by the test strips was estimated at the level 10⁻⁴ M. In conclusion, reported here amide derived from 3,4- dihydroxybenzoic acid proved to be an effective candidate for optical sensing of iron(III) in fully aqueous solutions. N. L. kindly acknowledges financial support from National Science Centre Poland the grant no. 2017/01/X/ST4/01680. Authors thank for financial support from Gdansk University of Technology grant no. 032406.

Keywords: ion-selective optode, iron(III) recognition, nanospheres, optical sensor

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Authors: Ashish Thakur

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This technical paper was written in view of focusing the biomaterials and its various applications in modern industries. Author tires to elaborate not only the medical, infect plenty of application in other industries. The scope of the research area covers the wide range of physical, biological and chemical sciences that underpin the design of biomaterials and the clinical disciplines in which they are used. A biomaterial is now defined as a substance that has been engineered to take a form which, alone or as part of a complex system, is used to direct, by control of interactions with components of living systems, the course of any therapeutic or diagnostic procedure. Biomaterials are invariably in contact with living tissues. Thus, interactions between the surface of a synthetic material and biological environment must be well understood. This paper reviews the benefits and challenges associated with surface modification of the metals in biomedical applications. The paper also elaborates how the surface characteristics of metallic biomaterials, such as surface chemistry, topography, surface charge, and wettability, influence the protein adsorption and subsequent cell behavior in terms of adhesion, proliferation, and differentiation at the biomaterial–tissue interface. The chapter also highlights various techniques required for surface modification and coating of metallic biomaterials, including physicochemical and biochemical surface treatments and calcium phosphate and oxide coatings. In this review, the attention is focused on the biomaterial-associated infections, from which the need for anti-infective biomaterials originates. Biomaterial-associated infections differ markedly for epidemiology, aetiology and severity, depending mainly on the anatomic site, on the time of biomaterial application, and on the depth of the tissues harbouring the prosthesis. Here, the diversity and complexity of the different scenarios where medical devices are currently utilised are explored, providing an overview of the emblematic applicative fields and of the requirements for anti-infective biomaterials. In addition to this, chapter introduces nanomedicine and the use of both natural and synthetic polymeric biomaterials, focuses on specific current polymeric nanomedicine applications and research, and concludes with the challenges of nanomedicine research. Infection is currently regarded as the most severe and devastating complication associated to the use of biomaterials. Osteoporosis is a worldwide disease with a very high prevalence in humans older than 50. The main clinical consequences are bone fractures, which often lead to patient disability or even death. A number of commercial biomaterials are currently used to treat osteoporotic bone fractures, but most of these have not been specifically designed for that purpose. Many drug- or cell-loaded biomaterials have been proposed in research laboratories, but very few have received approval for commercial use. Polymeric nanomaterial-based therapeutics plays a key role in the field of medicine in treatment areas such as drug delivery, tissue engineering, cancer, diabetes, and neurodegenerative diseases. Advantages in the use of polymers over other materials for nanomedicine include increased functionality, design flexibility, improved processability, and, in some cases, biocompatibility.

Keywords: nanomedicine, tissue, infections, biomaterials

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Authors: Sumeet Rai, Anuj Tyagi, B. T. Naveen Kumar, Shubhkaramjeet Kaur, Niraj K. Singh

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Since their discovery, indiscriminate use of antibiotics in human, veterinary and aquaculture systems has resulted in global emergence/spread of multidrug-resistant bacterial pathogens. Thus, the need for alternative approaches to control bacterial infections has become utmost important. High selectivity/specificity of bacteriophages (phages) permits the targeting of specific bacteria without affecting the desirable flora. In this study, a lytic phage (Ahp1) specific to Aeromonas hydrophila subsp. hydrophila was isolated from finfish aquaculture pond. The host range of Ahp1 range was tested against 10 isolates of A. hydrophila, 7 isolates of A. veronii, 25 Vibrio cholerae isolates, 4 V. parahaemolyticus isolates and one isolate each of V. harveyi and Salmonella enterica collected previously. Except the host A. hydrophila subsp. hydrophila strain, no lytic activity against any other bacterial was detected. During the adsorption rate and one-step growth curve analysis, 69.7% of phage particles were able to get adsorbed on host cell followed by the release of 93 ± 6 phage progenies per host cell after a latent period of ~30 min. Phage nucleic acid was extracted by column purification methods. After determining the nature of phage nucleic acid as dsDNA, phage genome was subjected to next-generation sequencing by generating paired-end (PE, 2 x 300bp) reads on Illumina MiSeq system. De novo assembly of sequencing reads generated circular phage genome of 42,439 bp with G+C content of 58.95%. During open read frame (ORF) prediction and annotation, 22 ORFs (out of 49 total predicted ORFs) were functionally annotated and rest encoded for hypothetical proteins. Proteins involved in major functions such as phage structure formation and packaging, DNA replication and repair, DNA transcription and host cell lysis were encoded by the phage genome. The complete genome sequence of Ahp1 along with gene annotation was submitted to NCBI GenBank (accession number MF683623). Stability of Ahp1 preparations at storage temperatures of 4 °C, 30 °C, and 40 °C was studied over a period of 9 months. At 40 °C storage, phage counts declined by 4 log units within one month; with a total loss of viability after 2 months. At 30 °C temperature, phage preparation was stable for < 5 months. On the other hand, phage counts decreased by only 2 log units over a period of 9 during storage at 4 °C. As some of the phages have also been reported as glycerol sensitive, the stability of Ahp1 preparations in (0%, 15%, 30% and 45%) glycerol stocks were also studied during storage at -80 °C over a period of 9 months. The phage counts decreased only by 2 log units during storage, and no significant difference in phage counts was observed at different concentrations of glycerol. The Ahp1 phage discovered in our study had a very narrow host range and it may be useful for phage typing applications. Moreover, the endolysin and holin genes in Ahp1 genome could be ideal candidates for recombinant cloning and expression of antimicrobial proteins.

Keywords: Aeromonas hydrophila, endolysin, phage, narrow host range

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Authors: Hanna Abbo, Siyasanga Noganta, Salam Titinchi

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The global lack of clean water for human sanitation and other purposes has become an emerging dilemma for human beings. The presence of organic pollutants in wastewater produced by textile industries, leather manufacturing and chemical industries is an alarming matter for a safe environment and human health. For the last decades, conventional methods have been applied for the purification of water but due to industrialization these methods fall short. Advanced oxidation processes and their reliable application in degradation of many contaminants have been reported as a potential method to reduce and/or alleviate this problem. Lately it has been assumed that incorporation of some metal nanoparticles such as magnetite nanoparticles as photocatalyst for Fenton reaction which could improve the degradation efficiency of contaminants. Core/shell nanoparticles, are extensively studied because of their wide applications in the biomedical, drug delivery, electronics fields and water treatment. The current study is centred on the synthesis of silver-doped Fe3O4/SiO2/TiO2 photocatalyst. Magnetically separable Fe3O4@SiO2@TiO2 composite with core–shell structure were synthesized by the deposition of uniform anatase TiO2 NPs on Fe3O4@SiO2 by using titanium butoxide (TBOT) as titanium source. Then, the silver is doped on SiO2 layer by hydrothermal method. Integration of magnetic nanoparticles was suggested to avoid the post separation difficulties associated with the powder form of the TiO2 catalyst, increase of the surface area and adsorption properties. The morphology, structure, composition, and magnetism of the resulting composites were characterized and their photocatalytic activities were also evaluated. The results demonstrate that TiO2 NPs were uniformly deposited on the Fe3O4@SiO2 surface. The silver nanoparticles were also uniformly distributed on the surface of TiO2 nanoparticles. The aim of this work is to study the suitability of photocatalysis for the treatment of aqueous streams containing organic pollutants such as methylene blue which is selected as a model compound to represent one of the pollutants existing in wastewaters. Various factors such as initial pollutant concentration, photocatalyst dose and wastewater matrix were studied for their effect on the photocatalytic degradation of the organic model pollutants using the as synthesized catalysts and compared with the commercial titanium dioxide (Aeroxide P25). Photocatalysis was found to be a potential purification method for the studied pollutant also in an industrial wastewater matrix with the removal percentages of over 81 % within 15 minutes. Methylene blue was removed most efficiently and its removal consumed the least of energy in terms of the specific applied energy. The magnetic Ag/SiO2/TiO2 composites show high photocatalytic performance and can be recycled three times by magnetic separation without major loss of activity, which meant that they can be used as efficient and conveniently renewable photocatalyst.

Keywords: Magnetite nanoparticles, Titanium, Photocatalyst, Organic pollutant, Water treatment

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Authors: Istvan Szilagyi, Marko Pavlovic, Paul Rouster

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Antioxidant enzymes are the most efficient defense systems against reactive oxygen species, which cause severe damage in living organisms and industrial products. However, their supplementation is problematic due to their high sensitivity to the environmental conditions. Immobilization on carrier nanoparticles is a promising research direction towards the improvement of their functional and colloidal stability. In that way, their applications in biomedical treatments and manufacturing processes in the food, textile and cosmetic industry can be extended. The main goal of the present research was to prepare and formulate antioxidant bionanocomposites composed of superoxide dismutase (SOD) enzyme, anionic clay (layered double hydroxide, LDH) nanoparticle and heparin (HEP) polyelectrolyte. To characterize the structure and the colloidal stability of the obtained compounds in suspension and solid state, electrophoresis, dynamic light scattering, transmission electron microscopy, spectrophotometry, thermogravimetry, X-ray diffraction, infrared and fluorescence spectroscopy were used as experimental techniques. LDH-SOD composite was synthesized by enzyme immobilization on the clay particles via electrostatic and hydrophobic interactions, which resulted in a strong adsorption of the SOD on the LDH surface, i.e., no enzyme leakage was observed once the material was suspended in aqueous solutions. However, the LDH-SOD showed only limited resistance against salt-induced aggregation and large irregularly shaped clusters formed during short term interval even at lower ionic strengths. Since sufficiently high colloidal stability is a key requirement in most of the applications mentioned above, the nanocomposite was coated with HEP polyelectrolyte to develop highly stable suspensions of primary LDH-SOD-HEP particles. HEP is a natural anticoagulant with one of the highest negative line charge density among the known macromolecules. The experimental results indicated that it strongly adsorbed on the oppositely charged LDH-SOD surface leading to charge inversion and to the formation of negatively charged LDH-SOD-HEP. The obtained hybrid materials formed stable suspension even under extreme conditions, where classical colloid chemistry theories predict rapid aggregation of the particles and unstable suspensions. Such a stabilization effect originated from electrostatic repulsion between the particles of the same sign of charge as well as from steric repulsion due to the osmotic pressure raised during the overlap of the polyelectrolyte chains adsorbed on the surface. In addition, the SOD enzyme kept its structural and functional integrity during the immobilization and coating processes and hence, the LDH-SOD-HEP bionanocomposite possessed excellent activity in decomposition of superoxide radical anions, as revealed in biochemical test reactions. In conclusion, due to the improved colloidal stability and the good efficiency in scavenging superoxide radical ions, the developed enzymatic system is a promising antioxidant candidate for biomedical or other manufacturing processes, wherever the aim is to decompose reactive oxygen species in suspensions.

Keywords: clay, enzyme, polyelectrolyte, formulation

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Authors: D. Malouch, M. Berchel, C. Dreanno, S. Stachowski-Haberkorn, P-A. Jaffres

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Biofouling is a complex natural phenomenon that involves biological, physical and chemical properties related to the environment, the submerged surface and the living organisms involved. Bio-colonization of artificial structures can cause various economic and environmental impacts. The increase in costs associated with the over-consumption of fuel from biocolonized vessels has been widely studied. Measurement drifts from submerged sensors, as well as obstructions in heat exchangers, and deterioration of offshore structures are major difficulties that industries are dealing with. Therefore, surfaces that inhibit biocolonization are required in different areas (water treatment, marine paints, etc.) and many efforts have been devoted to produce efficient and eco-compatible antifouling agents. The different steps of surface fouling are widely described in literature. Studying the biofilm and its stages provides a better understanding of how to elaborate more efficient antifouling strategies. Several approaches are currently applied, such as the use of biocide anti-fouling paint (mainly with copper derivatives) and super-hydrophobic coatings. While these two processes are proving to be the most effective, they are not entirely satisfactory, especially in a context of a changing legislation. Nowadays, the challenge is to prevent biofouling with non-biocide compounds, offering a cost effective solution, but with no toxic effects on marine organisms. Since the micro-fouling phase plays an important role in the regulation of the following steps of biofilm formation, it is desired to reduce or delate biofouling of a given surface by inhibiting the micro-fouling at its early stages. In our recent works, we reported that some amphiphilic compounds exhibited bacteriostatic or bactericidal properties at a concentration that did not affect mammalian eukaryotic cells. These remarkable properties invited us to assess this type of bio-inspired phospholipids to prevent the colonization of surfaces by marine bacteria. Of note, other studies reported that amphiphilic compounds interacted with bacteria leading to a reduction of their development. An amphiphilic compound is a molecule consisting of a hydrophobic domain and a polar head (ionic or non-ionic). These compounds appear to have interesting antifouling properties: some ionic compounds have shown antimicrobial activity, and zwitterions can reduce nonspecific adsorption of proteins. Herein, we investigate the potential of amphiphilic compounds as inhibitors of bacterial growth and marine biofilm formation. The aim of this study is to compare the efficacy of four synthetic phospholipids that features a cationic charge or a zwitterionic polar-head group to prevent microfouling with marine bacteria. Toxicity of these compounds was also studied in order to identify the most promising compounds that inhibit biofilm development and show low cytotoxicity on two links representative of coastal marine food webs: phytoplankton and oyster larvae.

Keywords: amphiphilic phospholipids, biofilm, marine fouling, non-toxique assays

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Authors: Masood Otarod, Ronald M. Supkowski

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This abstract discusses a method that reduces the general dispersion model in cylindrical coordinates to a second order linear ordinary differential equation with constant coefficients so that it can be utilized to conduct kinetic studies in packed bed tubular catalytic reactors at a broad range of Reynolds numbers. The model was tested by 13CO isotope transient tracing of the CO adsorption of Boudouard reaction in a differential reactor at an average Reynolds number of 0.2 over Pd-Al2O3 catalyst. Detailed experimental results have provided evidence for the validity of the theoretical framing of the model and the estimated parameters are consistent with the literature. The solution of the general dispersion model requires the knowledge of the radial distribution of axial velocity. This is not always known. Hence, up until now, the implementation of the dispersion model has been largely restricted to the plug-flow regime. But, ideal plug-flow is impossible to achieve and flow regimes approximating plug-flow leave much room for debate as to the validity of the results. The reduction of the general dispersion model transpires as a result of the application of a factorization theorem. Factorization theorem is derived from the observation that a cross section of a catalytic bed consists of a solid phase across which the reaction takes place and a void or porous phase across which no significant measure of reaction occurs. The disparity in flow and the heterogeneity of the catalytic bed cause the concentration of reacting compounds to fluctuate radially. These variabilities signify the existence of radial positions at which the radial gradient of concentration is zero. Succinctly, factorization theorem states that a concentration function of axial and radial coordinates in a catalytic bed is factorable as the product of the mean radial cup-mixing function and a contingent dimensionless function. The concentration of adsorbed compounds are also factorable since they are piecewise continuous functions and suffer the same variability but in the reverse order of the concentration of mobile phase compounds. Factorability is a property of packed beds which transforms the general dispersion model to an equation in terms of the measurable mean radial cup-mixing concentration of the mobile phase compounds and mean cross-sectional concentration of adsorbed species. The reduced model does not require the knowledge of the radial distribution of the axial velocity. Instead, it is characterized by new transport parameters so denoted by Ωc, Ωa, Ωc, and which are respectively denominated convection coefficient cofactor, axial dispersion coefficient cofactor, and radial dispersion coefficient cofactor. These cofactors adjust the dispersion equation as compensation for the unavailability of the radial distribution of the axial velocity. Together with the rest of the kinetic parameters they can be determined from experimental data via an optimization procedure. Our data showed that the estimated parameters Ωc, Ωa Ωr, are monotonically correlated with the Reynolds number. This is expected to be the case based on the theoretical construct of the model. Computer generated simulations of methanation reaction on nickel provide additional support for the utility of the newly conceptualized dispersion model.

Keywords: factorization, general dispersion model, isotope transient kinetic, partial differential equations

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Authors: Päärn Paiste, Margit Kõiv, Riho Mõtlep, Kalle Kirsimäe

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For small-scale wastewater management, the treatment wetlands (TWs) as a low cost alternative to conventional treatment facilities, can be used. However, P removal capacity of TW systems is usually problematic. P removal in TWs is mainly dependent on the physico–chemical and hydrological properties of the filter material. Highest P removal efficiency has been shown trough Ca-phosphate precipitation (i.e. active filtration) in Ca-rich alkaline filter materials, e.g. industrial by-products like hydrated oil shale ash (HOSA), metallurgical slags. In this contribution we report preliminary results of a full-scale TW system using HOSA material for P removal for a municipal wastewater at Nõo site, Estonia. The main goals of this ongoing project are to evaluate: a) the long-term P removal efficiency of HOSA using real waste water; b) the effect of high organic loading rate; c) variable P-loading effects on the P removal mechanism (adsorption/direct precipitation); and d) the form and composition of phosphate precipitates. Onsite full-scale experiment with two concurrent filter systems for treatment of municipal wastewater was established in September 2013. System’s pretreatment steps include septic tank (2 m2) and vertical down-flow LECA filters (3 m2 each), followed by horizontal subsurface HOSA filters (effective volume 8 m3 each). Overall organic and hydraulic loading rates of both systems are the same. However, the first system is operated in a stable hydraulic loading regime and the second in variable loading regime that imitates the wastewater production in an average household. Piezometers for water and perforated sample containers for filter material sampling were incorporated inside the filter beds to allow for continuous in-situ monitoring. During the 18 months of operation the median removal efficiency (inflow to outflow) of both systems were over 99% for TP, 93% for COD and 57% for TN. However, we observed significant differences in the samples collected in different points inside the filter systems. In both systems, we observed development of preferred flow paths and zones with high and low loadings. The filters show formation and a gradual advance of a “dead” zone along the flow path (zone with saturated filter material characterized by ineffective removal rates), which develops more rapidly in the system working under variable loading regime. The formation of the “dead” zone is accompanied by the growth of organic substances on the filter material particles that evidently inhibit the P removal. Phase analysis of used filter materials using X-ray diffraction method reveals formation of minor amounts of amorphous Ca-phosphate precipitates. This finding is supported by ATR-FTIR and SEM-EDS measurements, which also reveal Ca-phosphate and authigenic carbonate precipitation. Our first experimental results demonstrate that organic pollution and loading regime significantly affect the performance of hydrated ash filters. The material analyses also show that P is incorporated into a carbonate substituted hydroxyapatite phase.

Keywords: active filtration, apatite, hydrated oil shale ash, organic pollution, phosphorus

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Authors: Helen S. Joyner (Melito), Mohammad Anvari

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Concentrated emulsions stabilized by proteins are systems of great importance in food, pharmaceutical and cosmetic products. Controlling emulsion rheology is critical for ensuring desired properties during formation, storage, and consumption of emulsion-based products. Studies on concentrated emulsions have focused on rheology of monodispersed systems. However, emulsions used for industrial applications are polydispersed in nature, and this polydispersity is regarded as an important parameter that also governs the rheology of the concentrated emulsions. Therefore, the objective of this study was to characterize rheological (small and large deformation behaviors) and microstructural properties of concentrated emulsions which were not truly monodispersed as usually encountered in food products such as margarines, mayonnaise, creams, spreads, and etc. The concentrated emulsions were prepared at different concentrations of fish gelatin (0.2, 0.4, 0.8% w/v in the whole emulsion system), oil-water ratio 80-20 (w/w), homogenization speed 10000 rpm, and 25oC. Confocal laser scanning microscopy (CLSM) was used to determine the microstructure of the emulsions. To prepare samples for CLSM analysis, FG solutions were stained by Fluorescein isothiocyanate dye. Emulsion viscosity profiles were determined using shear rate sweeps (0.01 to 100 1/s). The linear viscoelastic regions (LVRs) of the emulsions were determined using strain sweeps (0.01 to 100% strain) for each sample. Frequency sweeps were performed in the LVR (0.1% strain) from 0.6 to 100 rad/s. Large amplitude oscillatory shear (LAOS) testing was conducted by collecting raw waveform data at 0.05, 1, 10, and 100% strain at 4 different frequencies (0.5, 1, 10, and 100 rad/s). All measurements were performed in triplicate at 25oC. The CLSM results revealed that increased fish gelatin concentration resulted in more stable oil-in-water emulsions with homogeneous, finely dispersed oil droplets. Furthermore, the protein concentration had a significant effect on emulsion rheological properties. Apparent viscosity and dynamic moduli at small deformations increased with increasing fish gelatin concentration. These results were related to increased inter-droplet network connections caused by increased fish gelatin adsorption at the surface of oil droplets. Nevertheless, all samples showed shear-thinning and weak gel behaviors over shear rate and frequency sweeps, respectively. Lissajous plots, or plots of stress versus strain, and phase lag values were used to determine nonlinear behavior of the emulsions in LAOS testing. Greater distortion in the elliptical shape of the plots followed by higher phase lag values was observed at large strains and frequencies in all samples, indicating increased nonlinear behavior. Shifts from elastic-dominated to viscous dominated behavior were also observed. These shifts were attributed to damage to the sample microstructure (e.g. gel network disruption), which would lead to viscous-type behaviors such as permanent deformation and flow. Unlike the small deformation results, the LAOS behavior of the concentrated emulsions was not dependent on fish gelatin concentration. Systems with different microstructures showed similar nonlinear viscoelastic behaviors. The results of this study provided valuable information that can be used to incorporate concentrated emulsions in emulsion-based food formulations.

Keywords: concentrated emulsion, fish gelatin, microstructure, rheology

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Authors: Ellana Boada, Eric Santos-Clotas, Alba Cabrera-Codony, Maria Martin, Lluis Baneras, Frederic Gich

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Volatile methylsiloxanes (VMS) are a group of manmade silicone compounds widely used in household and industrial applications that end up on the biogas produced through the anaerobic digestion of organic matter in landfills and wastewater treatment plants. The presence of VMS during the biogas energy conversion can cause damage on the engines, reducing the efficiency of this renewable energy source. Non regenerative adsorption onto activated carbon is the most widely used technology to remove siloxanes from biogas, while new trends point out that biotechnology offers a low-cost and environmentally friendly alternative to conventional technologies. The first objective of this research was to enrich, isolate and identify bacterial species able to grow using siloxane molecules as a sole carbon source: anoxic wastewater sludge was used as initial inoculum in liquid anoxic enrichments, adding D4 (as representative siloxane compound) previously adsorbed on activated carbon. After several months of acclimatization, liquid enrichments were plated onto solid media containing D4 and thirty-four bacterial isolates were obtained. 16S rRNA gene sequencing allowed the identification of strains belonging to the following species: Ciceribacter lividus, Alicycliphilus denitrificans, Pseudomonas aeruginosa and Pseudomonas citronellolis which are described to be capable to degrade toxic volatile organic compounds. Kinetic assays with 8 representative strains revealed higher cell growth in the presence of D4 compared to the control. Our second objective was to characterize the community composition and diversity of the microbial community present in the enrichments and to elucidate whether the isolated strains were representative members of the community or not. DNA samples were extracted, the 16S rRNA gene was amplified (515F & 806R primer pair), and the microbiome analyzed from sequences obtained with a MiSeq PE250 platform. Results showed that the retrieved isolates only represented a minor fraction of the microorganisms present in the enrichment samples, which were represented by Alpha, Beta, and Gamma proteobacteria as dominant groups in the category class thus suggesting that other microbial species and/or consortia may be important for D4 biodegradation. These results highlight the need of additional protocols for the isolation of relevant D4 degraders. Currently, we are developing molecular tools targeting key genes involved in siloxane biodegradation to identify and quantify the capacity of the isolates to metabolize D4 in batch cultures supplied with a synthetic gas stream of air containing 60 mg m⁻³ of D4 together with other volatile organic compounds found in the biogas mixture (i.e. toluene, hexane and limonene). The isolates were used as inoculum in a biotrickling filter containing lava rocks and activated carbon to assess their capacity for siloxane removal. Preliminary results of biotrickling filter performance showed 35% of siloxane biodegradation in a contact time of 14 minutes, denoting that biological siloxane removal is a promising technology for biogas upgrading.

Keywords: bacterial cultivation, biogas upgrading, microbiome, siloxanes

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