Search results for: organic matter digestibility
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Search results for: organic matter digestibility

269 Morphological Transformation of Traditional Cities: The Case Study of the Historic Center of the City of Najaf

Authors: Sabeeh Lafta Farhan, Ihsan Abbass Jasim, Sohaib Kareem Al-Mamoori

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This study addresses the subject of transformation of urban structures and how does this transformation affect the character of traditional cities, which represents the research issue. Hence, the research has aimed at studying and learning about the urban structure characteristics and morphological transformation features in the traditional cities centers, and to look for means and methods to preserve the character of those cities. Cities are not merely locations inhabited by a large number of people, they are political and legal entities, in addition to economic activities that distinguish these cities, thus, they are a complex set of institutions, and the transformation in urban environment cannot be recognized without understanding these relationships. The research presumes an existing impact of urbanization on the properties of traditional structure of the Holy City of Najaf. The research has defined urbanization as restructuring and re-planning of urban areas that have lost their functions and bringing them into social and cultural life in the city, to be able to serve economy in order to better respond to the needs of users. Sacred Cities provide the organic connection between acts of worship and dealings and reveal the mechanisms and reasons behind the regulatory nature of the sacred shrine and their role in achieving organizational assimilation of urban morphology. The research has reached a theoretical framework of the particulars of urbanization. This framework has been applied to the historic center of the old city of Najaf, where the most important findings of the research were that the visual and structural dominant presence of holy shrine of Imam Ali (peace be upon him) remains to emphasize the visual particularity, and the main role of the city, which hosts one of the most important Muslim shrines in the world, in addition to the visible golden dome rising above the skyline, and the Imam Ali Mosque the hub and the center for religious activities. Thus, in view of being a place of main importance and a symbol of religious and Islamic culture, it is very important to have the shrine of Imam Ali (AS) prevailing on all zones of re-development in the old city. Consequently, the research underlined that the distinctive and unique character of the city of Najaf did not proceed from nothing, but was achieved through the unrivaled characteristics and features possessed by the city of Najaf alone, which allowed it and enabled it to occupy this status among the Arab and Muslim cities. That is why the activities arising from the development have to enhance the historical role of the city in order to have this development as clear support, strength and further addition to the city assets and its cultural heritage, and not seeing the developmental activities crushing the city urban traditional fabric, cultural heritage and its historical specificity.

Keywords: Iraq, the city of Najaf, heritage, traditional cities, morphological transformation

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268 Re-Entrant Direct Hexagonal Phases in a Lyotropic System Induced by Ionic Liquids

Authors: Saheli Mitra, Ramesh Karri, Praveen K. Mylapalli, Arka. B. Dey, Gourav Bhattacharya, Gouriprasanna Roy, Syed M. Kamil, Surajit Dhara, Sunil K. Sinha, Sajal K. Ghosh

Abstract:

The most well-known structures of lyotropic liquid crystalline systems are the two dimensional hexagonal phase of cylindrical micelles with a positive interfacial curvature and the lamellar phase of flat bilayers with zero interfacial curvature. In aqueous solution of surfactants, the concentration dependent phase transitions have been investigated extensively. However, instead of changing the surfactant concentrations, the local curvature of an aggregate can be altered by tuning the electrostatic interactions among the constituent molecules. Intermediate phases with non-uniform interfacial curvature are still unexplored steps to understand the route of phase transition from hexagonal to lamellar. Understanding such structural evolution in lyotropic liquid crystalline systems is important as it decides the complex rheological behavior of the system, which is one of the main interests of the soft matter industry. Sodium dodecyl sulfate (SDS) is an anionic surfactant and can be considered as a unique system to tune the electrostatics by cationic additives. In present study, imidazolium-based ionic liquids (ILs) with different number of carbon atoms in their single hydrocarbon chain were used as the additive in the aqueous solution of SDS. At a fixed concentration of total non-aqueous components (SDS and IL), the molar ratio of these components was changed, which effectively altered the electrostatic interactions between the SDS molecules. As a result, the local curvature is observed to modify, and correspondingly, the structure of the hexagonal liquid crystalline phases are transformed into other phases. Polarizing optical microscopy of SDS and imidazole-based-IL systems have exhibited different textures of the liquid crystalline phases as a function of increasing concentration of the ILs. The small angle synchrotron x-ray diffraction (SAXD) study has indicated the hexagonal phase of direct cylindrical micelles to transform to a rectangular phase at the presence of short (two hydrocarbons) chain IL. However, the hexagonal phase is transformed to a lamellar phase at the presence of long (ten hydrocarbons) chain IL. Interestingly, at the presence of a medium (four hydrocarbons) chain IL, the hexagonal phase is transformed to another hexagonal phase of direct cylindrical micelles through the lamellar phase. To the best of our knowledge, such a phase sequence has not been reported earlier. Even though the small angle x-ray diffraction study has revealed the lattice parameters of these phases to be similar to each other, their rheological behavior has been distinctly different. These rheological studies have shed lights on how these phases differ in their viscoelastic behavior. Finally, the packing parameters, calculated for these phases based on the geometry of the aggregates, have explained the formation of the self-assembled aggregates.

Keywords: lyotropic liquid crystals, polarizing optical microscopy, rheology, surfactants, small angle x-ray diffraction

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267 Analysis of the Effects of Institutions on the Sub-National Distribution of Aid Using Geo-Referenced AidData

Authors: Savas Yildiz

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The article assesses the performance of international aid donors to determine the sub-national distribution of their aid projects dependent on recipient countries’ governance. The present paper extends the scope from a cross-country perspective to a more detailed analysis by looking at the effects of institutional qualities on the sub-national distribution of foreign aid. The analysis examines geo-referenced aid project in 37 countries and 404 regions at the first administrative division level in Sub-Saharan Africa from the World Bank (WB) and the African Development Bank (ADB) that were approved between the years 2000 and 2011. To measure the influence of institutional qualities on the distribution of aid the following measures are used: control of corruption, government effectiveness, regulatory quality and rule of law from the World Governance Indicators (WGI) and the corruption perception index from Transparency International. Furthermore, to assess the importance of ethnic heterogeneity on the sub-national distribution of aid projects, the study also includes interaction terms measuring ethnic fragmentation. The regression results indicate a general skew of aid projects towards regions which hold capital cities, however, being incumbent presidents’ birth region does not increase the allocation of aid projects significantly. Nevertheless, with increasing quality of institutions aid projects are less skewed towards capital regions and the previously estimated coefficients loose significance in most cases. Higher ethnic fragmentation also seems to impede the possibility to allocate aid projects mainly in capital city regions and presidents’ birth places. Additionally, to assess the performance of the WB based on its own proclaimed goal to aim the poor in a country, the study also includes sub-national wealth data from the Demographic and Health Surveys (DSH), and finds that, even with better institutional qualities, regions with a larger share from the richest quintile receive significantly more aid than regions with a larger share of poor people. With increasing ethnic diversity, the allocation of aid projects towards regions where the richest citizens reside diminishes, but still remains high and significant. However, regions with a larger share of poor people still do not receive significantly more aid. This might imply that the sub-national distribution of aid projects increases in general with higher ethnic fragmentation, independent of the diverse regional needs. The results provide evidence that institutional qualities matter to undermine the influence of incumbent presidents on the allocation of aid projects towards their birth regions and capital regions. Moreover, even for countries with better institutional qualities the WB and the ADB do not seem to be able to aim the poor in a country with their aid projects. Even, if one considers need-based variables, such as infant mortality and child mortality rates, aid projects do not seem to be allocated in districts with a larger share of people in need. Therefore, the study provides further evidence using more detailed information on the sub-national distribution of aid projects that aid is not being allocated effectively towards regions with a larger share of poor people to alleviate poverty in recipient countries directly. Institutions do not have any significant influence on the sub-national distribution of aid towards the poor.

Keywords: aid allocation, georeferenced data, institutions, spatial analysis

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266 The Potential of Edaphic Algae for Bioremediation of the Diesel-Contaminated Soil

Authors: C. J. Tien, C. S. Chen, S. F. Huang, Z. X. Wang

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Algae in soil ecosystems can produce organic matters and oxygen by photosynthesis. Heterocyst-forming cyanobacteria can fix nitrogen to increase soil nitrogen contents. Secretion of mucilage by some algae increases the soil water content and soil aggregation. These actions will improve soil quality and fertility, and further increase abundance and diversity of soil microorganisms. In addition, some mixotrophic and heterotrophic algae are able to degrade petroleum hydrocarbons. Therefore, the objectives of this study were to analyze the effects of algal addition on the degradation of total petroleum hydrocarbons (TPH), diversity and activity of bacteria and algae in the diesel-contaminated soil under different nutrient contents and frequency of plowing and irrigation in order to assess the potential bioremediation technique using edaphic algae. The known amount of diesel was added into the farmland soil. This diesel-contaminated soil was subject to five settings, experiment-1 with algal addition by plowing and irrigation every two weeks, experiment-2 with algal addition by plowing and irrigation every four weeks, experiment-3 with algal and nutrient addition by plowing and irrigation every two weeks, experiment-4 with algal and nutrient addition by plowing and irrigation every four weeks, and the control without algal addition. Soil samples were taken every two weeks to analyze TPH concentrations, diversity of bacteria and algae, and catabolic genes encoding functional degrading enzymes. The results show that the TPH removal rates of five settings after the two-month experimental period were in the order: experiment-2 > expermient-4 > experiment-3 > experiment-1 > control. It indicated that algal addition enhanced the degradation of TPH in the diesel-contaminated soil, but not for nutrient addition. Plowing and irrigation every four weeks resulted in more TPH removal than that every two weeks. The banding patterns of denaturing gradient gel electrophoresis (DGGE) revealed an increase in diversity of bacteria and algae after algal addition. Three petroleum hydrocarbon-degrading algae (Anabaena sp., Oscillatoria sp. and Nostoc sp.) and two added algal strains (Leptolyngbya sp. and Synechococcus sp.) were sequenced from DGGE prominent bands. The four hydrocarbon-degrading bacteria Gordonia sp., Mycobacterium sp., Rodococcus sp. and Alcanivorax sp. were abundant in the treated soils. These results suggested that growth of indigenous bacteria and algae were improved after adding edaphic algae. Real-time polymerase chain reaction results showed that relative amounts of four catabolic genes encoding catechol 2, 3-dioxygenase, toluene monooxygenase, xylene monooxygenase and phenol monooxygenase were appeared and expressed in the treated soil. The addition of algae increased the expression of these genes at the end of experiments to biodegrade petroleum hydrocarbons. This study demonstrated that edaphic algae were suitable biomaterials for bioremediating diesel-contaminated soils with plowing and irrigation every four weeks.

Keywords: catabolic gene, diesel, diversity, edaphic algae

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265 Microbial and SARS-CoV-2 Efficiency Analysis of Froumann HEPA Filter Air Cleaner Brand

Authors: Serap Gedikli, Hakan Çakmak, M. Buğra Güldiken, Duygu Yalnızoğlu

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Air, which is necessary for living things to survive; while it carries some useful substances in it, it can also carry foreign particles of different sizes that may be harmful to the health. All airborne organic substances of biological origin, including bacteria, fungi, fungal spores, viruses, pollen, and their components, are called "bioaerosols". Nowadays, everyone spends most of their time in closed areas such as home, workplace, school, etc. Although it is known that outdoor air pollution affects health, it is not known that indoor air pollution has harmful effects in terms of health. In this study, indoor air microbial load and SARS-CoV-2 virus cleaning efficiency of Froumann brand air cleaners were studied. This work in 300 m³, 600 m³, and 1000 m³ completely closed areas without any air circulation with Froumann N80, N90, and N100 air-cleaning devices. Analyzes were performed for both areas at 60 minutes before and after the device was operated using a particle measuring device (Particles Plus 7302) and an air sampler (Mas-100 ECO). The measurements were taken by placing the test equipment 1.5-2 m away from the air cleaner. At the same time, the efficiency of the HEPA filter was evaluated by taking samples from the air outlet point of the HEPA filter using the air sampling device (Mas-100 ECO) after the device was started. Nutrient agar and malt agar are used as total mesophilic bacteria and total fungi. The number of colony-forming units per m³ (cfu/m³) was calculated by counting colonies in Petri dishes after incubation for 48 hours at 37°C for bacteria and 72 hours at 30°C for fungi. The change in the number of colonies and the decrease in the microbial load was calculated as a percentage value. SARS-CoV-2 activity analysis studies were carried out by İnönü University Microbiology Department in accordance with the World Health Organization regulations. Finally, the HEPA filter in the devices used was taken and kept under a certain temperature and humidity, and the change in the microbial load on it was monitored over a 6-month period. At the end of the studies, a 91%-94% reduction was determined in the total mesophilic bacteria count of Frouman brand N80, N90, and N100 model air cleaners. A decrease of 94%-96% was detected in the total number of yeast/molds. HEPA filter efficiency was evaluated, and at the end of the analysis, 98% of the bacterial load and approximately 100% of yeast/mold load at the HEPA filter air outlet point were decreased. According to the SARS- CoV-2 analysis results, when the device is operating at the medium airflow level 3, it can filter virus-carrying aerosols by 99%. As a result, it was determined that the Froumann model air cleaner was effective in controlling and reducing the microbial load in the indoor air.

Keywords: HEPA filter, indoor air quality, microbial load, SARS-CoV-2

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264 Mesoporous BiVO4 Thin Films as Efficient Visible Light Driven Photocatalyst

Authors: Karolina Ordon, Sandrine Coste, Malgorzata Makowska-Janusik, Abdelhadi Kassiba

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Photocatalytic processes play key role in the production of a new source of energy (as hydrogen), design of self-cleaning surfaces or for the environment preservation. The most challenging task deals with the purification of water distinguished by high efficiency. In the mentioned process, organic pollutants in solutions are decomposed to the simple, non-toxic compounds as H2O and CO2. The most known photocatalytic materials are ZnO, CdS and TiO2 semiconductors with a particular involvement of TiO2 as an efficient photocatalysts even with a high band gap equal to 3.2 eV which exploit only UV radiation from solar emitted spectrum. However, promising material with visible light induced photoactivity was searched through the monoclinic polytype of BiVO4 which has energy gap about 2.4 eV. As required in heterogeneous photocatalysis, the high contact surface is required. Also, BiVO4 as photocatalyst can be optimized by increasing its surface area by achieving the mesoporous structure synthesize. The main goal of the present work consists in the synthesis and characterization of BiVO4 mesoporous thin film. The synthesis method based on sol-gel was carried out using a standard surfactants such as P123 and F127. The thin film was deposited by spin and dip coating method. Then, the structural analysis of the obtained material was performed thanks to X-ray diffraction (XRD) and Raman spectroscopy. The surface of resulting structure was investigated using a scanning electron microscopy (SEM). The computer simulations based on modeling the optical and electronic properties of bulk BiVO4 by using DFT (density functional theory) methodology were carried out. The semiempirical parameterized method PM6 was used to compute the physical properties of BiVO4 nanostructures. The Raman and IR absorption spectra were also measured for synthesized mesoporous material, and the results were compared with the theoretical predictions. The simulations of nanostructured BiVO4 have pointed out the occurrence of quantum confinement for nanosized clusters leading to widening of the band gap. This result overcame the relevance of nanosized objects to harvest wide part of the solar spectrum. Also, a balance was searched experimentally through the mesoporous nature of the films devoted to enhancing the contact surface as required for heterogeneous catalysis without to lower the nanocrystallite size under some critical sizes inducing an increased band gap. The present contribution will discuss the relevant features of the mesoporous films with respect to their photocatalytic responses.

Keywords: bismuth vanadate, photocatalysis, thin film, quantum-chemical calculations

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263 A Bilingual Didactic Sequence about Biological Control to Develop the Scientific Literacy on High School Students

Authors: André Melo Franco Lorena De Barros, Elida Geralda Campos

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The bilingual education has just started in Brazils public schools. This paper is a didactic sequence of biology bilingual lessons about biologic control in the Brazilian Savana. This sequence has been applied in the first year of a bilingual education program in the only public English and Portuguese bilingual high school in Brazil. The aim of this work is to develop and apply a didactic sequence capable of developing the scientific literacy through the bilingual education associated with Problem Based Learning. This didactic sequence was applied in a class of 30 students. It was divided in three lessons. In the first lesson the students were divided in groups and received a fiction Letter from a mayor explaining the problem and asking students for help. The organic soy plantation of the mayor’s is been attacked by caterpillars. The students read the text then raised hypothesis of how they could solve the problem. In the second lesson the students searched online to verify if theirs hypothesis were correct and to find answers for the question proposed. In the third lesson the groups got together and discussed about their results and wrote a final essay with the answers for the problem proposed. The tools used to acquire information about the didactic sequence were: researcher’s diary, survey, interview and essay developed by the students. Most of the initial hypothesis couldn’t answer the problem properly. By the second lesson most of the students could answer properly. During the third lesson all the groups figured out suitable answers. The forms of biological control, birds habits and transgenic were deeply studied by the students. This methodology was successful for developing the scientific literacy with most of the students and also concluded that the quality of learning is directly associated with the effort of each student during the process. [ARAÚJO, Denise Lino de. O que é (e como se faz) sequência didática. Entrepalavras, Fortaleza, v. 3, n. 3, p.322-334, jul. 2013.] [FRANCO, Aline Aparecida et al. Preferência alimentar de Anticarsia gemmatalis Hübner (Lepidoptera: Noctuidae) por cultivares de soja. Científica: Revista de Ciências Agrárias, Jaboticabal, v. 1, n. 42, p.32-38, 29 jan. 2014.] [RIBEIRO, Luis Roberto de Camargo. Aprendizagem baseada em problemas (PBL): Uma experiência no ensino superior. São Carlos: Editora da Universidade Federal de São Carlos Ribeiro, 2008. 151 p.] [TRIVELATO, Sílvia L. Frateschi; TONIDANDEL, Sandra M. Rudella. Ensino Por Investigação: Eixos Organizadores Para Sequências De Ensino De Biologia. Ensaio Pesquisa em Educação em Ciências, Belo Horizonte, v. 17, n. especial, p.97-114, nov. 2015.].

Keywords: Bilingual Education, Environmental Education, Problem Based Learning, Science education

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262 Effects of Drying and Extraction Techniques on the Profile of Volatile Compounds in Banana Pseudostem

Authors: Pantea Salehizadeh, Martin P. Bucknall, Robert Driscoll, Jayashree Arcot, George Srzednicki

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Banana is one of the most important crops produced in large quantities in tropical and sub-tropical countries. Of the total plant material grown, approximately 40% is considered waste and left in the field to decay. This practice allows fungal diseases such as Sigatoka Leaf Spot to develop, limiting plant growth and spreading spores in the air that can cause respiratory problems in the surrounding population. The pseudostem is considered a waste residue of production (60 to 80 tonnes/ha/year), although it is a good source of dietary fiber and volatile organic compounds (VOC’s). Strategies to process banana pseudostem into palatable, nutritious and marketable food materials could provide significant social and economic benefits. Extraction of VOC’s with desirable odor from dried and fresh pseudostem could improve the smell of products from the confectionary and bakery industries. Incorporation of banana pseudostem flour into bakery products could provide cost savings and improve nutritional value. The aim of this study was to determine the effects of drying methods and different banana species on the profile of volatile aroma compounds in dried banana pseudostem. The banana species analyzed were Musa acuminata and Musa balbisiana. Fresh banana pseudostem samples were processed by either freeze-drying (FD) or heat pump drying (HPD). The extraction of VOC’s was performed at ambient temperature using vacuum distillation and the resulting, mostly aqueous, distillates were analyzed using headspace solid phase microextraction (SPME) gas chromatography – mass spectrometry (GC-MS). Optimal SPME adsorption conditions were 50 °C for 60 min using a Supelco 65 μm PDMS/DVB Stableflex fiber1. Compounds were identified by comparison of their electron impact mass spectra with those from the Wiley 9 / NIST 2011 combined mass spectral library. The results showed that the two species have notably different VOC profiles. Both species contained VOC’s that have been established in literature to have pleasant appetizing aromas. These included l-Menthone, D-Limonene, trans-linlool oxide, 1-Nonanol, CIS 6 Nonen-1ol, 2,6 Nonadien-1-ol, Benzenemethanol, 4-methyl, 1-Butanol, 3-methyl, hexanal, 1-Propanol, 2-methyl- acid، 2-Methyl-2-butanol. Results show banana pseudostem VOC’s are better preserved by FD than by HPD. This study is still in progress and should lead to the optimization of processing techniques that would promote the utilization of banana pseudostem in the food industry.

Keywords: heat pump drying, freeze drying, SPME, vacuum distillation, VOC analysis

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261 Correlation between Visual Perception and Social Function in Patients with Schizophrenia

Authors: Candy Chieh Lee

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Objective: The purpose of this study is to investigate the relationship between visual perception and social function in patients with schizophrenia. The specific aims are: 1) To explore performances in visual perception and social function in patients with schizophrenia 2) to examine the correlation between visual perceptual skills and social function in patients with schizophrenia The long-term goal is to be able to provide the most adequate intervention program for promoting patients’ visual perceptual skills and social function, as well as compensatory techniques. Background: Perceptual deficits in schizophrenia have been well documented in the visual system. Clinically, a considerable portion (up to 60%) of schizophrenia patients report distorted visual experiences such as visual perception of motion, color, size, and facial expression. Visual perception is required for the successful performance of most activities of daily living, such as dressing, making a cup of tea, driving a car and reading. On the other hand, patients with schizophrenia usually exhibit psychotic symptoms such as auditory hallucination and delusions which tend to alter their perception of reality and affect their quality of interpersonal relationship and limit their participation in various social situations. Social function plays an important role in the prognosis of patients with schizophrenia; lower social functioning skills can lead to poorer prognosis. Investigations on the relationship between social functioning and perceptual ability in patients with schizophrenia are relatively new but important as the results could provide information for effective intervention on visual perception and social functioning in patients with schizophrenia. Methods: We recruited 50 participants with schizophrenia in the mental health hospital (Taipei City Hospital, Songde branch, Taipei, Taiwan) acute ward. Participants who have signed consent forms, diagnosis of schizophrenia and having no organic vision deficits were included. Participants were administered the test of visual-perceptual skills (non-motor), third edition (TVPS-3) and the personal and social performance scale (PSP) for assessing visual perceptual skill and social function. The assessments will take about 70-90 minutes to complete. Data Analysis: The IBM SPSS 21.0 will be used to perform the statistical analysis. First, descriptive statistics will be performed to describe the characteristics and performance of the participants. Lastly, Pearson correlation will be computed to examine the correlation between PSP and TVPS-3 scores. Results: Significant differences were found between the means of participants’ TVPS-3 raw scores of each subtest with the age equivalent raw score provided by the TVPS-3 manual. Significant correlations were found between all 7 subtests of TVPS-3 and PSP total score. Conclusions: The results showed that patients with schizophrenia do exhibit visual perceptual deficits and is correlated social functions. Understanding these facts of patients with schizophrenia can assist health care professionals in designing and implementing adequate rehabilitative treatment according to patients’ needs.

Keywords: occupational therapy, social function, schizophrenia, visual perception

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260 The Effect of Lead(II) Lone Electron Pair and Non-Covalent Interactions on the Supramolecular Assembly and Fluorescence Properties of Pb(II)-Pyrrole-2-Carboxylato Polymer

Authors: M. Kowalik, J. Masternak, K. Kazimierczuk, O. V. Khavryuchenko, B. Kupcewicz, B. Barszcz

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Recently, the growing interest of chemists in metal-organic coordination polymers (MOCPs) is primarily derived from their intriguing structures and potential applications in catalysis, gas storage, molecular sensing, ion exchanges, nonlinear optics, luminescence, etc. Currently, we are devoting considerable effort to finding the proper method of synthesizing new coordination polymers containing S- or N-heteroaromatic carboxylates as linkers and characterizing the obtained Pb(II) compounds according to their structural diversity, luminescence, and thermal properties. The choice of Pb(II) as the central ion of MOCPs was motivated by several reasons mentioned in the literature: i) a large ionic radius allowing for a wide range of coordination numbers, ii) the stereoactivity of the 6s2 lone electron pair leading to a hemidirected or holodirected geometry, iii) a flexible coordination environment, and iv) the possibility to form secondary bonds and unusual non-covalent interactions, such as classic hydrogen bonds and π···π stacking interactions, as well as nonconventional hydrogen bonds and rarely reported tetrel bonds, Pb(lone pair)···π interactions, C–H···Pb agostic-type interactions or hydrogen bonds, and chelate ring stacking interactions. Moreover, the construction of coordination polymers requires the selection of proper ligands acting as linkers, because we are looking for materials exhibiting different network topologies and fluorescence properties, which point to potential applications. The reaction of Pb(NO₃)₂ with 1H-pyrrole-2-carboxylic acid (2prCOOH) leads to the formation of a new four-nuclear Pb(II) polymer, [Pb4(2prCOO)₈(H₂O)]ₙ, which has been characterized by CHN, FT-IR, TG, PL and single-crystal X-ray diffraction methods. In view of the primary Pb–O bonds, Pb1 and Pb2 show hemidirected pentagonal pyramidal geometries, while Pb2 and Pb4 display hemidirected octahedral geometries. The topology of the strongest Pb–O bonds was determined as the (4·8²) fes topology. Taking the secondary Pb–O bonds into account, the coordination number of Pb centres increased, Pb1 exhibited a hemidirected monocapped pentagonal pyramidal geometry, Pb2 and Pb4 exhibited a holodirected tricapped trigonal prismatic geometry, and Pb3 exhibited a holodirected bicapped trigonal prismatic geometry. Moreover, the Pb(II) lone pair stereoactivity was confirmed by DFT calculations. The 2D structure was expanded into 3D by the existence of non-covalent O/C–H···π and Pb···π interactions, which was confirmed by the Hirshfeld surface analysis. The above mentioned interactions improve the rigidity of the structure and facilitate the charge and energy transfer between metal centres, making the polymer a promising luminescent compound.

Keywords: coordination polymers, fluorescence properties, lead(II), lone electron pair stereoactivity, non-covalent interactions

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259 Isolation of Clitorin and Manghaslin from Carica papaya L. Leaves by CPC and Its Quantitative Analysis by QNMR

Authors: Norazlan Mohmad Misnan, Maizatul Hasyima Omar, Mohd Isa Wasiman

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Papaya (Carica papaya L., Caricaceae) is a tree which mainly cultivated for its fruits in many tropical regions including Australia, Brazil, China, Hawaii, and Malaysia. Beside of fruits, its leaves, seeds, and latex have also been traditionally used for treating diseases, which also reported to possess anti-cancer and anti- malaria properties. Its leaves have been reported to consist of various chemical compounds such as alkaloids, flavonoids and phenolics. Clitorin and manghaslin are among major flavonoids presence. Thus, the aim of this study is to quantify the purity of these isolated compounds (clitorin and manghsalin) by using quantitative Nuclear Magnetic Resonance (qNMR) analysis. Only fresh C. papaya leaves were used for juice extraction procedure and subsequently was freeze-dried to obtain a dark green powdered form of the extract prior to Centrifugal Partition Chromatography (CPC) separation. The CPC experiments were performed using a two-phase solvent system comprising ethyl acetate/butanol/water (1:4:5, v/v/v/v) solvent. The upper organic phase was used as the stationary phase, and the lower aqueous phase was employed as the mobile phase. Ten fractions were obtained after an hour runtime analysis. Fraction 6 and fraction 8 has been identified as clitorin (m/z 739.21 [M-H]-) and manghaslin (m/z 755.21 [M-H]-), respectively, based on LCMS data and full analysis of NMR (1H NMR, 13C NMR, HMBC, and HSQC). The 1H-qNMR measurements were carried out using a 400 MHz NMR spectrometer (JEOL ECS 400MHz, Japan) and deuterated methanol was used as a solvent. Quantification was performed using the AQARI method (Accurate Quantitative NMR) with deuterated 1,4-Bis(trimethylsilyl)benzene (BTMSB) as an internal reference substances. This AQARI protocol includes not only NMR measurement but also sample preparation that provide highest precision and accuracy than other qNMR methods. The 90° pulse length and the T1 relaxation times for compounds and BTMSB were determined prior to the quantification to give the best signal-to-noise ratio. Regions containing the two downfield signals from aromatic part (6.00–6.89 ppm), and the singlet signal, (18H) arising from BTMSB (0.63-1.05ppm) were selected for integration. The purity of clitorin and manghaslin were calculated to be 52.22% and 43.36%, respectively. Further purification is needed in order to increase its purity. This finding has demonstrated the use of qNMR for quality control and standardization of various plant extracts and which can be applied for NMR fingerprinting of other plant-based products with good reproducibility and in the case where commercial standards is not readily available.

Keywords: Carica papaya, clitorin, manghaslin, quantitative Nuclear Magnetic Resonance, Centrifugal Partition Chromatography

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258 Formation of the Water Assisted Supramolecular Assembly in the Transition Structure of Organocatalytic Asymmetric Aldol Reaction: A DFT Study

Authors: Kuheli Chakrabarty, Animesh Ghosh, Atanu Roy, Gourab Kanti Das

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Aldol reaction is an important class of carbon-carbon bond forming reactions. One of the popular ways to impose asymmetry in aldol reaction is the introduction of chiral auxiliary that binds the approaching reactants and create dissymmetry in the reaction environment, which finally evolves to enantiomeric excess in the aldol products. The last decade witnesses the usage of natural amino acids as chiral auxiliary to control the stereoselectivity in various carbon-carbon bond forming processes. In this context, L-proline was found to be an effective organocatalyst in asymmetric aldol additions. In last few decades the use of water as solvent or co-solvent in asymmetric organocatalytic reaction is increased sharply. Simple amino acids like L-proline does not catalyze asymmetric aldol reaction in aqueous medium not only that, In organic solvent medium high catalytic loading (~30 mol%) is required to achieve moderate to high asymmetric induction. In this context, huge efforts have been made to modify L-proline and 4-hydroxy-L-proline to prepare organocatalyst for aqueous medium asymmetric aldol reaction. Here, we report the result of our DFT calculations on asymmetric aldol reaction of benzaldehyde, p-NO2 benzaldehyde and t-butyraldehyde with a number of ketones using L-proline hydrazide as organocatalyst in wet solvent free condition. Gaussian 09 program package and Gauss View program were used for the present work. Geometry optimizations were performed using B3LYP hybrid functional and 6-31G(d,p) basis set. Transition structures were confirmed by hessian calculation and IRC calculation. As the reactions were carried out in solvent free condition, No solvent effect were studied theoretically. Present study has revealed for the first time, the direct involvement of two water molecules in the aldol transition structures. In the TS, the enamine and the aldehyde is connected through hydrogen bonding by the assistance of two intervening water molecules forming a supramolecular network. Formation of this type of supramolecular assembly is possible due to the presence of protonated -NH2 group in the L-proline hydrazide moiety, which is responsible for the favorable entropy contribution to the aldol reaction. It is also revealed from the present study that, water assisted TS is energetically more favorable than the TS without involving any water molecule. It can be concluded from this study that, insertion of polar group capable of hydrogen bond formation in the L-proline skeleton can lead to a favorable aldol reaction with significantly high enantiomeric excess in wet solvent free condition by reducing the activation barrier of this reaction.

Keywords: aldol reaction, DFT, organocatalysis, transition structure

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257 The Processing of Context-Dependent and Context-Independent Scalar Implicatures

Authors: Liu Jia’nan

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The default accounts hold the view that there exists a kind of scalar implicature which can be processed without context and own a psychological privilege over other scalar implicatures which depend on context. In contrast, the Relevance Theorist regards context as a must because all the scalar implicatures have to meet the need of relevance in discourse. However, in Katsos, the experimental results showed: Although quantitatively the adults rejected under-informative utterance with lexical scales (context-independent) and the ad hoc scales (context-dependent) at almost the same rate, adults still regarded the violation of utterance with lexical scales much more severe than with ad hoc scales. Neither default account nor Relevance Theory can fully explain this result. Thus, there are two questionable points to this result: (1) Is it possible that the strange discrepancy is due to other factors instead of the generation of scalar implicature? (2) Are the ad hoc scales truly formed under the possible influence from mental context? Do the participants generate scalar implicatures with ad hoc scales instead of just comparing semantic difference among target objects in the under- informative utterance? In my Experiment 1, the question (1) will be answered by repetition of Experiment 1 by Katsos. Test materials will be showed by PowerPoint in the form of pictures, and each procedure will be done under the guidance of a tester in a quiet room. Our Experiment 2 is intended to answer question (2). The test material of picture will be transformed into the literal words in DMDX and the target sentence will be showed word-by-word to participants in the soundproof room in our lab. Reading time of target parts, i.e. words containing scalar implicatures, will be recorded. We presume that in the group with lexical scale, standardized pragmatically mental context would help generate scalar implicature once the scalar word occurs, which will make the participants hope the upcoming words to be informative. Thus if the new input after scalar word is under-informative, more time will be cost for the extra semantic processing. However, in the group with ad hoc scale, scalar implicature may hardly be generated without the support from fixed mental context of scale. Thus, whether the new input is informative or not does not matter at all, and the reading time of target parts will be the same in informative and under-informative utterances. People’s mind may be a dynamic system, in which lots of factors would co-occur. If Katsos’ experimental result is reliable, will it shed light on the interplay of default accounts and context factors in scalar implicature processing? We might be able to assume, based on our experiments, that one single dominant processing paradigm may not be plausible. Furthermore, in the processing of scalar implicature, the semantic interpretation and the pragmatic interpretation may be made in a dynamic interplay in the mind. As to the lexical scale, the pragmatic reading may prevail over the semantic reading because of its greater exposure in daily language use, which may also lead the possible default or standardized paradigm override the role of context. However, those objects in ad hoc scale are not usually treated as scalar membership in mental context, and thus lexical-semantic association of the objects may prevent their pragmatic reading from generating scalar implicature. Only when the sufficient contextual factors are highlighted, can the pragmatic reading get privilege and generate scalar implicature.

Keywords: scalar implicature, ad hoc scale, dynamic interplay, default account, Mandarin Chinese processing

Procedia PDF Downloads 295
256 Study on the Rapid Start-up and Functional Microorganisms of the Coupled Process of Short-range Nitrification and Anammox in Landfill Leachate Treatment

Authors: Lina Wu

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The excessive discharge of nitrogen in sewage greatly intensifies the eutrophication of water bodies and poses a threat to water quality. Nitrogen pollution control has become a global concern. Currently, the problem of water pollution in China is still not optimistic. As a typical high ammonia nitrogen organic wastewater, landfill leachate is more difficult to treat than domestic sewage because of its complex water quality, high toxicity, and high concentration.Many studies have shown that the autotrophic anammox bacteria in nature can combine nitrous and ammonia nitrogen without carbon source through functional genes to achieve total nitrogen removal, which is very suitable for the removal of nitrogen from leachate. In addition, the process also saves a lot of aeration energy consumption than the traditional nitrogen removal process. Therefore, anammox plays an important role in nitrogen conversion and energy saving. The process composed of short-range nitrification and denitrification coupled an ammo ensures the removal of total nitrogen and improves the removal efficiency, meeting the needs of the society for an ecologically friendly and cost-effective nutrient removal treatment technology. Continuous flow process for treating late leachate [an up-flow anaerobic sludge blanket reactor (UASB), anoxic/oxic (A/O)–anaerobic ammonia oxidation reactor (ANAOR or anammox reactor)] has been developed to achieve autotrophic deep nitrogen removal. In this process, the optimal process parameters such as hydraulic retention time and nitrification flow rate have been obtained, and have been applied to the rapid start-up and stable operation of the process system and high removal efficiency. Besides, finding the characteristics of microbial community during the start-up of anammox process system and analyzing its microbial ecological mechanism provide a basis for the enrichment of anammox microbial community under high environmental stress. One research developed partial nitrification-Anammox (PN/A) using an internal circulation (IC) system and a biological aerated filter (BAF) biofilm reactor (IBBR), where the amount of water treated is closer to that of landfill leachate. However, new high-throughput sequencing technology is still required to be utilized to analyze the changes of microbial diversity of this system, related functional genera and functional genes under optimal conditions, providing theoretical and further practical basis for the engineering application of novel anammox system in biogas slurry treatment and resource utilization.

Keywords: nutrient removal and recovery, leachate, anammox, partial nitrification

Procedia PDF Downloads 28
255 Monitoring Air Pollution Effects on Children for Supporting Public Health Policy: Preliminary Results of MAPEC_LIFE Project

Authors: Elisabetta Ceretti, Silvia Bonizzoni, Alberto Bonetti, Milena Villarini, Marco Verani, Maria Antonella De Donno, Sara Bonetta, Umberto Gelatti

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Introduction: Air pollution is a global problem. In 2013, the International Agency for Research on Cancer (IARC) classified air pollution and particulate matter as carcinogenic to human. The study of the health effects of air pollution in children is very important because they are a high-risk group in terms of the health effects of air pollution and early exposure during childhood can increase the risk of developing chronic diseases in adulthood. The MAPEC_LIFE (Monitoring Air Pollution Effects on Children for supporting public health policy) is a project founded by EU Life+ Programme which intends to evaluate the associations between air pollution and early biological effects in children and to propose a model for estimating the global risk of early biological effects due to air pollutants and other factors in children. Methods: The study was carried out on 6-8-year-old children living in five Italian towns in two different seasons. Two biomarkers of early biological effects, primary DNA damage detected with the comet assay and frequency of micronuclei, were investigated in buccal cells of children. Details of children diseases, socio-economic status, exposures to other pollutants and life-style were collected using a questionnaire administered to children’s parents. Child exposure to urban air pollution was assessed by analysing PM0.5 samples collected in the school areas for PAHs and nitro-PAHs concentration, lung toxicity and in vitro genotoxicity on bacterial and human cells. Data on the chemical features of the urban air during the study period were obtained from the Regional Agency for Environmental Protection. The project created also the opportunity to approach the issue of air pollution with the children, trying to raise their awareness on air quality, its health effects and some healthy behaviors by means of an educational intervention in the schools. Results: 1315 children were recruited for the study and participate in the first sampling campaign in the five towns. The second campaign, on the same children, is still ongoing. The preliminary results of the tests on buccal mucosa cells of children will be presented during the conference as well as the preliminary data about the chemical composition and the toxicity and genotoxicity features of PM0.5 samples. The educational package was tested on 250 children of the primary school and showed to be very useful, improving children knowledge about air pollution and its effects and stimulating their interest. Conclusions: The associations between levels of air pollutants, air mutagenicity and biomarkers of early effects will be investigated. A tentative model to calculate the global absolute risk of having early biological effects for air pollution and other variables together will be proposed and may be useful to support policy-making and community interventions to protect children from possible health effects of air pollutants.

Keywords: air pollution exposure, biomarkers of early effects, children, public health policy

Procedia PDF Downloads 307
254 Unfolding Architectural Assemblages: Mapping Contemporary Spatial Objects' Affective Capacity

Authors: Panagiotis Roupas, Yota Passia

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This paper aims at establishing an index of design mechanisms - immanent in spatial objects - based on the affective capacity of their material formations. While spatial objects (design objects, buildings, urban configurations, etc.) are regarded as systems composed of interacting parts, within the premises of assemblage theory, their ability to affect and to be affected has not yet been mapped or sufficiently explored. This ability lies in excess, a latent potentiality they contain, not transcendental but immanent in their pre-subjective aesthetic power. As spatial structures are theorized as assemblages - composed of heterogeneous elements that enter into relations with one another - and since all assemblages are parts of larger assemblages, their components' ability to engage is contingent. We thus seek to unfold the mechanisms inherent in spatial objects that allow to the constituent parts of design assemblages to perpetually enter into new assemblages. To map architectural assemblage's affective ability, spatial objects are analyzed in two axes. The first axis focuses on the relations that the assemblage's material and expressive components develop in order to enter the assemblages. Material components refer to those material elements that an assemblage requires in order to exist, while expressive components includes non-linguistic (sense impressions) as well as linguistic (beliefs). The second axis records the processes known as a-signifying signs or a-signs, which are the triggering mechanisms able to territorialize or deterritorialize, stabilize or destabilize the assemblage and thus allow it to assemble anew. As a-signs cannot be isolated from matter, we point to their resulting effects, which without entering the linguistic level they are expressed in terms of intensity fields: modulations, movements, speeds, rhythms, spasms, etc. They belong to a molecular level where they operate in the pre-subjective world of perceptions, effects, drives, and emotions. A-signs have been introduced as intensities that transform the object beyond meaning, beyond fixed or known cognitive procedures. To that end, from an archive of more than 100 spatial objects by contemporary architects and designers, we have created an effective mechanisms index is created, where each a-sign is now connected with the list of effects it triggers and which thoroughly defines it. And vice versa, the same effect can be triggered by different a-signs, allowing the design object to lie in a perpetual state of becoming. To define spatial objects, A-signs are categorized in terms of their aesthetic power to affect and to be affected on the basis of the general categories of form, structure and surface. Thus, different part's degree of contingency are evaluated and measured and finally, we introduce as material information that is immanent in the spatial object while at the same time they confer no meaning; they only convey some information without semantic content. Through this index, we are able to analyze and direct the final form of the spatial object while at the same time establishing the mechanism to measure its continuous transformation.

Keywords: affective mechanisms index, architectural assemblages, a-signifying signs, cartography, virtual

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253 Impact of Traffic Restrictions due to Covid19, on Emissions from Freight Transport in Mexico City

Authors: Oscar Nieto-Garzón, Angélica Lozano

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In urban areas, on-road freight transportation creates several social and environmental externalities. Then, it is crucial that freight transport considers not only economic aspects, like retailer distribution cost reduction and service improvement, but also environmental effects such as global CO2 and local emissions (e.g. Particulate Matter, NOX, CO) and noise. Inadequate infrastructure development, high rate of urbanization, the increase of motorization, and the lack of transportation planning are characteristics that urban areas from developing countries share. The Metropolitan Area of Mexico City (MAMC), the Metropolitan Area of São Paulo (MASP), and Bogota are three of the largest urban areas in Latin America where air pollution is often a problem associated with emissions from mobile sources. The effect of the lockdown due to COVID-19 was analyzedfor these urban areas, comparing the same period (January to August) of years 2016 – 2019 with 2020. A strong reduction in the concentration of primary criteria pollutants emitted by road traffic were observed at the beginning of 2020 and after the lockdown measures.Daily mean concentration of NOx decreased 40% in the MAMC, 34% in the MASP, and 62% in Bogota. Daily mean ozone levels increased after the lockdown measures in the three urban areas, 25% in MAMC, 30% in the MASP and 60% in Bogota. These changes in emission patterns from mobile sources drastically changed the ambient atmospheric concentrations of CO and NOX. The CO/NOX ratioat the morning hours is often used as an indicator of mobile sources emissions. In 2020, traffic from cars and light vehicles was significantly reduced due to the first lockdown, but buses and trucks had not restrictions. In theory, it implies a decrease in CO and NOX from cars or light vehicles, maintaining the levels of NOX by trucks(or lower levels due to the congestion reduction). At rush hours, traffic was reduced between 50% and 75%, so trucks could get higher speeds, which would reduce their emissions. By means an emission model, it was found that an increase in the average speed (75%) would reduce the emissions (CO, NOX, and PM) from diesel trucks by up to 30%. It was expected that the value of CO/NOXratio could change due to thelockdownrestrictions. However, although there was asignificant reduction of traffic, CO/NOX kept its trend, decreasing to 8-9 in 2020. Hence, traffic restrictions had no impact on the CO/NOX ratio, although they did reduce vehicle emissions of CO and NOX. Therefore, these emissions may not adequately represent the change in the vehicle emission patterns, or this ratio may not be a good indicator of emissions generated by vehicles. From the comparison of the theoretical data and those observed during the lockdown, results that the real NOX reduction was lower than the theoretical reduction. The reasons could be that there are other sources of NOX emissions, so there would be an over-representation of NOX emissions generated by diesel vehicles, or there is an underestimation of CO emissions. Further analysis needs to consider this ratioto evaluate the emission inventories and then to extend these results forthe determination of emission control policies to non-mobile sources.

Keywords: COVID-19, emissions, freight transport, latin American metropolis

Procedia PDF Downloads 115
252 A Supply Chain Risk Management Model Based on Both Qualitative and Quantitative Approaches

Authors: Henry Lau, Dilupa Nakandala, Li Zhao

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In today’s business, it is well-recognized that risk is an important factor that needs to be taken into consideration before a decision is made. Studies indicate that both the number of risks faced by organizations and their potential consequences are growing. Supply chain risk management has become one of the major concerns for practitioners and researchers. Supply chain leaders and scholars are now focusing on the importance of managing supply chain risk. In order to meet the challenge of managing and mitigating supply chain risk (SCR), we must first identify the different dimensions of SCR and assess its relevant probability and severity. SCR has been classified in many different ways, and there are no consistently accepted dimensions of SCRs and several different classifications are reported in the literature. Basically, supply chain risks can be classified into two dimensions namely disruption risk and operational risk. Disruption risks are those caused by events such as bankruptcy, natural disasters and terrorist attack. Operational risks are related to supply and demand coordination and uncertainty, such as uncertain demand and uncertain supply. Disruption risks are rare but severe and hard to manage, while operational risk can be reduced through effective SCM activities. Other SCRs include supply risk, process risk, demand risk and technology risk. In fact, the disorganized classification of SCR has created confusion for SCR scholars. Moreover, practitioners need to identify and assess SCR. As such, it is important to have an overarching framework tying all these SCR dimensions together for two reasons. First, it helps researchers use these terms for communication of ideas based on the same concept. Second, a shared understanding of the SCR dimensions will support the researchers to focus on the more important research objective: operationalization of SCR, which is very important for assessing SCR. In general, fresh food supply chain is subject to certain level of risks, such as supply risk (low quality, delivery failure, hot weather etc.) and demand risk (season food imbalance, new competitors). Effective strategies to mitigate fresh food supply chain risk are required to enhance operations. Before implementing effective mitigation strategies, we need to identify the risk sources and evaluate the risk level. However, assessing the supply chain risk is not an easy matter, and existing research mainly use qualitative method, such as risk assessment matrix. To address the relevant issues, this paper aims to analyze the risk factor of the fresh food supply chain using an approach comprising both fuzzy logic and hierarchical holographic modeling techniques. This novel approach is able to take advantage the benefits of both of these well-known techniques and at the same time offset their drawbacks in certain aspects. In order to develop this integrated approach, substantial research work is needed to effectively combine these two techniques in a seamless way, To validate the proposed integrated approach, a case study in a fresh food supply chain company was conducted to verify the feasibility of its functionality in a real environment.

Keywords: fresh food supply chain, fuzzy logic, hierarchical holographic modelling, operationalization, supply chain risk

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251 Evaluation Method for Fouling Risk Using Quartz Crystal Microbalance

Authors: Natsuki Kishizawa, Keiko Nakano, Hussam Organji, Amer Shaiban, Mohammad Albeirutty

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One of the most important tasks in operating desalination plants using a reverse osmosis (RO) method is preventing RO membrane fouling caused by foulants found in seawater. Optimal design of the pre-treatment process of RO process for plants enables the reduction of foulants. Therefore, a quantitative evaluation of the fouling risk in pre-treated water, which is fed to RO, is required for optimal design. Some measurement methods for water quality such as silt density index (SDI) and total organic carbon (TOC) have been conservatively applied for evaluations. However, these methods have not been effective in some situations for evaluating the fouling risk of RO feed water. Furthermore, stable management of plants will be possible by alerts and appropriate control of the pre-treatment process by using the method if it can be applied to the inline monitoring system for the fouling risk of RO feed water. The purpose of this study is to develop a method to evaluate the fouling risk of RO feed water. We applied a quartz crystal microbalance (QCM) to measure the amount of foulants found in seawater using a sensor whose surface is coated with polyamide thin film, which is the main material of a RO membrane. The increase of the weight of the sensor after a certain length of time in which the sample water passes indicates the fouling risk of the sample directly. We classified the values as “FP: Fouling Potential”. The characteristics of the method are to measure the very small amount of substances in seawater in a short time: < 2h, and from a small volume of the sample water: < 50mL. Using some RO cell filtration units, a higher correlation between the pressure increase given by RO fouling and the FP from the method than SDI and TOC was confirmed in the laboratory-scale test. Then, to establish the correlation in the actual bench-scale RO membrane module, and to confirm the feasibility of the monitoring system as a control tool for the pre-treatment process, we have started a long-term test at an experimental desalination site by the Red Sea in Jeddah, Kingdom of Saudi Arabia. Implementing inline equipment for the method made it possible to measure FP intermittently (4 times per day) and automatically. Moreover, for two 3-month long operations, the RO operation pressure among feed water samples of different qualities was compared. The pressure increase through a RO membrane module was observed at a high FP RO unit in which feed water was treated by a cartridge filter only. On the other hand, the pressure increase was not observed at a low FP RO unit in which feed water was treated by an ultra-filter during the operation. Therefore, the correlation in an actual scale RO membrane was established in two runs of two types of feed water. The result suggested that the FP method enables the evaluation of the fouling risk of RO feed water.

Keywords: fouling, monitoring, QCM, water quality

Procedia PDF Downloads 197
250 Harvesting Value-added Products Through Anodic Electrocatalytic Upgrading Intermediate Compounds Utilizing Biomass to Accelerating Hydrogen Evolution

Authors: Mehran Nozari-Asbemarz, Italo Pisano, Simin Arshi, Edmond Magner, James J. Leahy

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Integrating electrolytic synthesis with renewable energy makes it feasible to address urgent environmental and energy challenges. Conventional water electrolyzers concurrently produce H₂ and O₂, demanding additional procedures in gas separation to prevent contamination of H₂ with O₂. Moreover, the oxygen evolution reaction (OER), which is sluggish and has a low overall energy conversion efficiency, does not deliver a significant value product on the electrode surface. Compared to conventional water electrolysis, integrating electrolytic hydrogen generation from water with thermodynamically more advantageous aqueous organic oxidation processes can increase energy conversion efficiency and create value-added compounds instead of oxygen at the anode. One strategy is to use renewable and sustainable carbon sources from biomass, which has a large annual production capacity and presents a significant opportunity to supplement carbon sourced from fossil fuels. Numerous catalytic techniques have been researched in order to utilize biomass economically. Because of its safe operating conditions, excellent energy efficiency, and reasonable control over production rate and selectivity using electrochemical parameters, electrocatalytic upgrading stands out as an appealing choice among the numerous biomass refinery technologies. Therefore, we propose a broad framework for coupling H2 generation from water splitting with oxidative biomass upgrading processes. Four representative biomass targets were considered for oxidative upgrading that used a hierarchically porous CoFe-MOF/LDH @ Graphite Paper bifunctional electrocatalyst, including glucose, ethanol, benzyl, furfural, and 5-hydroxymethylfurfural (HMF). The potential required to support 50 mA cm-2 is considerably lower than (~ 380 mV) the potential for OER. All four compounds can be oxidized to yield liquid byproducts with economic benefit. The electrocatalytic oxidation of glucose to the value-added products, gluconic acid, glucuronic acid, and glucaric acid, was examined in detail. The cell potential for combined H₂ production and glucose oxidation was substantially lower than for water splitting (1.44 V(RHE) vs. 1.82 V(RHE) for 50 mA cm-2). In contrast, the oxidation byproduct at the anode was significantly more valuable than O₂, taking advantage of the more favorable glucose oxidation in comparison to the OER. Overall, such a combination of HER and oxidative biomass valorization using electrocatalysts prevents the production of potentially explosive H₂/O₂mixtures and produces high-value products at both electrodes with lower voltage input, thereby increasing the efficiency and activity of electrocatalytic conversion.

Keywords: biomass, electrocatalytic, glucose oxidation, hydrogen evolution

Procedia PDF Downloads 73
249 Photochemical Behaviour of Carbamazepine in Natural Waters

Authors: Fanny Desbiolles, Laure Malleret, Isabelle Laffont-Schwob, Christophe Tiliacos, Anne Piram, Mohamed Sarakha, Pascal Wong-Wah-Chung

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Pharmaceuticals in the environment have become a very hot topic in the recent years. This interest is related to the large amounts dispensed and to their release in urine or faeces from treated patients, resulting in their ubiquitous presence in water resources and wastewater treatment plants (WWTP) effluents. Thereby, many studies focused on the prediction of pharmaceuticals’ behaviour, to assess their fate and impacts in the environment. Carbamazepine is a widely consumed psychotropic pharmaceutical, thus being one of the most commonly detected drugs in the environment. This organic pollutant was proved to be persistent, especially with respect to its non-biodegradability, rendering it recalcitrant to usual biological treatment processes. Consequently, carbamazepine is very little removed in WWTP with a maximum abatement rate of 5 % and is then often released in natural surface waters. To better assess the environmental fate of carbamazepine in aqueous media, its photochemical transformation was undertaken in four natural waters (two French rivers, the Berre salt lagoon, Mediterranean Sea water) representative of coastal and inland water types. Kinetic experiments were performed in the presence of light using simulated solar irradiation (Xe lamp 300W). Formation of short-lifetime species was highlighted using chemical trap and laser flash photolysis (nanosecond). Identification of transformation by-products was assessed by LC-QToF-MS analyses. Carbamazepine degradation was observed after a four-day exposure and an abatement of 20% maximum was measured yielding to the formation of many by-products. Moreover, the formation of hydroxyl radicals (•OH) was evidenced in waters using terephthalic acid as a probe, considering the photochemical instability of its specific hydroxylated derivative. Correlations were implemented using carbamazepine degradation rate, estimated hydroxyl radical formation and chemical contents of waters. In addition, laser flash photolysis studies confirmed •OH formation and allowed to evidence other reactive species, such as chloride (Cl2•-)/bromine (Br2•-) and carbonate (CO3•-) radicals in natural waters. Radicals mainly originate from dissolved phase and their occurrence and abundance depend on the type of water. Rate constants between reactive species and carbamazepine were determined by laser flash photolysis and competitive reactions experiments. Moreover, LC-QToF-MS analyses of by-products help us to propose mechanistic pathways. The results will bring insights to the fate of carbamazepine in various water types and could help to evaluate more precisely potential ecotoxicological effects.

Keywords: carbamazepine, kinetic and mechanistic approaches, natural waters, photodegradation

Procedia PDF Downloads 352
248 Use of Locomotor Activity of Rainbow Trout Juveniles in Identifying Sublethal Concentrations of Landfill Leachate

Authors: Tomas Makaras, Gintaras Svecevičius

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Landfill waste is a common problem as it has an economic and environmental impact even if it is closed. Landfill waste contains a high density of various persistent compounds such as heavy metals, organic and inorganic materials. As persistent compounds are slowly-degradable or even non-degradable in the environment, they often produce sublethal or even lethal effects on aquatic organisms. The aims of the present study were to estimate sublethal effects of the Kairiai landfill (WGS: 55°55‘46.74“, 23°23‘28.4“) leachate on the locomotor activity of rainbow trout Oncorhynchus mykiss juveniles using the original system package developed in our laboratory for automated monitoring, recording and analysis of aquatic organisms’ activity, and to determine patterns of fish behavioral response to sublethal effects of leachate. Four different concentrations of leachate were chosen: 0.125; 0.25; 0.5 and 1.0 mL/L (0.0025; 0.005; 0.01 and 0.002 as part of 96-hour LC50, respectively). Locomotor activity was measured after 5, 10 and 30 minutes of exposure during 1-minute test-periods of each fish (7 fish per treatment). The threshold-effect-concentration amounted to 0.18 mL/L (0.0036 parts of 96-hour LC50). This concentration was found to be even 2.8-fold lower than the concentration generally assumed to be “safe” for fish. At higher concentrations, the landfill leachate solution elicited behavioral response of test fish to sublethal levels of pollutants. The ability of the rainbow trout to detect and avoid contaminants occurred after 5 minutes of exposure. The intensity of locomotor activity reached a peak within 10 minutes, evidently decreasing after 30 minutes. This could be explained by the physiological and biochemical adaptation of fish to altered environmental conditions. It has been established that the locomotor activity of juvenile trout depends on leachate concentration and exposure duration. Modeling of these parameters showed that the activity of juveniles increased at higher leachate concentrations, but slightly decreased with the increasing exposure duration. Experiment results confirm that the behavior of rainbow trout juveniles is a sensitive and rapid biomarker that can be used in combination with the system for fish behavior monitoring, registration and analysis to determine sublethal concentrations of pollutants in ambient water. Further research should be focused on software improvement aimed to include more parameters of aquatic organisms’ behavior and to investigate the most rapid and appropriate behavioral responses in different species. In practice, this study could be the basis for the development and creation of biological early-warning systems (BEWS).

Keywords: fish behavior biomarker, landfill leachate, locomotor activity, rainbow trout juveniles, sublethal effects

Procedia PDF Downloads 250
247 Country Experience on Regulation of Traditional Medicine in Eritrea

Authors: Liya Abraham

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Eritrea is located along the Red Sea, north of the Horn of Africa, between Djibouti and Sudan and has a population of about 3.2 million as of 2010. It has six administrative regions; Anseba, Debub, Debubawi K’eyih Bahri, Gash-Barka, Ma'akel, and Semenawi K’eyih Bahri. Eritrea has got its independence in 1991 after 30 years war of liberation. The country is blessed with various medicinal flora and fauna, and marine and terrestrial biodiversity. Traditional Medicine (TM) has been an integral part of the Eritrean culture for centuries. So far, more than 19 TM modalities have been recognized, and are broadly categorized as; herbal, procedure-based and spiritual. Despite the availability of modern medicine to the majority of the population, TM is still widely practiced. The rationale behind widespread use is accessibility, affordability and cultural acceptability. Hence, TM is of great contribution to the Eritrean health care system. As a matter of fact, harnessing the potential contribution of effective and safe TM in order to attain Universal Health Coverage (UHC) has been emphasized in the WHO TM strategy 2014-2023. The Eritrean TM, however, was operating without regulation and reliable scientific justification behind its safety and efficacy. Thus, the Ministry of Health (MoH), in recognition of the role of TM in primary healthcare and safeguard public health, established a regulatory body for TM so-called as Traditional Medicine Unit (TMU) in 2012. The mission of the unit is to ensure rational TM use through an integrated health service delivery system and contribute to the country’s economic and social development. The unit has established its national TM policy in 2017. The activities of the unit are guided by the National TM Advisory Committee (TMAC), responsible for the provision of technical assistance and advisory role. Moreover, the Legal Framework and Code of Ethics and Practice which provide a legal basis for the regulation of TM have also been drafted. In recognition of the importance of TM research and development, the unit launched a nationwide TM survey in 2017 and had surveyed two zones (Gash-Barka and Debub). The findings of the survey were subjected to a research dissemination workshop and publication in international journals. Furthermore, TM-related adverse events reporting tool (Green Form) aiming to guide regulatory interventions and researches have been established by the unit, and ever since reports are flowing. The unit has also been offering training to THPs, pharmacy students and health care professionals regarding TM and its regulatory activities. In addition, as part of the establishment of the national medicinal plants' database and herbal monograph, more than 329 and 30 medicinal plants, have been compiled respectively. In conclusion, TM is still widely accepted and practiced in Eritrea. The TMU ever since its establishment is endeavoring to ensure the safety and efficacy of the TM, and its integration in the mainstream health service delivery system.

Keywords: efficacy, regulation, safety, traditional medicine, traditional medicine unit, universal health coverage

Procedia PDF Downloads 156
246 Mechanical Properties of Diamond Reinforced Ni Nanocomposite Coatings Made by Co-Electrodeposition with Glycine as Additive

Authors: Yanheng Zhang, Lu Feng, Yilan Kang, Donghui Fu, Qian Zhang, Qiu Li, Wei Qiu

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Diamond-reinforced Ni matrix composite has been widely applied in engineering for coating large-area structural parts owing to its high hardness, good wear resistance and corrosion resistance compared with those features of pure nickel. The mechanical properties of Ni-diamond composite coating can be promoted by the high incorporation and uniform distribution of diamond particles in the nickel matrix, while the distribution features of particles are affected by electrodeposition process parameters, especially the additives in the plating bath. Glycine has been utilized as an organic additive during the preparation of pure nickel coating, which can effectively increase the coating hardness. Nevertheless, to author’s best knowledge, no research about the effects of glycine on the Ni-diamond co-deposition has been reported. In this work, the diamond reinforced Ni nanocomposite coatings were fabricated by a co-electrodeposition technique from a modified Watt’s type bath in the presence of glycine. After preparation, the SEM morphology of the composite coatings was observed combined with energy dispersive X-ray spectrometer, and the diamond incorporation was analyzed. The surface morphology and roughness were obtained by a three-dimensional profile instrument. 3D-Debye rings formed by XRD were analyzed to characterize the nickel grain size and orientation in the coatings. The average coating thickness was measured by a digital micrometer to deduce the deposition rate. The microhardness was tested by automatic microhardness tester. The friction coefficient and wear volume were measured by reciprocating wear tester to characterize the coating wear resistance and cutting performance. The experimental results confirmed that the presence of glycine effectively improved the surface morphology and roughness of the composite coatings. By optimizing the glycine concentration, the incorporation of diamond particles was increased, while the nickel grain size decreased with increasing glycine. The hardness of the composite coatings was increased as the glycine concentration increased. The friction and wear properties were evaluated as the glycine concentration was optimized, showing a decrease in the wear volume. The wear resistance of the composite coatings increased as the glycine content was increased to an optimum value, beyond which the wear resistance decreased. Glycine complexation contributed to the nickel grain refinement and improved the diamond dispersion in the coatings, both of which made a positive contribution to the amount and uniformity of embedded diamond particles, thus enhancing the microhardness, reducing the friction coefficient, and hence increasing the wear resistance of the composite coatings. Therefore, additive glycine can be used during the co-deposition process to improve the mechanical properties of protective coatings.

Keywords: co-electrodeposition, glycine, mechanical properties, Ni-diamond nanocomposite coatings

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245 Garnet-based Bilayer Hybrid Solid Electrolyte for High-Voltage Cathode Material Modified with Composite Interface Enabler on Lithium-Metal Batteries

Authors: Kumlachew Zelalem Walle, Chun-Chen Yang

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Solid-state lithium metal batteries (SSLMBs) are considered promising candidates for next-generation energy storage devices due to their superior energy density and excellent safety. However, recent findings have shown that the formation of lithium (Li) dendrites in SSLMBs still exhibits a terrible growth ability, which makes the development of SSLMBs have to face the challenges posed by the Li dendrite problem. In this work, an inorganic/organic mixture coating material (g-C3N4/ZIF-8/PVDF) was used to modify the surface of lithium metal anode (LMA). Then the modified LMA (denoted as g-C₃N₄@Li) was assembled with lithium nafion (LiNf) coated commercial NCM811 (LiNf@NCM811) using a bilayer hybrid solid electrolyte (Bi-HSE) that incorporated 20 wt.% (vs. polymer) LiNf coated Li6.05Ga0.25La3Zr2O11.8F0.2 ([email protected]) filler faced to the positive electrode and the other layer with 80 wt.% (vs. polymer) filler content faced to the g-C₃N₄@Li. The garnet-type Li6.05Ga0.25La3Zr2O11.8F0.2 (LG0.25LZOF) solid electrolyte was prepared via co-precipitation reaction process from Taylor flow reactor and modified using lithium nafion (LiNf), a Li-ion conducting polymer. The Bi-HSE exhibited high ionic conductivity of 6.8  10–4 S cm–1 at room temperature, and a wide electrochemical window (0–5.0 V vs. Li/Li+). The coin cell was charged between 2.8 to 4.5 V at 0.2C and delivered an initial specific discharge capacity of 194.3 mAh g–1 and after 100 cycles it maintained 81.8% of its initial capacity at room temperature. The presence of a nano-sheet g-C3N4/ZIF-8/PVDF as a composite coating material on the LMA surface suppress the dendrite growth and enhance the compatibility as well as the interfacial contact between anode/electrolyte membrane. The g-C3N4@Li symmetrical cells incorporating this hybrid electrolyte possessed excellent interfacial stability over 1000 h at 0.1 mA cm–2 and a high critical current density (1 mA cm–2). Moreover, the in-situ formation of Li3N on the solid electrolyte interface (SEI) layer as depicted from the XPS result also improves the ionic conductivity and interface contact during the charge/discharge process. Therefore, these novel multi-layered fabrication strategies of hybrid/composite solid electrolyte membranes and modification of the LMA surface using mixed coating materials have potential applications in the preparation of highly safe high-voltage cathodes for SSLMBs.

Keywords: high-voltage cathodes, hybrid solid electrolytes, garnet, graphitic-carbon nitride (g-C3N4), ZIF-8 MOF

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244 Influence of a Cationic Membrane in a Double Compartment Filter-Press Reactor on the Atenolol Electro-Oxidation

Authors: Alan N. A. Heberle, Salatiel W. Da Silva, Valentin Perez-Herranz, Andrea M. Bernardes

Abstract:

Contaminants of emerging concern are substances widely used, such as pharmaceutical products. These compounds represent risk for both wild and human life since they are not completely removed from wastewater by conventional wastewater treatment plants. In the environment, they can be harm even in low concentration (µ or ng/L), causing bacterial resistance, endocrine disruption, cancer, among other harmful effects. One of the most common taken medicine to treat cardiocirculatory diseases is the Atenolol (ATL), a β-Blocker, which is toxic to aquatic life. In this way, it is necessary to implement a methodology, which is capable to promote the degradation of the ATL, to avoid the environmental detriment. A very promising technology is the advanced electrochemical oxidation (AEO), which mechanisms are based on the electrogeneration of reactive radicals (mediated oxidation) and/or on the direct substance discharge by electron transfer from contaminant to electrode surface (direct oxidation). The hydroxyl (HO•) and sulfate (SO₄•⁻) radicals can be generated, depending on the reactional medium. Besides that, at some condition, the peroxydisulfate (S₂O₈²⁻) ion is also generated from the SO₄• reaction in pairs. Both radicals, ion, and the direct contaminant discharge can break down the molecule, resulting in the degradation and/or mineralization. However, ATL molecule and byproducts can still remain in the treated solution. On this wise, some efforts can be done to implement the AEO process, being one of them the use of a cationic membrane to separate the cathodic (reduction) from the anodic (oxidation) reactor compartment. The aim of this study is investigate the influence of the implementation of a cationic membrane (Nafion®-117) to separate both cathodic and anodic, AEO reactor compartments. The studied reactor was a filter-press, with bath recirculation mode, flow 60 L/h. The anode was an Nb/BDD2500 and the cathode a stainless steel, both bidimensional, geometric surface area 100 cm². The solution feeding the anodic compartment was prepared with ATL 100 mg/L using Na₂SO₄ 4 g/L as support electrolyte. In the cathodic compartment, it was used a solution containing Na₂SO₄ 71 g/L. Between both solutions was placed the membrane. The applied currents densities (iₐₚₚ) of 5, 20 and 40 mA/cm² were studied over 240 minutes treatment time. Besides that, the ATL decay was analyzed by ultraviolet spectroscopy (UV/Vis). The mineralization was determined performing total organic carbon (TOC) in TOC-L CPH Shimadzu. In the cases without membrane, the iₐₚₚ 5, 20 and 40 mA/cm² resulted in 55, 87 and 98 % ATL degradation at the end of treatment time, respectively. However, with membrane, the degradation, for the same iₐₚₚ, was 90, 100 and 100 %, spending 240, 120, 40 min for the maximum degradation, respectively. The mineralization, without membrane, for the same studied iₐₚₚ, was 40, 55 and 72 %, respectively at 240 min, but with membrane, all tested iₐₚₚ reached 80 % of mineralization, differing only in the time spent, 240, 150 and 120 min, for the maximum mineralization, respectively. The membrane increased the ATL oxidation, probably due to avoid oxidant ions (S₂O₈²⁻) reduction on the cathode surface.

Keywords: contaminants of emerging concern, advanced electrochemical oxidation, atenolol, cationic membrane, double compartment reactor

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243 Application of a Submerged Anaerobic Osmotic Membrane Bioreactor Hybrid System for High-Strength Wastewater Treatment and Phosphorus Recovery

Authors: Ming-Yeh Lu, Shiao-Shing Chen, Saikat Sinha Ray, Hung-Te Hsu

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Recently, anaerobic membrane bioreactors (AnMBRs) has been widely utilized, which combines anaerobic biological treatment process and membrane filtration, that can be present an attractive option for wastewater treatment and water reuse. Conventional AnMBR is having several advantages, such as improving effluent quality, compact space usage, lower sludge yield, without aeration and production of energy. However, the removal of nitrogen and phosphorus in the AnMBR permeate was negligible which become the biggest disadvantage. In recent years, forward osmosis (FO) is an emerging technology that utilizes osmotic pressure as driving force to extract clean water without additional external pressure. The pore size of FO membrane is kindly mentioned the pore size, so nitrogen or phosphorus could effectively improve removal of nitrogen or phosphorus. Anaerobic bioreactor with FO membrane (AnOMBR) can retain the concentrate organic matters and nutrients. However, phosphorus is a non-renewable resource. Due to the high rejection property of FO membrane, the high amount of phosphorus could be recovered from the combination of AnMBR and FO. In this study, development of novel submerged anaerobic osmotic membrane bioreactor integrated with periodic microfiltration (MF) extraction for simultaneous phosphorus and clean water recovery from wastewater was evaluated. A laboratory-scale AnOMBR utilizes cellulose triacetate (CTA) membranes with effective membrane area of 130 cm² was fully submerged into a 5.5 L bioreactor at 30-35℃. Active layer-facing feed stream orientation was utilized, for minimizing fouling and scaling. Additionally, a peristaltic pump was used to circulate draw solution (DS) at a cross flow velocity of 0.7 cm/s. Magnesium sulphate (MgSO₄) solution was used as DS. Microfiltration membrane periodically extracted about 1 L solution when the TDS reaches to 5 g/L to recover phosphorus and simultaneous control the salt accumulation in the bioreactor. During experiment progressed, the average water flux was achieved around 1.6 LMH. The AnOMBR process show greater than 95% removal of soluble chemical oxygen demand (sCOD), nearly 100% of total phosphorous whereas only partial removal of ammonia, and finally average methane production of 0.22 L/g sCOD was obtained. Therefore, AnOMBR system periodically utilizes MF membrane extracted for phosphorus recovery with simultaneous pH adjustment. The overall performance demonstrates that a novel submerged AnOMBR system is having potential for simultaneous wastewater treatment and resource recovery from wastewater, and hence, the new concept of this system can be used to replace for conventional AnMBR in the future.

Keywords: anaerobic treatment, forward osmosis, phosphorus recovery, membrane bioreactor

Procedia PDF Downloads 243
242 Distribution, Source Apportionment and Assessment of Pollution Level of Trace Metals in Water and Sediment of a Riverine Wetland of the Brahmaputra Valley

Authors: Kali Prasad Sarma, Sanghita Dutta

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Deepor Beel (DB), the lone Ramsar site and an important wetland of the Brahmaputra valley in the state of Assam. The local people from fourteen peripheral villages traditionally utilize the wetland for harvesting vegetables, flowers, aquatic seeds, medicinal plants, fish, molluscs, fodder for domestic cattle etc. Therefore, it is of great importance to understand the concentration and distribution of trace metals in water-sediment system of the beel in order to protect its ecological environment. DB lies between26°05′26′′N to 26°09′26′′N latitudes and 90°36′39′′E to 91°41′25′′E longitudes. Water samples from the surface layer of water up to 40cm deep and sediment samples from the top 5cm layer of surface sediments were collected. The trace metals in waters and sediments were analysed using ICP-OES. The organic Carbon was analysed using the TOC analyser. The different mineral present in the sediments were confirmed by X-ray diffraction method (XRD). SEM images were recorded for the samples using SEM, attached with energy dispersive X-ray unit, with an accelerating voltage of 20 kv. All the statistical analyses were performed using SPSS20.0 for windows. In the present research, distribution, source apportionment, temporal and spatial variability, extent of pollution and the ecological risk of eight toxic trace metals in sediments and water of DB were investigated. The average concentrations of chromium(Cr) (both the seasons), copper(Cu) and lead(Pb) (pre-monsoon) and zinc(Zn) and cadmium(Cd) (post-monsoon) in sediments were higher than the consensus based threshold concentration(TEC). The persistent exposure of toxic trace metals in sediments pose a potential threat, especially to sediment dwelling organisms. The degree of pollution in DB sediments for Pb, Cobalt (Co) Zn, Cd, Cr, Cu and arsenic (As) was assessed using Enrichment Factor (EF), Geo-accumulation index (Igeo) and Pollution Load Index (PLI). The results indicated that contamination of surface sediments in DB is dominated by Pb and Cd and to a lesser extent by Co, Fe, Cu, Cr, As and Zn. A significant positive correlation among the pairs of element Co/Fe, Zn/As in water, and Cr/Zn, Fe/As in sediments indicates similar source of origin of these metals. The effects of interaction among trace metals between water and sediments shows significant variations (F =94.02, P < 0.001), suggesting maximum mobility of trace metals in DB sediments and water. The source apportionment of the heavy metals was carried out using Principal Component Analysis (PCA). SEM-EDS detects the presence of Cd, Cu, Cr, Zn, Pb, As and Fe in the sediment sample. The average concentration of Cd, Zn, Pb and As in the bed sediments of DB are found to be higher than the crustal abundance. The EF values indicate that Cd and Pb are significantly enriched. From source apportionment studies of the eight metals using PCA revealed that Cd was anthropogenic in origin; Pb, As, Cr, and Zn had mixed sources; whereas Co, Cu and Fe were natural in origin.

Keywords: Deepor Beel, enrichment factor, principal component analysis, trace metals

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241 Lesbians, Gays and Bisexuals of Botswana: Progressive Steps by the Botswana Court of Appeal towards Recognition and Advancement of Fundamental Human Rights of the Most Vulnerable within Society

Authors: Tashwill Esterhuizen

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Throughout Africa, several countries continue to have laws which criminalise same-sex sexual activities, which increases the vulnerability of the LGBT community to stigma, discrimination, and persecution. These criminal provisions often form the basis upon which states deny LGBT activists the right to freely associate with other like-minded individuals and form organizations that protect their interests and advocate for the rights and aspirations of the LGBT community. Over the past year, however, there has been significant progress in the advancement of universal, fundamental rights of LGBT persons throughout Africa. In many instances, these advancements came about through the bravery of activists who have publically insisted (in environments where same-sex sexual practices are criminalised) that their rights should be respected. Where meaningful engagement with the State was fruitless, activists took their plight to the judiciary and have successfully sought to uphold the fundamental rights of LGBT persons, paving the way for a more inclusive and tolerant society. Litigation Progress: Botswana is a prime example. For several years, the State denied a group of LGBT activists their right to freely associate and form their organisation Lesbians, Gays, and Bisexuals of Botswana (LEGABIBO), which aimed to promote the interests of the LGBT community in Botswana. In March 2016, the Botswana Court of Appeal found that the government’s refusal to register LEGABIBO violated the activists’ right to associate freely. The Court held that the right freedom of association applies to all persons regardless of their sexual orientation or gender identity. It does not matter that the views of the organisation are unpopular or unacceptable amongst the majority. In particular, the Court rejected the government of Botswana’s contention that registering LEGABIBO would disturb public peace and is contrary to public morality. Quite remarkably, the Court of Appeal recognised that while LGBT individuals are a minority group within the country, they are nonetheless persons entitled to constitutional protections of their dignity, regardless of whether they are unacceptable to others on religious or any other grounds. Furthermore, the Court held that human rights and fundamental freedoms are granted to all, including criminals or social outcasts because the denial of an individual’s humanity is the denial of their human dignity. This is crucial observation by the Court of Appeal, as once it is accepted that human rights apply to all human beings, then it becomes much easier for vulnerable groups to assert their own rights. Conclusion: The Botswana Court of Appeal decision, therefore, represents significant progress in the promotion of the rights of lesbian, gay, bisexual and transgender persons. The judgment has broader implications for many other countries which do not provide recognition of sexual minorities. It highlights the State’s duty to uphold basic rights and to ensure dignity, tolerance, and acceptance for marginalised persons.

Keywords: acceptance, freedom of association, freedom of expression, fundamental rights and freedoms, gender identity, human rights are universal, inclusive, inherent human dignity, progress, sexual orientation, tolerance

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240 Synthesis of Functionalized-2-Aryl-2, 3-Dihydroquinoline-4(1H)-Ones via Fries Rearrangement of Azetidin-2-Ones

Authors: Parvesh Singh, Vipan Kumar, Vishu Mehra

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Quinoline-4-ones represent an important class of heterocyclic scaffolds that have attracted significant interest due to their various biological and pharmacological activities. This heterocyclic unit also constitutes an integral component in drugs used for the treatment of neurodegenerative diseases, sleep disorders and in antibiotics viz. norfloxacin and ciprofloxacin. The synthetic accessibility and possibility of fictionalization at varied positions in quinoline-4-ones exemplifies an elegant platform for the designing of combinatorial libraries of functionally enriched scaffolds with a range of pharmacological profles. They are also considered to be attractive precursors for the synthesis of medicinally imperative molecules such as non-steroidal androgen receptor antagonists, antimalarial drug Chloroquine and martinellines with antibacterial activity. 2-Aryl-2,3-dihydroquinolin-4(1H)-ones are present in many natural and non-natural compounds and are considered to be the aza-analogs of favanones. The β-lactam class of antibiotics is generally recognized to be a cornerstone of human health care due to the unparalleled clinical efficacy and safety of this type of antibacterial compound. In addition to their biological relevance as potential antibiotics, β-lactams have also acquired a prominent place in organic chemistry as synthons and provide highly efficient routes to a variety of non-protein amino acids, such as oligopeptides, peptidomimetics, nitrogen-heterocycles, as well as biologically active natural and unnatural products of medicinal interest such as indolizidine alkaloids, paclitaxel, docetaxel, taxoids, cyptophycins, lankacidins, etc. A straight forward route toward the synthesis of quinoline-4-ones via the triflic acid assisted Fries rearrangement of N-aryl-βlactams has been reported by Tepe and co-workers. The ring expansion observed in this case was solely attributed to the inherent ring strain in β-lactam ring because -lactam failed to undergo rearrangement under reaction conditions. Theabovementioned protocol has been recently extended by our group for the synthesis of benzo[b]-azocinon-6-ones via a tandem Michael addition–Fries rearrangement of sorbyl anilides as well as for the single-pot synthesis of 2-aryl-quinolin-4(3H)-ones through the Fries rearrangement of 3-dienyl-βlactams. In continuation with our synthetic endeavours with the β-lactam ring and in view of the lack of convenient approaches for the synthesis of C-3 functionalized quinolin-4(1H)-ones, the present work describes the single-pot synthesis of C-3 functionalized quinolin-4(1H)-ones via the trific acid promoted Fries rearrangement of C-3 vinyl/isopropenyl substituted β-lactams. In addition, DFT calculations and MD simulations were performed to investigate the stability profles of synthetic compounds.

Keywords: dihydroquinoline, fries rearrangement, azetidin-2-ones, quinoline-4-ones

Procedia PDF Downloads 226