Search results for: liquid chromatography

Authors: Nikhil John Kollannur, Dali Naidu Arnepalli

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Most of the surface related phenomena in the case of fine-grained soil are attributed to their unique surface charge properties and specific surface area. The temporal variations in soil behavior, to some extent, can be credited to the changes in these properties. Among the multitude of factors that affect the charge and surface area of clay minerals, the inherent system chemistry occupies the cardinal position. The impact is more profound when the chemistry change is manifested in terms of the system pH. pH plays a significant role by modifying the edge charges of clay minerals and facilitating mineral dissolution. Hence there is a need to address the variations in physical and charge properties of fine-grained soils treated over a range of acidic as well as alkaline conditions. In the present study, three soils (two soils commercially procured and one natural soil) exhibiting distinct mineralogical compositions are subjected to different pH environment over a range of 2 to 13. The soil-solutions prepared at a definite liquid to solid ratio are adjusted to the required pH value by adding measured quantities of 0.1M HCl/0.1M NaOH. The studies are conducted over a range of interaction time, varying from 1 to 96 hours. The treated soils are then analyzed for their physical properties in terms of specific surface area and particle size characteristics. Further, modifications in surface morphology are evaluated from scanning electron microscope (SEM) imaging. Changes in the surface charge properties are assessed in terms of zeta potential measurements. Studies show significant variations in total surface area, probably because of the dissolution of clay minerals. This observation is further substantiated by the morphological analysis with SEM imaging. The zeta potential measurements on soils indicate noticeable variation upon pH treatment, which is partially ascribed to the modifications in the pH-dependant edge charges and partially due to the clay mineral dissolution. The results provide valuable insight into the role of pH in a clay-electrolyte system upon surface related phenomena such as species adsorption, fabric modification etc.

Keywords: acid and alkali treatment, mineral dissolution , specific surface area, zeta potential

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Authors: Emma O’ Keeffe, Helen Hughes, Peter McLoughlin, Shiau Pin Tan, Nick McCarthy

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Biosecurity is emerging as one of the most important issues facing the agricultural and forestry community. This is as a result of increased invasion from new pests and diseases with the main protocol for dealing with these species being the use of synthetic pesticides. However, these chemicals have been shown to exhibit negative effects on the environment. Seaweeds represent a vast untapped resource of bio-molecules with a broad range of biological activities including pesticidal. This project investigated both the antifungal and antibacterial activity of seaweed species against two problematic root rot fungi, Armillaria mellea and Heterobasidion annosum and ten quarantine bacterial plant pathogens including Xanthomonas arboricola, Xanthomonas fragariae, and Erwinia amylovora. Four seaweed species were harvested from the South-East coast of Ireland including brown, red and green varieties. The powdered seaweeds were extracted using four different solvents by liquid extraction. The poisoned food technique was employed to establish the antifungal efficacy, and the standard disc diffusion assay was used to assess the antibacterial properties of the seaweed extracts. It was found that extracts of the green seaweed exhibited antifungal activity against H. annosum, with approximately 50% inhibition compared to the negative control. The protectant activities of the active extracts were evaluated on disks of Picea sitchensis, a plant species sensitive to infection from H. annosum and compared to the standard chemical control product urea. The crude extracts exhibited very similar activity to the 10% and 20% w/v concentrations of urea, demonstrating the ability of seaweed extracts to compete with commercially available products. Antibacterial activity was exhibited by a number of seaweed extracts with the red seaweed illustrating the strongest activity, with a zone of inhibition of 15.83 ± 0.41 mm exhibited against X. arboricola whilst the positive control (10 μg/disk of chloramphenicol) had a zone of 26.5 ± 0.71 mm. These results highlight the potential application of seaweed extracts in the forestry and agricultural industries for use as biopesticides. Further work is now required to identify the bioactive molecules that are responsible for this antifungal and antibacterial activity in the seaweed extracts, including toxicity studies to ensure the extracts are non-toxic to plants and humans.

Keywords: antibacterial, antifungal, biopesticides, seaweeds

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Authors: Emma J. Dale, Christina D. Buesching, Kevin R. Theis, David W. Macdonald

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This study investigates the oral and intestinal microbiomes of wild-living European badgers (Meles meles) and will relate inter-individual differences to social contact networks, somatic and reproductive fitness, varying susceptibility to bovine tuberculous (bTB) and to the olfactory advertisement. Badgers are an interesting model for this research, as they have great variation in body condition, despite living in complex social networks and having access to the same resources. This variation in somatic fitness, in turn, affects breeding success, particularly in females. We postulate that microbiota have a central role to play in determining the successfulness of an individual. Our preliminary results, characterising the microbiota of individual badgers, indicate unique compositions of microbiota communities within social groups of badgers. This basal information will inform further questions related to the extent microbiota influence fitness. Hitherto, the potential role of microbiota has not been considered in determining host condition, but also other key fitness variables, namely; communication and resistance to disease. Badgers deposit their faeces in communal latrines, which play an important role in olfactory communication. Odour profiles of anal and subcaudal gland secretions are highly individual-specific and encode information about group-membership and fitness-relevant parameters, and their chemical composition is strongly dependent on symbiotic microbiota. As badgers sniff/ lick (using their Vomeronasal organ) and over-mark faecal deposits of conspecifics, these microbial communities can be expected to vary with social contact networks. However, this is particularly important in the context of bTB, where badgers are assumed to transmit bTB to cattle as well as conspecifics. Interestingly, we have found that some individuals are more susceptible to bTB than are others. As acquired immunity and thus potential susceptibility to infectious diseases are known to depend also on symbiotic microbiota in other members of the mustelids, a role of particularly oral microbiota can currently not be ruled out as a potential explanation for inter-individual differences in infection susceptibility of bTB in badgers. Tri annually badgers are caught in the context of a long-term population study that began in 1987. As all badgers receive an individual tattoo upon first capture, age, natal as well as previous and current social group-membership and other life history parameters are known for all animals. Swabs (subcaudal ‘scent gland’, anal, genital, nose, mouth and ear) and fecal samples will be taken from all individuals, stored at -80oC until processing. Microbial samples will be processed and identified at Wayne State University’s Theis (Host-Microbe Interactions) Lab, using High Throughput Sequencing (16S rRNA-encoding gene amplification and sequencing). Acknowledgments: Gas-Chromatography/ Mass-spectrometry (in the context of olfactory communication) analyses will be performed through an established collaboration with Dr. Veronica Tinnesand at Telemark University, Norway.

Keywords: communication, energetics, fitness, free-ranging animals, immunology

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Authors: Sami Khan, Kripa Varanasi

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Corrosion is a widespread problem in several industries and developing surfaces that resist corrosion has been an area of interest since the last several decades. Superhydrophobic surfaces that combine hydrophobic coatings along with surface texture have been shown to improve corrosion resistance by creating voids filled with air that minimize the contact area between the corrosive liquid and the solid surface. However, these air voids can incorporate corrosive liquids over time, and any mechanical faults such as cracks can compromise the coating and provide pathways for corrosion. As such, there is a need for self-healing corrosion-resistance surfaces. In this work, the anti-corrosion properties of textured surfaces impregnated with a lubricant have been systematically studied. Since corrosion resistance depends on the area and physico-chemical properties of the material exposed to the corrosive medium, lubricant-impregnated surfaces (LIS) have been designed based on the surface tension, viscosity and chemistry of the lubricant and its spreading coefficient on the solid. All corrosion experiments were performed in a standard three-electrode cell using iron, which readily corrodes in a 3.5% sodium chloride solution. In order to obtain textured iron surfaces, thin films (~500 nm) of iron were sputter-coated on silicon wafers textured using photolithography, and subsequently impregnated with lubricants. Results show that the corrosion rate on LIS is greatly reduced, and offers an over hundred-fold improvement in corrosion protection. Furthermore, it is found that the spreading characteristics of the lubricant are significant in ensuring corrosion protection: a spreading lubricant (e.g., Krytox 1506) that covers both inside the texture, as well as the top of the texture, provides a two-fold improvement in corrosion protection as compared to a non-spreading lubricant (e.g., Silicone oil) that does not cover texture tops. To enhance corrosion protection of surfaces coated with a non-spreading lubricant, pyramid-shaped textures have been developed that minimize exposure to the corrosive solution, and a consequent twenty-fold increased in corrosion protection is observed. An increase in viscosity of the lubricant scales with greater corrosion protection. Finally, an equivalent cell-circuit model is developed for the lubricant-impregnated systems using electrochemical impedance spectroscopy. Lubricant-impregnated surfaces find attractive applications in harsh corrosive environments, especially where the ability to self-heal is advantageous.

Keywords: lubricant-impregnated surfaces, self-healing surfaces, wettability, nano-engineered surfaces

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Authors: Luisa Maria Arrechea Fajardo, Luz Stella Cadavid Rodriguez

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Fish is one of the most commercialized foods worldwide. However, this industry only takes advantage of about 55% of the product's weight, the rest is converted into waste, which is mainly composed of viscera, gills, scales and spines. Consequently, if these wastes are not used or disposed of properly, they cause serious environmental impacts. This is the case of Tumaco (Colombia), the second largest producer of marine fisheries on the Colombian Pacific coast, where artisanal fishermen process more than 50% of the commercialized volume. There, fishing waste is disposed primarily in the ocean, causing negative impacts on the environment and society. Therefore, in the present research, a proposal was made to take advantage of fishing waste through anaerobic treatments, through which it is possible to obtain products with high added value from organic waste. The research was carried out in four stages. First, the production of volatile fatty acids (VFA) in semi-continuous 4L reactors was studied, evaluating three hydraulic retention times (HRT) (10, 7 and 5 days) with four organic loading rates (OLR) (16, 14, 12 and 10 gVS/L/day), the experiment was carried out for 150 days. Subsequently, biogas production was evaluated from the solid digestate generated in the VFA production reactors, initially evaluating the biochemical methane potential (BMP) of 4 total solid concentrations (1, 2, 4 and 6% TS), for 40 days and then, with the optimum TS concentration (2 gVS/L/day), 2 HRT (15 and 20 days) in semi-continuous reactors, were evaluated for 100 days. Finally, the integration of the processes was carried out with the best conditions found, a first phase of VFA production from fishing waste and a second phase of biogas production from unrecovered VFAs and unprocessed material Additionally, an VFA membrane extraction system was included. In the first phase, a liquid digestate with a concentration and VFA production yield of 59.04 gVFA/L and 0.527 gVFA/gVS, respectively, was obtained, with the best condition found (HRT:7 days and OLR: 16 gVS/L/día), where acetic acid and isobutyric acid were the predominant acids. In the second phase of biogas production, a BMP of 0.349 Nm3CH4/KgVS was reached, and it was found as best HRT 20 days. In the integration, the isovaleric, butyric and isobutyric acid were the VFA with the highest percentage of extraction, additionally a 106.67% increase in biogas production was achieved. This research shows that anaerobic treatments are a promising technology for an environmentally safe management of fishing waste and presents the basis of a possible biorefinery.

Keywords: biogas production, fishing waste, VFA membrane extraction, VFA production

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Authors: A. K. Tursunova, O. V. Chebonenko, A. Zh. Amirkulova, A. O. Abaildayev, O. A. Sapko, Y. M. Dyo, A. Sh. Utarbaeva

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Fusarium solani and its variants cause root and stem rot of plants. Dry rot is the most common disease of potato tubers during storage. The causative agents of fusariosis in contact with plants behave as antagonists, growth stimulants or parasites. The diversity of host-parasite relationships is explained by the parasite’s ability to produce a wide spectrum of biologically active compounds including toxins, enzymes, oligosaccharides, antibiotic substances, enniatins and gibberellins. Many of these metabolites contribute to the creation of compatible relations; others behave as elicitors, inducing various protective responses in plants. An important part of the strategy for developing plant resistance against pathogens is the activation of protein synthesis to produce protective ‘pathogenesis-related’ proteins. The family of PR-proteins known to confer the most protective response is chitinases (EC 3.2.1.14, Cht) and β-1,3-glucanases (EC 3.2.1.39, Glu). PR-proteins also include a large multigene family of peroxidases (EC 1.11.1.7, Pod), and increased activity of Pod and expression of the Pod genes leads to the development of resistance to a broad class of pathogens. Despite intensive research on the role of PR-proteins, the question of their participation in the mechanisms of formation of the F.solani–S.tuberosum pathosуstem is not sufficiently studied. Our aim was to investigate the effect of different classes of F. solani metabolites on the activity of chitinase, β-1,3-glucanases and peroxidases in tubers of Solanum tuberosum. Metabolite culture filtrate (CF) and cytoplasmic components were fractionated by extraction of the mycelium with organic solvents, salting out techniques, dialysis, column chromatography and ultrafiltration. Protein, lipid, carbohydrate and polyphenolic fractions of fungal metabolites were derived. Using enzymatic hydrolysis we obtained oligo glycans from fungal cell walls with different molecular weights. The activity of the metabolites was tested using potato tuber discs (d = 16mm, h = 5mm). The activity of PR-proteins of tubers was analyzed in a time course of 2–24 hours. The involvement of the analysed metabolites in the modulation of both early non-specific and late related to pathogenesis reactions was demonstrated. The most effective inducer was isolated from the CF (fraction of total phenolic compounds including naphtazarins). Induction of PR-activity by this fraction was: chitinase - 340-360%, glucanase - 435-450%, soluble forms of peroxidase - 400-560%, related forms of peroxidase - 215-237%. High-inducing activity was observed by the chloroform and acetonitrile extracts of the mycelium (induction of chitinase and glucanase activity was 176-240%, of soluble and bound forms of peroxidase - 190-400%). The fraction of oligo glycans mycelium cell walls of 1.2 kDa induced chitinase and β-1,3-glucanase to 239-320%; soluble forms and related peroxidase to 198-426%. Oligo glycans cell walls of 5-10 kDa had a weak suppressor effect - chitinase (21-25%) and glucanase (25-28%) activity; had no effect on soluble forms of peroxidase, but induced to 250-270% activity related forms. The CF polysaccharides of 8.5 kDa and 3.1 kDa inhibited synchronously the glucanase and chitinase specific response in step (after 24 hours at 42-50%) and the step response induced nonspecific peroxidase activity: soluble forms 4.8 -5.2 times, associated forms 1.4-1.6 times.

Keywords: fusarium solani, PR-proteins, peroxidase, solanum tuberosum

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Authors: Moshe Mello, Hilary Rutto, Tumisang Seodigeng

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The nature of tires makes them extremely challenging to recycle due to the available chemically cross-linked polymer and, therefore, they are neither fusible nor soluble and, consequently, cannot be remolded into other shapes without serious degradation. Open dumping of tires pollutes the soil, contaminates underground water and provides ideal breeding grounds for disease carrying vermins. The thermal decomposition of tires by pyrolysis produce char, gases and oil. The composition of oils derived from waste tires has common properties to commercial diesel fuel. The problem associated with the light oil derived from pyrolysis of waste tires is that it has a high sulfur content (> 1.0 wt.%) and therefore emits harmful sulfur oxide (SOx) gases to the atmosphere when combusted in diesel engines. Desulphurization of TPO is necessary due to the increasing stringent environmental regulations worldwide. Hydrodesulphurization (HDS) is the commonly practiced technique for the removal of sulfur species in liquid hydrocarbons. However, the HDS technique fails in the presence of complex sulfur species such as Dibenzothiopene (DBT) present in TPO. This study aims to investigate the viability of photodegradation (Photocatalytic oxidative desulphurization) and adsorptive desulphurization technologies for efficient removal of complex and non-complex sulfur species in TPO. This study focuses on optimizing the cleaning (removal of impurities and asphaltenes) process by varying process parameters; temperature, stirring speed, acid/oil ratio and time. The treated TPO will then be sent for vacuum distillation to attain the desired diesel like fuel. The effect of temperature, pressure and time will be determined for vacuum distillation of both raw TPO and the acid treated oil for comparison purposes. Polycyclic sulfides present in the distilled (diesel like) light oil will be oxidized dominantly to the corresponding sulfoxides and sulfone via a photo-catalyzed system using TiO2 as a catalyst and hydrogen peroxide as an oxidizing agent and finally acetonitrile will be used as an extraction solvent. Adsorptive desulphurization will be used to adsorb traces of sulfurous compounds which remained during photocatalytic desulphurization step. This desulphurization convoy is expected to give high desulphurization efficiency with reasonable oil recovery.

Keywords: adsorption, asphaltenes, photocatalytic oxidation, pyrolysis

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Authors: Zbigniew Szklarz, Aldona Garbacz-Klempka, Magdalena Bisztyga-Szklarz

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Typical metallic alloys bases on one major alloying component, where the addition of other elements is intended to improve or modify certain properties, most of all the mechanical properties. However, in 1995 a new concept of metallic alloys was described and defined. High Entropy Alloys (HEA) contains at least five alloying elements in an amount from 5 to 20 at.%. A common feature this type of alloys is an absence of intermetallic phases, high homogeneity of the microstructure and unique chemical composition, what leads to obtaining materials with very high strength indicators, stable structures (also at high temperatures) and excellent corrosion resistance. Hence, HEA can be successfully used as a substitutes for typical metallic alloys in various applications where a sufficiently high properties are desirable. For fabricating HEA, a few ways are applied: 1/ from liquid phase i.e. casting (usually arc melting); 2/ from solid phase i.e. powder metallurgy (sintering methods preceded by mechanical synthesis) and 3/ from gas phase e.g. sputtering or 4/ other deposition methods like electrodeposition from liquids. Application of different production methods creates different microstructures of HEA, which can entail differences in their properties. The last two methods also allows to obtain coatings with HEA structures, hereinafter referred to as High Entropy Films (HEF). With reference to above, the crucial aim of this work was the optimization of the manufacturing process of the multi-component metallic layers (HEF) by the low- and high temperature electrochemical deposition ( ED). The low-temperature deposition process was crried out at ambient or elevated temperature (up to 100 ᵒC) in organic electrolyte. The high-temperature electrodeposition (several hundred Celcius degrees), in turn, allowed to form the HEF layer by electrochemical reduction of metals from molten salts. The basic chemical composition of the coatings was CoCrFeMnNi (known as Cantor’s alloy). However, it was modified by other, selected elements like Al or Cu. The optimization of the parameters that allow to obtain as far as it possible homogeneous and equimolar composition of HEF is the main result of presented studies. In order to analyse and compare the microstructure, SEM/EBSD, TEM and XRD techniques were employed. Morover, the determination of corrosion resistance of the CoCrFeMnNi(Cu or Al) layers in selected electrolytes (i.e. organic and non-organic liquids) was no less important than the above mentioned objectives.

Keywords: high entropy alloys, electrodeposition, corrosion behavior, microstructure

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Authors: Wei-Shan Wang, Klaus Vogel, Felix Gabler, Maik Wiemer, Thomas Gessner

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Metallic glasses, which are free of grain boundaries, have superior properties including large elastic limits, high strength, and excellent wear and corrosion resistance. Therefore, bulk metallic glasses (BMG) and thin film metallic glasses (TFMG) have been widely developed and investigated. Among various kinds of metallic glasses, Pd-Cu-Si TFMG, which has lower elastic modulus and better resistance of oxidation and corrosions compared to Zr- and Fe-based TFMGs, can be a promising candidate for MEMS applications. However, the study of Pd-TFMG membrane is still limited. This paper presents free-standing Pd-based metallic glass membranes with large area fabricated on wafer level for the first time. Properties of Pd-Cu-Si thin film metallic glass (TFMG) with various deposition parameters are investigated first. When deposited at 25°C, compressive stress occurs in the Pd76Cu6Si18 thin film regardless of Ar pressure. When substrate temperature is increased to 275°C, the stress state changes from compressive to tensile. Thin film stresses are slightly decreased when Ar pressure is higher. To show the influence of temperature on Pd-TFMGs, thin films without and with post annealing below (275°C) and within (370°C) supercooled liquid region are investigated. Results of XRD and TEM analysis indicate that Pd-TFMGs remain amorphous structure with well-controlled parameters. After verification of amorphous structure of the Pd-TFMGs, free-standing Pd-Cu-Si membranes were fabricated by depositing Pd-Cu-Si thin films directly on 200nm-thick silicon nitride membranes, followed by post annealing and dry etching of silicon nitride layer. Post annealing before SiNx removal is used to further release internal stress of Pd-TFMGs. The edge length of the square membrane ranges from 5 to 8mm. The effect of post annealing on Pd-Cu-Si membranes are discussed as well. With annealing at 370°C for 5 min, Pd-MG membranes are fully distortion-free after removal of SiNx layer. Results show that, by introducing annealing process, the stress-relief, distortion-free Pd-TFMG membranes with large area can be a promising candidate for sensing applications such as pressure and gas sensors.

Keywords: amorphous alloy, annealing, metallic glasses, TFMG membrane

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Authors: T. Ewetumo, K. D. Adedayo, Festus Ben

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Knowledge of the thermal properties of foods is of fundamental importance in the food industry to establish the design of processing equipment. However, for tropical fruit juice, there is very little information in literature, seriously hampering processing procedures. This research work describes the development of an instrument for automated thermal conductivity and thermal diffusivity measurement of tropical fruit juice using a transient thermal probe technique based on line heat principle. The system consists of two thermocouple sensors, constant current source, heater, thermocouple amplifier, microcontroller, microSD card shield and intelligent liquid crystal. A fixed distance of 6.50mm was maintained between the two probes. When heat is applied, the temperature rise at the heater probe measured with time at time interval of 4s for 240s. The measuring element conforms as closely as possible to an infinite line source of heat in an infinite fluid. Under these conditions, thermal conductivity and thermal diffusivity are simultaneously measured, with thermal conductivity determined from the slope of a plot of the temperature rise of the heating element against the logarithm of time while thermal diffusivity was determined from the time it took the sample to attain a peak temperature and the time duration over a fixed diffusivity distance. A constant current source was designed to apply a power input of 16.33W/m to the probe throughout the experiment. The thermal probe was interfaced with a digital display and data logger by using an application program written in C++. Calibration of the instrument was done by determining the thermal properties of distilled water. Error due to convection was avoided by adding 1.5% agar to the water. The instrument has been used for measurement of thermal properties of banana, orange and watermelon. Thermal conductivity values of 0.593, 0.598, 0.586 W/m^o C and thermal diffusivity values of 1.053 ×〖10〗^(-7), 1.086 ×〖10〗^(-7), and 0.959 ×〖10〗^(-7) 〖m/s〗^2 were obtained for banana, orange and water melon respectively. Measured values were stored in a microSD card. The instrument performed very well as it measured the thermal conductivity and thermal diffusivity of the tropical fruit juice samples with statistical analysis (ANOVA) showing no significant difference (p>0.05) between the literature standards and estimated averages of each sample investigated with the developed instrument.

Keywords: thermal conductivity, thermal diffusivity, tropical fruit juice, diffusion equation

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Authors: Faijal Ali, Darga Kumar N., Ravikant Singh, Rajnil Lal

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Fiji has three major landforms such as plains, low mountains, and hills. The low land soils are formed on beach sand. Fiji soils contain high concentration of iron (III), aluminum oxides and hydroxides. The soil possesses reddish or yellowish colour. The characterization of lateritic soils collected from different locations along the national highway in Viti Levu, Fiji Islands. The research has been carried out mainly to understand the physical and strength properties to assess their suitability for the highway and building construction. In this paper, the field tests such as dynamic cone penetrometer test, field vane shear, field density and laboratory tests such as unconfined compression stress, compaction, grain size analysis and Atterberg limits are conducted. The test results are analyzed and presented. From the results, it is revealed that the soils are having more percentage of silt and clay which is more than 80% and 5 to 15% of fine to medium sand is noticed. The dynamic cone penetrometer results up to 3m depth had similar penetration resistance. For the first 1m depth, the rate of penetration is found 300mm per 3 to 4 blows. In all the sites it is further noticed that the rate of penetration at depths beyond 1.5 m is decreasing for the same number of blows as compared to the top soil. From the penetration resistance measured through dynamic cone penetrometer test, the California bearing ratio and allowable bearing capacities are 4 to 5% and 50 to 100 kPa for the top 1m layer and below 1m these values are increasing. The California bearing ratio of these soils for below 1m depth is in the order of 10% to 20%. The safe bearing capacity of these soils below 1m and up to 3m depth is varying from 150 kPa to 250 kPa. The field vane shear was measured within a depth of 1m from the surface and the values were almost similar varying from 60 kPa to 120 kPa. The liquid limit and plastic limits of these soils are in the range of 40 to 60% and 20 to 25%. Overall it is found that the top 1m soil along the national highway in majority places possess a soft to medium stiff behavior with low to medium bearing capacity as well low California bearing ratio values. It is recommended to ascertain these soils behavior in terms of geotechnical parameters before taking up any construction activity.

Keywords: California bearing ratio, dynamic cone penetrometer test, field vane shear, unconfined compression stress.

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Authors: Vedanki Khandenwal, Pawan Srivastava, Kartick Tarafder, Subhasis Ghosh

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We present here the experimental realization of controlled doping of graphene monolayers through charge transfer by trapping selected organic molecules between the graphene layer and underlying substrates. This charge transfer between graphene and trapped molecule leads to controlled n-type or p-type doping in monolayer graphene (MLG), depending on whether the trapped molecule acts as an electron donor or an electron acceptor. Doping controllability has been validated by a shift in corresponding Raman peak positions and a shift in Dirac points. In the transfer characteristics of field effect transistors, a significant shift of Dirac point towards positive or negative gate voltage region provides the signature of p-type or n-type doping of graphene, respectively, as a result of the charge transfer between graphene and the organic molecules trapped within it. In order to facilitate the charge transfer interaction, it is crucial for the trapped molecules to be situated in close proximity to the graphene surface, as demonstrated by findings in Raman and infrared spectroscopies. However, the mechanism responsible for this charge transfer interaction has remained unclear at the microscopic level. Generally, it is accepted that the dipole moment of adsorbed molecules plays a crucial role in determining the charge-transfer interaction between molecules and graphene. However, our findings clearly illustrate that the doping effect primarily depends on the reactivity of the constituent atoms in the adsorbed molecules rather than just their dipole moment. This has been illustrated by trapping various molecules at the graphene−substrate interface. Dopant molecules such as acetone (containing highly reactive oxygen atoms) promote adsorption across the entire graphene surface. In contrast, molecules with less reactive atoms, such as acetonitrile, tend to adsorb at the edges due to the presence of reactive dangling bonds. In the case of low-dipole moment molecules like toluene, there is a lack of substantial adsorption anywhere on the graphene surface. Observation of (i) the emergence of the Raman D peak exclusively at the edges for trapped molecules without reactive atoms and throughout the entire basal plane for those with reactive atoms, and (ii) variations in the density of attached molecules (with and without reactive atoms) to graphene with their respective dipole moments provides compelling evidence to support our claim. Additionally, these observations were supported by first principle density functional calculations.

Keywords: graphene, doping, charge transfer, liquid phase exfoliation

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Authors: Ahmed M. Eed, Adam H. Burgoyne

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Jojoba (Simmondsia chinensis (Link) Schneider), is a desert shrub which tolerates saline, alkyle soils and drought. The seeds contain a characteristic liquid wax of economic importance in industry as a machine lubricant and cosmetics. A major problem in seed propagation is that jojoba is a dioecious plant whose sex is not easily determined prior to flowering (3-4 years from germination). To overcome this phenomenon, asexual propagation using vegetative methods such as cutting can be used. This research was conducted to find out the effect of different Plant Growth Regulators (PGRs) and rooting media on Jojoba rhizogenesis. An experiment was carried out in a Factorial Completely Randomized Design (FCRD) with three replications, each with sixty cuttings per replication in fiberglass house of Natural Jojoba Corporation at Yemen. The different rooting media used were peat moss + perlite + vermiculite (1:1:1), peat moss + perlite (1:1) and peat moss + sand (1:1). Plant materials used were semi-hard wood cuttings of jojoba plants with length of 15 cm. The cuttings were collected in the month of June during 2012 and 2013 from the sub-terminal growth of the mother plants of Amman farm and introduced to Yemen. They were wounded, treated with Indole butyric acid (IBA), α-naphthalene acetic acid (NAA) or Indole-3-acetic acid (IAA) all @ 4000 ppm (part per million) and cultured on different rooting media under intermittent mist propagation conditions. IBA gave significantly higher percentage of rooting (66.23%) compared to NAA and IAA in all media used. However, the lowest percentage of rooting (5.33%) was recorded with IAA in the medium consisting of peat moss and sand (1:1). No significant difference was observed at all types of PGRs used with rooting media in respect of root length. Maximum number of roots was noticed in medium consisting of peat moss, perlite and vermiculite (1:1:1); peat moss and perlite (1:1) and peat moss and sand (1:1) using IBA, NAA and IBA, respectively. The interaction among rooting media was statistically significant with respect to rooting percentage character. Similarly, the interactions among PGRs were significant in terms of rooting percentage and also root length characters. The results demonstrated suitability of propagation of jojoba plants by semi-hard wood cuttings.

Keywords: cutting, IBA, Jojoba, propagation, rhizogenesis

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Authors: Naresh Kumar, Savita Kumari, Naresh Kochhar

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The objective of the study was to assess the role of mineralogy and subsurface structure on water quality of Tosham, Malani Igneous Suite (MIS), Western Rajasthan, India. MIS is the largest (55,000 km2) A-type, anorogenic and high heat producing acid magmatism in the peninsular India and owes its origin to hot spot tectonics. Apart from agricultural and industrial wastes, geogenic activities cause fluctuations in quality parameters of water resources. Twenty water samples (20) selected from Tosham and surrounding areas were analyzed for As, Pb, B, Al, Zn, Fe, Ni using Inductive coupled plasma emission and F by Ion Chromatography. The concentration of As, Pb, B, Ni and F was above the stipulated level specified by BIS (Bureau of Indian Standards IS-10500, 2012). The concentration of As and Pb in surrounding areas of Tosham ranged from 1.2 to 4.1 mg/l and from 0.59 to 0.9 mg/l respectively which is higher than limits of 0.05mg/l (As) and 0.01 mg/l (Pb). Excess trace metal accumulation in water is toxic to humans and adversely affects the central nervous system, kidneys, gastrointestinal tract, skin and cause mental confusion. Groundwater quality is defined by nature of rock formation, mineral water reaction, physiography, soils, environment, recharge and discharge conditions of the area. Fluoride content in groundwater is due to the solubility of fluoride-bearing minerals like fluorite, cryolite, topaz, and mica, etc. Tosham is comprised of quartz mica schist, quartzite, schorl, tuff, quartz porphyry and associated granites, thus, fluoride is leached out and dissolved in groundwater. In the study area, Ni concentration ranged from 0.07 to 0.5 mg/l (permissible limit 0.02 mg/l). The primary source of nickel in drinking water is leached out nickel from ore-bearing rocks. Higher concentration of As is found in some igneous rocks specifically containing minerals as arsenopyrite (AsFeS), realgar (AsS) and orpiment (As2S3). MIS consists of granite (hypersolvus and subsolvus), rhyolite, dacite, trachyte, andesite, pyroclasts, basalt, gabbro and dolerite which increased the trace elements concentration in groundwater. Nakora, a part of MIS rocks has high concentration of trace and rare earth elements (Ni, Rb, Pb, Sr, Y, Zr, Th, U, La, Ce, Nd, Eu and Yb) which percolates the Ni and Pb to groundwater by weathering, contacts and joints/fractures in rocks. Additionally, geological setting of MIS also causes dissolution of trace elements in water resources beneath the surface. NE–SW tectonic lineament, radial pattern of dykes and volcanic vent at Nakora created a way for leaching of these elements to groundwater. Rain water quality might be altered by major minerals constituents of host Tosham rocks during its percolation through the rock fracture, joints before becoming the integral part of groundwater aquifer. The weathering process like hydration, hydrolysis and solution might be the cause of change in water chemistry of particular area. These studies suggest that geological relation of soil-water horizon with MIS rocks via mineralogical variations, structures and tectonic setting affects the water quality of the studied area.

Keywords: geochemistry, groundwater, malani igneous suite, tosham

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Authors: Amal E. Ahmed, Levent Trabzon

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Due to the low concentration of the analytes in biological samples, the use of Biological Microelectromechanical System (Bio-MEMS) biosensors for biomolecules detection results in a minuscule output signal that is not good enough for practical applications. In response to this, a need has arisen for an optimized biosensor capable of giving high output signal in response the detection of few analytes in the sample; the ultimate goal is being able to convert the attachment of a single biomolecule into a measurable quantity. For this purpose, MEMS microcantilevers based biosensors emerged as a promising sensing solution because it is simple, cheap, very sensitive and more importantly does not need analytes optical labeling (Label-free). Among the different microcantilever transducing techniques, piezoresistive based microcantilever biosensors became more prominent because it works well in liquid environments and has an integrated readout system. However, the design of piezoresistive microcantilevers is not a straightforward problem due to coupling between the design parameters, constraints, process conditions, and performance. It was found that the parameters that can be optimized to enhance the sensitivity of Piezoresistive microcantilever-based sensors are: cantilever dimensions, cantilever material, cantilever shape, piezoresistor material, piezoresistor doping level, piezoresistor dimensions, piezoresistor position, Stress Concentration Region's (SCR) shape and position. After a systematic analyzation of the effect of each design and process parameters on the sensitivity, a step-wise optimization approach was developed in which almost all these parameters were variated one at each step while fixing the others to get the maximum possible sensitivity at the end. At each step, the goal was to optimize the parameter in a way that it maximizes and concentrates the stress in the piezoresistor region for the same applied force thus get the higher sensitivity. Using this approach, an optimized sensor that has 73.5x times higher electrical sensitivity (ΔR⁄R) than the starting sensor was obtained. In addition to that, this piezoresistive microcantilever biosensor it is more sensitive than the other similar sensors previously reported in the open literature. The mechanical sensitivity of the final senior is -1.5×10-8 Ω/Ω ⁄pN; which means that for each 1pN (10-10 g) biomolecules attach to this biosensor; the piezoresistor resistivity will decrease by 1.5×10-8 Ω. Throughout this work COMSOL Multiphysics 5.0, a commercial Finite Element Analysis (FEA) tool, has been used to simulate the sensor performance.

Keywords: biosensor, microcantilever, piezoresistive, stress concentration region (SCR)

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Authors: A. Kouloumpis, P. Zygouri, G. Potsi, K. Spyrou, D. Gournis

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Much of the research effort on graphene focuses on its use as building block for the development of new hybrid nanostructures with well-defined dimensions and behavior suitable for applications among else in gas storage, heterogeneous catalysis, gas/liquid separations, nanosensing and biology. Towards this aim, here we describe a new bottom-up approach, which combines the self-assembly with the Langmuir Schaefer technique, for the production of fullerene-intercalated graphene hybrid materials. This new method uses graphene nanosheets as a template for the grafting of various fullerene C60 molecules (pure C60, bromo-fullerenes, C60Br24, and fullerols, C60(OH)24) in a bi-dimensional array, and allows for perfect layer-by-layer growth with control at the molecular level. Our film preparation approach involves a bottom-up layer-by-layer process that includes the formation of a hybrid organo-graphene Langmuir film hosting fullerene molecules within its interlayer spacing. A dilute water solution of chemically oxidized graphene (GO) was used as subphase on the Langmuir-Blodgett deposition system while an appropriate amino surfactant (that binds covalently with the GO) was applied for the formation of hybridized organo-GO. After the horizontal lift of a hydrophobic substrate, a surface modification of the GO platelets was performed by bringing the surface of the transferred Langmuir film in contact with a second amino surfactant solution (capable to interact strongly with the fullerene derivatives). In the final step, the hybrid organo-graphene film was lowered in the solution of the appropriate fullerene derivative. Multilayer films were constructed by repeating this procedure. Hybrid fullerene-based thin films deposited on various hydrophobic substrates were characterized by X-ray diffraction (XRD) and X-ray reflectivity (XRR), FTIR, and Raman spectroscopies, Atomic Force Microscopy, and optical measurements. Acknowledgments. This research has been co‐financed by the European Union (European Social Fund – ESF) and Greek national funds through the Operational Program "Education and Lifelong Learning" of the National Strategic Reference Framework (NSRF)‐Research Funding Program: THALES. Investing in knowledge society through the European Social Fund (no. 377285).

Keywords: hybrids, graphene oxide, fullerenes, langmuir-blodgett, intercalated structures

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Authors: Swati Gautam, Amita Jain, Shyampyari Jaiswar

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Objective: To elucidate the role of (ApaI&TaqI) VDR gene polymorphism in the pathogenesis of female genital tuberculosis (FGTB) cases. Background: Female genital TB represents about 15-20% of total extra-pulmonary TB (EPTB). Female subjects with vitamin D deficiency have been shown to be at higher risk of pulmonary TB as well as FGTB. In same context few functional polymorphism in vitamin D receptor (VDR) gene has been considered as an important genetic risk factor that modulate the development of FGTB. Therefore we aimed, to elucidate the role of (ApaI&TaqI) VDR gene polymorphism in the pathogenesis of FGTB. Study design: Case-Control study. Sample size: Cases (60) and Controls (60). Study site: Department of Obstetrics & Gynecology & Department of Microbiology, K.G.M.U. Lucknow, (UP). Inclusion criteria: Cases: Women with age group 20-35 years, premenstrual endometrial aspiration collected and included in the study, those were positive with acid-fast bacilli (AFB)/ TB-PCR/ LJ culture/ liquid culture. Controls: Women with age group 20-35 years having no history of ATT and all test negative for TB recruited as control. Exclusion criteria: -Women with endometriosis, polycystic ovaries (PCOD), positive on Chlamydia & gonorrhea, already on anti-tubercular therapy (ATT) excluded. Materials and Methods: Blood samples were collected in EDTA tubes from cases and controls stored at -20ºC. Genomic DNA extraction was carried out by salting-out method. Genotyping of VDR gene (ApaI&TaqI) polymorphism was performed by using single amplification refractory mutation system (ARMS) PCR technique. PCR products were analyzed by electrophoresis on 2% agarose gel. Statistical analysis was done by SPSS16.3 software & computing odds ratio (OR) with 95% CI. Results: Increased risk of female genital tuberculosis was observed in AA genotype (OR =1.1419-6.212 95% CI, P*<0.036) and A allele (OR =1.255-3.518, 95% CI, P* < 0.006) in FGTB as compared to controls. Moreover A allele was found more frequent in FGTB patients. No significant difference was observed in TaqI gene polymorphism of VDR gene. Conclusion: The ApaI polymorphism is significantly associated with etiology of FGTB and plays an important role as a genetic risk factor in FGTB women.

Keywords: ARMS, ATT, EPTB, FGTB, VDR

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Authors: Igor B. Sivaev

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Design of molecular machines is an extraordinary growing and very important area of research that it was recognized by awarding Sauvage, Stoddart and Feringa the Nobel Prize in Chemistry in 2016 'for the design and synthesis of molecular machines'. Based on the type of motion being performed, molecular machines can be divided into two main types: molecular motors and molecular switches. Molecular switches are molecules or supramolecular complexes having bistability, i.e., the ability to exist in two or more stable forms, among which may be reversible transitions under external influence (heating, lighting, changing the medium acidity, the action of chemicals, exposure to magnetic or electric field). Molecular switches are the main structural element of any molecular electronics devices. Therefore, the design and the study of molecules and supramolecular systems capable of performing mechanical movement is an important and urgent problem of modern chemistry. There is growing interest in molecular switches and other devices of molecular electronics based on transition metal complexes; therefore choice of suitable stable organometallic unit is of great importance. An example of such unit is bis(dicarbollide) complexes of transition metals [3,3’-M(1,2-C₂B₉H₁₁)₂]ⁿ⁻. The control on the ligand rotation in such complexes can be reached by introducing substituents which could provide stabilization of certain rotamers due to specific interactions between the ligands, on the one hand, and which can participate as Lewis bases in complex formation with external metals resulting in a change in the rotation angle of the ligands, on the other hand. A series of isomeric methyl sulfide derivatives of cobalt bis(dicarbollide) complexes containing methyl sulfide substituents at boron atoms in different positions of the pentagonal face of the dicarbollide ligands [8,8’-(MeS)₂-3,3’-Co(1,2-C₂B₉H₁₀)₂]⁻, rac-[4,4’-(MeS)₂-3,3’-Co(1,2-C₂B₉H₁₀)₂]⁻ and meso-[4,7’-(MeS)₂-3,3’-Co(1,2-C₂B₉H₁₀)₂]⁻ were synthesized by the reaction of CoCl₂ with the corresponding methyl sulfide carborane derivatives [10-MeS-7,8-C₂B₉H₁₁)₂]⁻ and [10-MeS-7,8-C₂B₉H₁₁)₂]⁻. In the case of asymmetrically substituted cobalt bis(dicarbollide) complexes the corresponding rac- and meso-isomers were successfully separated by column chromatography as the tetrabutylammonium salts. The compounds obtained were studied by the methods of ¹H, ¹³C, and ¹¹B NMR spectroscopy, single crystal X-ray diffraction, cyclic voltammetry, controlled potential coulometry and quantum chemical calculations. It was found that in the solid state, the transoid- and gauche-conformations of the 8,8’- and 4,4’-isomers are stabilized by four intramolecular CH···S(Me)B hydrogen bonds each one (2.683-2.712 Å and 2.709-2.752 Å, respectively), whereas gauche-conformation of the 4,7’-isomer is stabilized by two intramolecular CH···S hydrogen bonds (2.699-2.711 Å). The existence of the intramolecular CH·S(Me)B hydrogen bonding in solutions was supported by the 1H NMR spectroscopy. These data are in a good agreement with results of the quantum chemical calculations. The corresponding iron and nickel complexes were synthesized as well. The reaction of the methyl sulfide derivatives of cobalt bis(dicarbollide) with various labile transition metal complexes results in rupture of intramolecular hydrogen bonds and complexation of the methyl sulfide groups with external metal. This results in stabilization of other rotational conformation of cobalt bis(dicarbollide) and can be used in design of molecular switches. This work was supported by the Russian Science Foundation (16-13-10331).

Keywords: molecular switches, NMR spectroscopy, single crystal X-ray diffraction, transition metal bis(dicarbollide) complexes, quantum chemical calculations

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Authors: Debanjan Dey, Tamal Banerjee, Kaustubha Mohanty

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Global scalar properties are calculated based on higher occupied molecular orbital (HOMO) and lower unoccupied molecular orbital (LUMO) energy to study the interaction between ionic liquids with Bituminous and Anthracite coal using density function theory (DFT) method. B3LYP/6-31G* calculation predicts HOMO-LUMO energy gap, electronegativity, global hardness, global softness, chemical potential and global softness for individual compounds with their clusters. HOMO-LUMO interaction, electron delocalization, electron donating and accepting is the main source of attraction between individual compounds with their complexes. Cation used in this study: 1-butyl-1-methylpyrrolidinium [BMPYR], 1-methyl -3-propylimmidazolium [MPIM], Tributylmethylammonium [TMA] and Tributylmethylphosphonium [MTBP] with the combination of anion: bis(trifluromethylsulfonyl)imide [Tf2N], methyl carbonate [CH3CO3], dicyanamide [N(CN)2] and methylsulfate [MESO4]. Basically three-tier approach comprising HOMO/LUMO energy, Scalar quantity and infinite dilution activity coefficient (IDAC) by sigma profile generation with COSMO-RS (Conductor like screening model for real solvent) model was chosen for simultaneous interaction. [BMPYR]CH3CO3] (1-butyl-1-methylpyrrolidinium methyl carbonate) and [MPIM][CH3CO3] (1-methyl -3-propylimmidazolium methyl carbonate ) are the best effective ILs on the basis of HOMO-LUMO band gap for Anthracite and Bituminous coal respectively and the corresponding band gap is 0.10137 hartree for Anthracite coal and 0.12485 hartree for Bituminous coal. Further ionic liquids are screened quantitatively with all the scalar parameters and got the same result based on CH-π interaction which is found for HOMO-LUMO gap. To check our findings IDAC were predicted using quantum chemical based COSMO-RS methodology which gave the same trend as observed our scalar quantity calculation. Thereafter a qualitative measurement is doing by sigma profile analysis which gives complementary behavior between IL and coal that means highly miscible with each other.

Keywords: coal-ionic liquids cluster, COSMO-RS, DFT method, HOMO-LUMO interaction

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Authors: Monika Konieczyńska, Joanna Fajfer, Olga Lipińska

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In Poland works related to the exploration and prospection of unconventional hydrocarbons (natural gas accumulated in the Silurian shale formations) started in 2007, based on the experience of the other countries that have created new possibilities for the use of existing hydrocarbons resources. The highly water-consuming process of hydraulic fracturing is required for the exploitation of shale gas which implies a need to ensure large volume of water available. As a result considerable amount of mining waste is generated, particularly liquid waste, i.e. flowback fluid with variable chemical composition. The chemical composition of the flowback fluid depends on the composition of the fracturing fluid and the chemistry of the fractured geological formations. Typically, flowback fluid is highly salinated, can be enriched in heavy metals, including rare earth elements, naturally occurring radioactive materials and organic compounds. The generated fluids considered as the extractive waste should be properly managed in the recovery or disposal facility. Problematic issue is both high hydration of waste as well as their variable chemical composition. Also the limited capacity of currently operating facilities is a growing problem. Based on the estimates, currently operating facilities will not be sufficient for the need of waste disposal when extraction of unconventional hydrocarbons starts. Further more, the content of metals in flowback fluids including rare earth elements is a considerable incentive to develop technology of metals recovery. Also recycling is a key factor in terms of selection of treatment process, which should provide that the thresholds required for reuse are met. The paper will present the study of the flowback fluids chemical composition, based on samples from hydraulic fracturing processes performed in Poland. The scheme of flowback fluid cleaning and recovering technology will be reviewed along with a discussion of the results and an assessment of environmental impact, including all generated by-products. The presented technology is innovative due to the metal recovery, as well as purified water supply for hydraulic fracturing process, which is significant contribution to reducing water consumption.

Keywords: environmental impact, flowback fluid, management of special waste streams, metals recovery, shale gas

Procedia PDF Downloads 232

Authors: Yena Lee, Vassilis M. Charitopoulos, Karthik Thyagarajan, Ian Morris, Jose M. Pinto, Lazaros G. Papageorgiou

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With globalisation, the need to have better coordination of production and distribution decisions has become increasingly important for industrial gas companies in order to remain competitive in the marketplace. In this work, we investigate a problem that integrates production, inventory, and routing decisions in a liquid oxygen supply chain. The oxygen supply chain consists of production facilities, external third-party suppliers, and multiple customers, including hospitals and industrial customers. The product produced by the plants or sourced from the competitors, i.e., third-party suppliers, is distributed by a fleet of heterogenous vehicles to satisfy customer demands. The objective is to minimise the total operating cost involving production, third-party, and transportation costs. The key decisions for production include production and inventory levels and product amount from third-party suppliers. In contrast, the distribution decisions involve customer allocation, delivery timing, delivery amount, and vehicle routing. The optimisation of the coordinated production, inventory, and routing decisions is a challenging problem, especially when dealing with large-size problems. Thus, we present a two-stage procedure to solve the integrated problem efficiently. First, the problem is formulated as a mixed-integer linear programming (MILP) model by simplifying the routing component. The solution from the first-stage MILP model yields the optimal customer allocation, production and inventory levels, and delivery timing and amount. Then, we fix the previous decisions and solve a detailed routing. In the second stage, we propose a column generation scheme to address the computational complexity of the resulting detailed routing problem. A case study considering a real-life oxygen supply chain in the UK is presented to illustrate the capability of the proposed models and solution method. Furthermore, a comparison of the solutions from the proposed approach with the corresponding solutions provided by existing metaheuristic techniques (e.g., guided local search and tabu search algorithms) is presented to evaluate the efficiency.

Keywords: production planning, inventory routing, column generation, mixed-integer linear programming

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Authors: Raul Guerrero, Sandro Machado, Miriam Carvalho

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Soil and aquifer pollution, caused by hydrocarbon liquid spilling, is induced by misguided operational practices and inefficient safety guidelines. According to the Environmental Brazilian Institute (IBAMA), during 2013 alone, over 472.13 m3 of diesel oil leaked into the environment nationwide for those reported cases only. Regarding the aforementioned information, there’s an indisputable need to adopt appropriate environmental safeguards specially in those areas intended for the production, treatment, transportation and storage of hydrocarbon fluids. According to Brazilian norm, ABNT-NBR 7505-1:2000, compacted soil or mineral barriers used in structural contingency levees, such as storage tanks, are required to present a maximum water permeability coefficient, k, of 1x10-6 cm/s. However, as discussed by several authors, water can not be adopted as the reference fluid to determine the site’s containment performance against organic fluids. Mainly, due to the great discrepancy observed in polarity values (dielectric constant) between water and most organic fluids. Previous studies, within this same research group, proposed an optimal range of values for the soil’s index properties for mineral barrier composition focused on organic fluid containment. Unfortunately, in some circumstances, it is not possible to encounter a type of soil with the required geotechnical characteristics near the containment site, increasing prevention and construction costs, as well as environmental risks. For these specific cases, the use of an organic product or material as an additive to enhance mineral-barrier containment performance may be an attractive geotechnical solution. This paper evaluates the effect of activated carbon (AC) content additions into a clayey soil towards hydrocarbon fluid permeability. Variables such as compaction energy, carbon texture and addition content (0%, 10% and 20%) were analyzed through laboratory falling-head permeability tests using distilled water and commercial diesel as percolating fluids. The obtained results showed that the AC with smaller particle-size reduced k values significantly against diesel, indicating a direct relationship between particle-size reduction (surface area increase) of the organic product and organic fluid containment.

Keywords: activated carbon, clayey soils, permeability, surface area

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Authors: Konstantin Nefedev, Petr Andriushchenko

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Usually under the frustrated magnetics, it understands such materials, in which ones the interaction between located magnetic moments or spins has competing character, and can not to be satisfied simultaneously. The most well-known and simplest example of the frustrated system is antiferromagnetic Ising model on the triangle. Physically, the existence of frustrations means, that one cannot select all three pairs of spins anti-parallel in the basic unit of the triangle. In physics of the interacting particle systems, the vector models are used, which are constructed on the base of the pair-interaction law. Each pair interaction energy between one-component vectors can take two opposite in sign values, excluding the case of zero. Mathematically, the existence of frustrations in system means that it is impossible to have all negative energies of pair interactions in the Hamiltonian even in the ground state (lowest energy). In fact, the frustration is the excitation, which leaves in system, when thermodynamics does not work, i.e. at the temperature absolute zero. The origin of the frustration is the presence at least of one ''unsatisfied'' pair of interacted spins (magnetic moments). The minimal relative quantity of these excitations (relative quantity of frustrations in ground state) can be used as parameter of frustration. If the energy of the ground state is Egs, and summary energy of all energy of pair interactions taken with a positive sign is Emax, that proposed frustration parameter pf takes values from the interval [0,1] and it is defined as pf=(Egs+Emax)/2Emax. For antiferromagnetic Ising model on the triangle pf=1/3. We calculated the parameters of frustration in thermodynamic limit for different 2D periodical structures of Ising dipoles, which were on the ribs of the lattice and interact by means of the long-range dipolar interaction. For the honeycomb lattice pf=0.3415, triangular - pf=0.2468, kagome - pf=0.1644. All dependencies of frustration parameter from 1/N obey to the linear law. The given frustration parameter allows to consider the thermodynamics of all magnetic systems from united point of view and to compare the different lattice systems of interacting particle in the frame of vector models. This parameter can be the fundamental characteristic of frustrated systems. It has no dependence from temperature and thermodynamic states, in which ones the system can be found, such as spin ice, spin glass, spin liquid or even spin snow. It shows us the minimal relative quantity of excitations, which ones can exist in system at T=0.

Keywords: frustrations, parameter of order, statistical physics, magnetism

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Authors: Irene Buj-Corral, Ali Bagheri, Alejandro Dominguez-Fernandez

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In recent years, use of ceramic prostheses as an implant in some parts of body has become common. In the present study, research has focused on replacement of the acetabulum bone, which is a part of the pelvis bone. Metallic prostheses have shown some problems such as release of metal ions into patient's blood. In addition, fracture of liners and squeezing between surface of femoral head and inner surface of acetabulum have been reported. Ceramic prostheses have the advantage of low debris and high strength, although they are more difficult to be manufactured than metallic ones. Specifically, new designs try to attempt an acetabulum in which the outer surface will be porous for proliferation of cells and fixation of the prostheses by means of osteointegration, while inner surface must be smooth enough to assure that the movement between femoral head and inner surface will be carried out with on feasibility. In the present study, 3D printing technologies are used for manufacturing ceramic prostheses. In Fused Deposition Modelling (FDM) process, 3D printed plastic prostheses are obtained by means of melting of a plastic filament and subsequent deposition on a glass surface. A similar process is applied to ceramics in which ceramic powders need to be mixed with a liquid polymer before depositing them. After 3D printing, parts are subjected to a sintering process in an oven so that they can achieve final strength. In the present paper, influence of printing parameters on surface roughness 3D printed ceramic parts are presented. Three parameter full factorial design of experiments was used. Selected variables were layer height, infill and nozzle diameter. Responses were average roughness Ra and mean roughness depth Rz. Regression analysis was applied to responses in order to obtain mathematical models for responses. Results showed that surface roughness depends mainly on layer height and nozzle diameter employed, while infill was found not to be significant. In order to get low surface roughness, low layer height and low infill should be selected. As a conclusion, layer height and infill are important parameters for obtaining good surface finish in ceramic 3D printed prostheses. However, use of too low infill could lead to prostheses with low mechanical strength. Such prostheses could not be able to bear the static and dynamic charges to which they are subjected once they are implanted in the body. This issue will be addressed in further research.

Keywords: ceramic, hip prostheses, surface roughness, 3D printing

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Authors: Maryam Firouzmandi, Moosa Miri

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Aim and background: esthetic and structural reconstruction of anterior teeth may require the application of different restoration material. In this regard combination of direct composite veneer and ceramic crown is a common treatment option. Despite the initial matching, their long term harmony in term of optical and surface characteristics is a matter of concern. The purpose of this study is to evaluate and compare optical and surface characteristic of direct composite polished and glazed ceramic materials after exposure to tooth brush abrasion and staining solution. Materials and Methods: ten 2 mm thick disk shape specimens were prepared from IPS empress direct composite and twenty specimens from IPS e.max CAD blocks. Composite specimens and ten ceramic specimens were polished by using D&Z composite and ceramic polishing kit. The other ten specimens of ceramic were glazed with glazing liquid. Baseline measurement of roughness, CIElab coordinate, and luminance were recorded. Then the specimens underwent thermocycling, tooth brushing, and coffee staining. Afterword, the final measurements were recorded. Color coordinate were used to calculate ΔE76, ΔE00, translucency parameter, and contrast ratio. Data were analyzed by One-way ANOVA and post hoc LSD test. Results: baseline and final roughness of the study group were not different. At baseline, the order of roughness for the study group were as follows: composite < glazed ceramic < polished ceramic, but after aging, no difference. Between ceramic groups was not detected. The comparison of baseline and final luminance was similar to roughness but in reverse order. Unlike differential roughness which was comparable between the groups, changes in luminance of the glazed ceramic group was higher than other groups. ΔE76 and ΔE00 in the composite group were 18.35 and 12.84, in the glazed ceramic group were 1.3 and 0.79, and in polished ceramic were 1.26 and 0.85. These values for the composite group were significantly different from ceramic groups. Translucency of composite at baseline was significantly higher than final, but there was no significant difference between these values in ceramic groups. Composite was more translucency than ceramic at baseline and final measurement. Conclusion: Glazed ceramic surface was smoother than polished ceramic. Aging did not change the roughness. Optical properties (color and translucency) of the composite were influenced by aging. Luminance of composite, glazed ceramic, and polished ceramic decreased after aging, but the reduction in glazed ceramic was more pronounced.

Keywords: ceramic, tooth-brush abrasion, staining solution, composite resin

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Authors: Chabungbam Niranjit Khuman, Makarand Madhao Ghangrekar, Arunabha Mitra

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The cost of aeration is one of the limiting factors in the upscaling of microbial fuel cells (MFC) for field-scale applications. Wetland macrophytes have the ability to release oxygen into the water to maintain aerobic conditions in their root zone. In this experiment, the efficacy of rhizospheric oxygen release of wetland macrophytes as a source of oxygen in the cathodic chamber of MFC was conducted. The experiment was conducted in an MFC consisting of a three-liter anodic chamber made of ceramic cylinder and a 27 L cathodic chamber. Untreated carbon felts were used as electrodes (i.e., anode and cathode) and connected to an external load of 100 Ω using stainless steel wire. Wetland macrophytes (Canna indica) were grown in the cathodic chamber of the MFC in a hydroponic fashion using a styrofoam sheet (termed as macrophytes assisted-microbial fuel cell, M-MFC). The catholyte (i.e., water) in the M-MFC had negligible contact with atmospheric air due to the styrofoam sheet used for maintaining the hydroponic condition. There was no mixing of the catholyte in the M-MFC. Sucrose based synthetic wastewater having chemical oxygen demand (COD) of 3000 mg/L was fed into the anodic chamber of the MFC in fed-batch mode with a liquid retention time of four days. The C. indica thrived well throughout the duration of the experiment without much care. The average dissolved oxygen (DO) concentration and pH value in the M-MFC were 3.25 mg/L and 7.07, respectively, in the catholyte. Since the catholyte was not in contact with air, the DO in the catholyte might be considered as solely liberated from the rhizospheric oxygen release of C. indica. The maximum COD removal efficiency of M-MFC observed during the experiment was 76.9%. The inadequacy of terminal electron acceptor in the cathodic chamber in M-MFC might have hampered the electron transfer, which in turn, led to slower specific microbial activity, thereby resulting in lower COD removal efficiency than the traditional MFC with aerated catholyte. The average operating voltage (OV) and open-circuit voltage (OCV) of 294 mV and 594 mV, respectively, were observed in M-MFC. The maximum power density observed during polarization was 381 mW/m³, and the maximum sustainable power density observed during the experiment was 397 mW/m³ in M-MFC. The maximum normalized energy recovery and coulombic efficiency of 38.09 Wh/m³ and 1.27%, respectively, were observed. Therefore, it was evidenced that rhizospheric oxygen release of wetland macrophytes (C. indica) was capable of sustaining the cathodic reaction in MFC for field-scale applications.

Keywords: hydroponic, microbial fuel cell, rhizospheric oxygen release, wetland macrophytes

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Authors: Farzana Esmailkassam, Usakorn Kunanuvat, Zahraa Mohammed Ali

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Objective: The key barrier in Clozapine treatment of treatment-resistant schizophrenia (TRS) includes frequent bloods draws to monitor neutropenia, the main drug side effect. WBC and ANC monitoring must occur throughout treatment. Accurate WBC and ANC counts are necessary for clinical decisions to halt, modify or continue clozapine treatment. The CSAN Pronto point-of-care (POC) analyzer generates white blood cells (WBC) and absolute neutrophils (ANC) through image analysis of capillary blood. POC monitoring offers significant advantages over central laboratory testing. This study evaluated the performance of the CSAN Pronto against the Beckman DxH900 Hematology laboratory analyzer. Methods: Forty venous samples (EDTA whole blood) with varying concentrations of WBC and ANC as established on the DxH900 analyzer were tested in duplicates on three CSAN Pronto analyzers. Additionally, both venous and capillary samples were concomitantly collected from 20 volunteers and assessed on the CSAN Pronto and the DxH900 analyzer. The analytical performance including precision using liquid quality controls (QCs) as well as patient samples near the medical decision points, and linearity using a mix of high and low patient samples to create five concentrations was also evaluated. Results: In the precision study for QCs and whole blood, WBC and ANC showed CV inside the limits established according to manufacturer and laboratory acceptability standards. WBC and ANC were found to be linear across the measurement range with a correlation of 0.99. WBC and ANC from all analyzers correlated well in venous samples on the DxH900 across the tested sample ranges with a correlation of > 0.95. Mean bias in ANC obtained on the CSAN pronto versus the DxH900 was 0.07× 109 cells/L (95% L.O.A -0.25 to 0.49) for concentrations <4.0 × 109 cells/L, which includes decision-making cut-offs for continuing clozapine treatment. Mean bias in WBC obtained on the CSAN pronto versus the DxH900 was 0.34× 109 cells/L (95% L.O.A -0.13 to 0.72) for concentrations <5.0 × 109 cells/L. The mean bias was higher (-11% for ANC, 5% for WBC) at higher concentrations. The correlations between capillary and venous samples showed more variability with mean bias of 0.20 × 109 cells/L for the ANC. Conclusions: The CSAN pronto showed acceptable performance in WBC and ANC measurements from venous and capillary samples and was approved for clinical use. This testing will facilitate treatment decisions and improve clozapine uptake and compliance.

Keywords: absolute neutrophil counts, clozapine, point of care, white blood cells

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Authors: Himani Sharma, Amit Agrawal

Abstract:

Stability of the Cassie and Wenzel wetting states depends on intrinsic contact angle and geometric features on a surface that was exploited in capturing biofluids in microwells. However, the mechanism of imbibition of biofluids in the microwells is not well implied in terms of wettability of a substrate. In this work, we experimentally demonstrated filling dynamics in hydrophilic and hydrophobic microwells by protein solutions. Towards this, we utilized lotus leaf as a mold to fabricate microwells on a Polydimethylsiloxane (PDMS) surface. Lotus leaf containing micrometer-sized blunt-conical shaped pillars with a height of 8-15 µm and diameter of 3-8 µm were transferred on to PDMS. Furthermore, PDMS surface was treated with oxygen plasma to render the hydrophilic nature. A 10µL droplets containing fluorescein isothiocyanate (FITC) - labelled bovine serum albumin (BSA) were rested on both hydrophobic (θa = 108o, where θa is the apparent contact angle) and hydrophilic (θa = 60o) PDMS surfaces. A time-dependent fluorescence microscopy was conducted on these modified PDMS surfaces by recording the fluorescent intensity over a 5 minute period. It was observed that, initially (at t=1 min) FITC-BSA was accumulated on the periphery of both hydrophilic and hydrophobic microwells due to incomplete penetration of liquid-gas meniscus. This deposition of FITC-BSA on periphery of microwell was not changed with time for hydrophobic surfaces, whereas, a complete filling was occurred in hydrophilic microwells (at t=5 mins). This attributes to a gradual movement of three-phase contact line along the vertical surface of the hydrophilic microwells as compared to stable pinning in the hydrophobic microwells as confirmed by Surface Evolver simulations. In addition, if the cavities are presented on hydrophobic surfaces, air bubbles will be trapped inside the cavities once the aqueous solution is placed over these surfaces, resulting in the Cassie-Baxter wetting state. This condition hinders trapping of proteins inside the microwells. Thus, it is necessary to impart hydrophilicity to the microwell surfaces so as to induce the Wenzel state, such that, an entire solution will be fully in contact with the walls of microwells. Imbibition of microwells by protein solutions was analyzed in terms fluorescent intensity versus time. The present work underlines the importance of geometry of microwells and surface wettability of substrate in wetting and effective capturing of solid sub-phases in biofluids.

Keywords: BSA, microwells, surface evolver, wettability

Procedia PDF Downloads 172

Authors: Rajashree Bothale, Venkateswara Rao

Abstract:

Indian Himalayas also known as third pole with 0.9 Million SQ km area, contain the largest reserve of ice and snow outside poles and affect global climate and water availability in the perennial rivers. The variations in the extent of snow are indicative of climate change. The snow melt is sensitive to climate change (warming) and also an influencing factor to the climate change. A study of the spatio-temporal dynamics of snow cover and melt/freeze conditions is carried out using space based observations in visible and microwave bands. An analysis period of 2003 to 2015 is selected to identify and map the changes and trend in snow cover using Indian Remote Sensing (IRS) Advanced Wide Field Sensor (AWiFS) and Moderate Resolution Imaging Spectroradiometer(MODIS) data. For mapping of wet snow, microwave data is used, which is sensitive to the presence of liquid water in the snow. The present study uses Ku-band scatterometer data from QuikSCAT and Oceansat satellites. The enhanced resolution images at 2.25 km from the 13.6GHz sensor are used to analyze the backscatter response to dry and wet snow for the period of 2000-2013 using threshold method. The study area is divided into three major river basins namely Brahmaputra, Ganges and Indus which also represent the diversification in Himalayas as the Eastern Himalayas, Central Himalayas and Western Himalayas. Topographic variations across different zones show that a majority of the study area lies in 4000–5500 m elevation range and the maximum percent of high elevated areas (>5500 m) lies in Western Himalayas. The effect of climate change could be seen in the extent of snow cover and also on the melt/freeze status in different parts of Himalayas. Melt onset day increases from east (March11+11) to west (May12+15) with large variation in number of melt days. Western Himalayas has shorter melt duration (120+15) in comparison to Eastern Himalayas (150+16) providing lesser time for melt. Eastern Himalaya glaciers are prone for enhanced melt due to large melt duration. The extent of snow cover coupled with the status of melt/freeze indicating solar radiation can be used as precursor for monsoon prediction.

Keywords: Indian Himalaya, Scatterometer, Snow Melt/Freeze, AWiFS, Cryosphere

Procedia PDF Downloads 229

Authors: C. C. Alamanjo, A. O. Adepoju, H. Martin, R. N. Baines

Abstract:

Peri-urban agriculture in Jos Nigeria serves as a major means of livelihood for both urban and peri-urban poor, and constitutes huge commercial inclination with a target market that has spanned beyond Plateau State. Yet, the sustainability of this sector is threatened by intensive application of urban refuse ash contaminated with heavy metals, as a result of the highly heterogeneous materials used in ash production. Hence, this research aimed to understand the current fertilizer employed by farmers, their perception and acceptability in utilization of household sewage sludge for agricultural purposes and their capacity in mitigating risks associated with such practice. Mixed methods approach was adopted, and data collection tools used include survey questionnaire, focus group discussion with farmers, participants and field observation. The study identified that farmers maintain a complex mixture of organic and chemical fertilizers, with mixture composition that is dependent on fertilizer availability and affordability. Also, farmers have decreased the rate of utilization of urban refuse ash due to labor and increased logistic cost and are keen to utilize household sewage sludge for soil fertility improvement but are mainly constrained by accessibility of this waste product. Nevertheless, farmers near to sewage disposal points have commenced utilization of household sewage sludge for improving soil fertility. Farmers were knowledgeable on composting but find their strategic method of dewatering and sun drying more convenient. Irrigation farmers were not enthusiastic for treatment, as they desired both water and sludge. Secondly, household sewage sludge observed in the field is heterogeneous due to nearness between its disposal point and that of urban refuse, which raises concern for possible cross-contamination of pollutants and also portrays lack of extension guidance as regards to treatment and management of household sewage sludge for agricultural purposes. Hence, farmers concerns need to be addressed, particularly in providing extension advice and establishment of decentralized household sewage sludge collection centers, for continuous availability of liquid and concentrated sludge. Urgent need is also required for the Federal Government of Nigeria to increase commitment towards empowering her subsidiaries for efficient discharge of corporate responsibilities.

Keywords: ash, farmers, household, peri-urban, refuse, sewage, sludge, urban

Procedia PDF Downloads 101