Search results for: transport of intensity equation
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Paper Count: 5340

Search results for: transport of intensity equation

150 Optimization of the Jatropha curcas Supply Chain as a Criteria for the Implementation of Future Collection Points in Rural Areas of Manabi-Ecuador

Authors: Boris G. German, Edward Jiménez, Sebastián Espinoza, Andrés G. Chico, Ricardo A. Narváez

Abstract:

The unique flora and fauna of The Galapagos Islands has leveraged a tourism-driven growth in the islands. Nonetheless, such development is energy-intensive and requires thousands of gallons of diesel each year for thermoelectric electricity generation. The needed transport of fossil fuels from the continent has generated oil spillages and affectations to the fragile ecosystem of the islands. The Zero Fossil Fuels initiative for The Galapagos proposed by the Ecuadorian government as an alternative to reduce the use of fossil fuels in the islands, considers the replacement of diesel in thermoelectric generators, by Jatropha curcas vegetable oil. However, the Jatropha oil supply cannot entirely cover yet the demand for electricity generation in Galapagos. Within this context, the present work aims to provide an optimization model that can be used as a selection criterion for approving new Jatropha Curcas collection points in rural areas of Manabi-Ecuador. For this purpose, existing Jatropha collection points in Manabi were grouped under three regions: north (7 collection points), center (4 collection points) and south (9 collection points). Field work was carried out in every region in order to characterize the collection points, to establish local Jatropha supply and to determine transportation costs. Data collection was complemented using GIS software and an objective function was defined in order to determine the profit associated to Jatropha oil production. The market price of both Jatropha oil and residual cake, were considered for the total revenue; whereas Jatropha price, transportation and oil extraction costs were considered for the total cost. The tonnes of Jatropha fruit and seed, transported from collection points to the extraction plant, were considered as variables. The maximum and minimum amount of the collected Jatropha from each region constrained the optimization problem. The supply chain was optimized using linear programming in order to maximize the profits. Finally, a sensitivity analysis was performed in order to find a profit-based criterion for the acceptance of future collection points in Manabi. The maximum profit reached a value of $ 4,616.93 per year, which represented a total Jatropha collection of 62.3 tonnes Jatropha per year. The northern region of Manabi had the biggest collection share (69%), followed by the southern region (17%). The criteria for accepting new Jatropha collection points in the rural areas of Manabi can be defined by the current maximum profit of the zone and by the variation in the profit when collection points are removed one at a time. The definition of new feasible collection points plays a key role in the supply chain associated to Jatropha oil production. Therefore, a mathematical model that assists decision makers in establishing new collection points while assuring profitability, contributes to guarantee a continued Jatropha oil supply for Galapagos and a sustained economic growth in the rural areas of Ecuador.

Keywords: collection points, Jatropha curcas, linear programming, supply chain

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149 Gis Based Flash Flood Runoff Simulation Model of Upper Teesta River Besin - Using Aster Dem and Meteorological Data

Authors: Abhisek Chakrabarty, Subhraprakash Mandal

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Flash flood is one of the catastrophic natural hazards in the mountainous region of India. The recent flood in the Mandakini River in Kedarnath (14-17th June, 2013) is a classic example of flash floods that devastated Uttarakhand by killing thousands of people.The disaster was an integrated effect of high intensityrainfall, sudden breach of Chorabari Lake and very steep topography. Every year in Himalayan Region flash flood occur due to intense rainfall over a short period of time, cloud burst, glacial lake outburst and collapse of artificial check dam that cause high flow of river water. In Sikkim-Derjeeling Himalaya one of the probable flash flood occurrence zone is Teesta Watershed. The Teesta River is a right tributary of the Brahmaputra with draining mountain area of approximately 8600 Sq. km. It originates in the Pauhunri massif (7127 m). The total length of the mountain section of the river amounts to 182 km. The Teesta is characterized by a complex hydrological regime. The river is fed not only by precipitation, but also by melting glaciers and snow as well as groundwater. The present study describes an attempt to model surface runoff in upper Teesta basin, which is directly related to catastrophic flood events, by creating a system based on GIS technology. The main object was to construct a direct unit hydrograph for an excess rainfall by estimating the stream flow response at the outlet of a watershed. Specifically, the methodology was based on the creation of a spatial database in GIS environment and on data editing. Moreover, rainfall time-series data collected from Indian Meteorological Department and they were processed in order to calculate flow time and the runoff volume. Apart from the meteorological data, background data such as topography, drainage network, land cover and geological data were also collected. Clipping the watershed from the entire area and the streamline generation for Teesta watershed were done and cross-sectional profiles plotted across the river at various locations from Aster DEM data using the ERDAS IMAGINE 9.0 and Arc GIS 10.0 software. The analysis of different hydraulic model to detect flash flood probability ware done using HEC-RAS, Flow-2D, HEC-HMS Software, which were of great importance in order to achieve the final result. With an input rainfall intensity above 400 mm per day for three days the flood runoff simulation models shows outbursts of lakes and check dam individually or in combination with run-off causing severe damage to the downstream settlements. Model output shows that 313 Sq. km area were found to be most vulnerable to flash flood includes Melli, Jourthang, Chungthang, and Lachung and 655sq. km. as moderately vulnerable includes Rangpo,Yathang, Dambung,Bardang, Singtam, Teesta Bazarand Thangu Valley. The model was validated by inserting the rain fall data of a flood event took place in August 1968, and 78% of the actual area flooded reflected in the output of the model. Lastly preventive and curative measures were suggested to reduce the losses by probable flash flood event.

Keywords: flash flood, GIS, runoff, simulation model, Teesta river basin

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148 Characterization of Carbazole-Based Host Material for Highly Efficient Thermally Activated Delayed Fluorescence Emitter

Authors: Malek Mahmoudi, Jonas Keruckas, Dmytro Volyniuk, Jurate Simokaitiene, Juozas V. Grazulevicius

Abstract:

Host materials have been discovered as one of the most appealing methods for harvesting triplet states in organic materials for application in organic light-emitting diodes (OLEDs). The ideal host-guest system for emission in thermally delayed fluorescence OLEDs with 20% guest concentration for efficient energy transfer has been demonstrated in the present investigation. In this work, 3,3'-bis[9-(4-fluorophenyl) carbazole] (bFPC) has been used as the host, which induces balanced charge carrier transport for high-efficiency OLEDs.For providing a complete characterization of the synthesized compound, photophysical, photoelectrical, charge-transporting, and electrochemical properties of the compound have been examined. Excited-state lifetimes and singlet-triplet energy gaps were measured for characterization of photophysical properties, while thermogravimetric analysis, as well as differential scanning calorimetry measurements, were performed for probing of electrochemical and thermal properties of the compound. The electrochemical properties of this compound were investigated by cyclic voltammetry (CV) method, and ionization potential (IPCV) value of 5.68 eV was observed. UV–Vis absorption and photoluminescence spectrum of a solution of the compound in toluene (10-5 M) showed maxima at 302 and 405 nm, respectively. Photoelectron emission spectrometry was used for the characterization of charge-injection properties of the studied compound in solid. The ionization potential of this material was found to be 5.78 eV, and time-of-flight measurement was used for testing charge-transporting properties and hole mobility estimated using this technique in a vacuum-deposited layer reached 4×10-4 cm2 V-1s-1. Since the compound with high charge mobilities was tested as a host in an organic light-emitting diode. The device was fabricated by successive deposition onto a pre-cleaned indium tin oxide (ITO) coated glass substrate under a vacuum of 10-6 Torr and consisting of an indium-tin-oxide anode, hole injection and transporting layer(MoO3, NPB), emitting layer with bFPC as a host and 4CzIPN (2,4,5,6-tetra(9-carbazolyl)isophthalonitrile) which is a new highly efficient green thermally activated delayed fluorescence (TADF) material as an emitter, an electron transporting layer(TPBi) and lithium fluoride layer topped with aluminum layer as a cathode exhibited the highest maximum current efficiency and power efficiency of 33.9 cd/A and 23.5 lm/W, respectively and the electroluminescence spectrum showed only a peak at 512nm. Furthermore, the new bicarbazole-based compound was tested as a host in thermally activated delayed fluorescence organic light-emitting diodes are reaching luminance of 25300 cd m-2 and external quantum efficiency of 10.1%. Interestingly, the turn-on voltage was low enough (3.8 V), and such a device can be used for highly efficient light sources.

Keywords: thermally-activated delayed fluorescence, host material, ionization energy, charge mobility, electroluminescence

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147 Assessing Measures and Caregiving Experiences of Thai Caregivers of Persons with Dementia

Authors: Piyaorn Wajanatinapart, Diane R. Lauver

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The number of persons with dementia (PWD) has increased. Informal caregivers are the major providing care. They can have perceived gains and burdens. Caregivers who reported high in perceived gains may report low in burdens and better health. Gaps of caregiving literature were: no report psychometrics in a few studies and unclear definitions of gains; most studies with no theory-guided and conducting in Western countries; not fully described relationships among caregiving variables: motivations, satisfaction with psychological needs, social support, gains, burdens, and physical and psycho-emotional health. Those gaps were filled by assessing psychometric properties of selected measures, providing clearly definitions of gains, using self-determination theory (SDT) to guide the study, and developing the study in Thailand. The study purposes were to evaluate six measures for internal consistency reliability, content validity, and construct validity. This study also examined relationships of caregiving variables: motivations (controlled and autonomous motivations), satisfaction with psychological needs (autonomy, competency, and relatedness), perceived social support, perceived gains, perceived burdens, and physical and psycho-emotional health. This study was a cross-sectional and correlational descriptive design with two convenience samples. Sample 1 was five Thai experts to assess content validity of measures. Sample 2 was 146 Thai caregivers of PWD to assess construct validity, reliability, and relationships among caregiving variables. Experts rated questionnaires and sent them back via e-mail. Caregivers answered questionnaires at clinics of four Thai hospitals. Data analysis was used descriptive statistics and bivariate and multivariate analyses using the composite indicator structural equation model to control measurement errors. For study results, most caregivers were female (82%), middle age (M =51.1, SD =11.9), and daughters (57%). They provided care for 15 hours/day with 4.6 years. The content validity indices of items and scales were .80 or higher for clarity and relevance. Experts suggested item revisions. Cronbach’s alphas were .63 to .93 of ten subscales of four measures and .26 to .57 of three subscales. The gain scale was acceptable for construct validity. With controlling covariates, controlled motivations, the satisfaction with three subscales of psychological needs, and perceived social support had positive relationships with physical and psycho-emotional health. Both satisfaction with autonomy subscale and perceived social support had negative relationship with perceived burdens. The satisfaction with three subscales of psychological needs had positive relationships among them. Physical and psycho-emotional health subscales had positive relationships with each other. Furthermore, perceived burdens had negative relationships with physical and psycho-emotional health. This study was the first use SDT to describe relationships of caregiving variables in Thailand. Caregivers’ characteristics were consistent with literature. Four measures were valid and reliable except two measures. Breadth knowledge about relationships was provided. Interpretation of study results was cautious because of using same sample to evaluate psychometric properties of measures and relationships of caregiving variables. Researchers could use four measures for further caregiving studies. Using a theory would help describe concepts, propositions, and measures used. Researchers may examine the satisfaction with psychological needs as mediators. Future studies to collect data with caregivers in communities are needed.

Keywords: caregivers, caregiving, dementia, measures

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146 Accounting and Prudential Standards of Banks and Insurance Companies in EU: What Stakes for Long Term Investment?

Authors: Sandra Rigot, Samira Demaria, Frederic Lemaire

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The starting point of this research is the contemporary capitalist paradox: there is a real scarcity of long term investment despite the boom of potential long term investors. This gap represents a major challenge: there are important needs for long term financing in developed and emerging countries in strategic sectors such as energy, transport infrastructure, information and communication networks. Moreover, the recent financial and sovereign debt crises, which have respectively reduced the ability of financial banking intermediaries and governments to provide long term financing, questions the identity of the actors able to provide long term financing, their methods of financing and the most appropriate forms of intermediation. The issue of long term financing is deemed to be very important by the EU Commission, as it issued a 2013 Green Paper (GP) on long-term financing of the EU economy. Among other topics, the paper discusses the impact of the recent regulatory reforms on long-term investment, both in terms of accounting (in particular fair value) and prudential standards for banks. For banks, prudential and accounting standards are also crucial. Fair value is indeed well adapted to the trading book in a short term view, but this method hardly suits for a medium and long term portfolio. Banks’ ability to finance the economy and long term projects depends on their ability to distribute credit and the way credit is valued (fair value or amortised cost) leads to different banking strategies. Furthermore, in the banking industry, accounting standards are directly connected to the prudential standards, as the regulatory requirements of Basel III use accounting figures with prudential filter to define the needs for capital and to compute regulatory ratios. The objective of these regulatory requirements is to prevent insolvency and financial instability. In the same time, they can represent regulatory constraints to long term investing. The balance between financial stability and the need to stimulate long term financing is a key question raised by the EU GP. Does fair value accounting contributes to short-termism in the investment behaviour? Should prudential rules be “appropriately calibrated” and “progressively implemented” not to prevent banks from providing long-term financing? These issues raised by the EU GP lead us to question to what extent the main regulatory requirements incite or constrain banks to finance long term projects. To that purpose, we study the 292 responses received by the EU Commission during the public consultation. We analyze these contributions focusing on particular questions related to fair value accounting and prudential norms. We conduct a two stage content analysis of the responses. First, we proceed to a qualitative coding to identify arguments of respondents and subsequently we run a quantitative coding in order to conduct statistical analyses. This paper provides a better understanding of the position that a large panel of European stakeholders have on these issues. Moreover, it adds to the debate on fair value accounting and its effects on prudential requirements for banks. This analysis allows us to identify some short term bias in banking regulation.

Keywords: basel 3, fair value, securitization, long term investment, banks, insurers

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145 Global Evidence on the Seasonality of Enteric Infections, Malnutrition, and Livestock Ownership

Authors: Aishwarya Venkat, Anastasia Marshak, Ryan B. Simpson, Elena N. Naumova

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Livestock ownership is simultaneously linked to improved nutritional status through increased availability of animal-source protein, and increased risk of enteric infections through higher exposure to contaminated water sources. Agrarian and agro-pastoral households, especially those with cattle, goats, and sheep, are highly dependent on seasonally various environmental conditions, which directly impact nutrition and health. This study explores global spatiotemporally explicit evidence regarding the relationship between livestock ownership, enteric infections, and malnutrition. Seasonal and cyclical fluctuations, as well as mediating effects, are further examined to elucidate health and nutrition outcomes of individual and communal livestock ownership. The US Agency for International Development’s Demographic and Health Surveys (DHS) and the United Nations International Children's Emergency Fund’s Multi-Indicator Cluster Surveys (MICS) provide valuable sources of household-level information on anthropometry, asset ownership, and disease outcomes. These data are especially important in data-sparse regions, where surveys may only be conducted in the aftermath of emergencies. Child-level disease history, anthropometry, and household-level asset ownership information have been collected since DHS-V (2003-present) and MICS-III (2005-present). This analysis combines over 15 years of survey data from DHS and MICS to study 2,466,257 children under age five from 82 countries. Subnational (administrative level 1) measures of diarrhea prevalence, mean livestock ownership by type, mean and median anthropometric measures (height for age, weight for age, and weight for height) were investigated. Effects of several environmental, market, community, and household-level determinants were studied. Such covariates included precipitation, temperature, vegetation, the market price of staple cereals and animal source proteins, conflict events, livelihood zones, wealth indices and access to water, sanitation, hygiene, and public health services. Children aged 0 – 6 months, 6 months – 2 years, and 2 – 5 years of age were compared separately. All observations were standardized to interview day of year, and administrative units were harmonized for consistent comparisons over time. Geographically weighted regressions were constructed for each outcome and subnational unit. Preliminary results demonstrate the importance of accounting for seasonality in concurrent assessments of malnutrition and enteric infections. Household assets, including livestock, often determine the intensity of these outcomes. In many regions, livestock ownership affects seasonal fluxes in malnutrition and enteric infections, which are also directly affected by environmental and local factors. Regression analysis demonstrates the spatiotemporal variability in nutrition outcomes due to a variety of causal factors. This analysis presents a synthesis of evidence from global survey data on the interrelationship between enteric infections, malnutrition, and livestock. These results provide a starting point for locally appropriate interventions designed to address this nexus in a timely manner and simultaneously improve health, nutrition, and livelihoods.

Keywords: diarrhea, enteric infections, households, livestock, malnutrition, seasonality

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144 Thermal Energy Storage Based on Molten Salts Containing Nano-Particles: Dispersion Stability and Thermal Conductivity Using Multi-Scale Computational Modelling

Authors: Bashar Mahmoud, Lee Mortimer, Michael Fairweather

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New methods have recently been introduced to improve the thermal property values of molten nitrate salts (a binary mixture of NaNO3:KNO3in 60:40 wt. %), by doping them with minute concentration of nanoparticles in the range of 0.5 to 1.5 wt. % to form the so-called: Nano-heat-transfer-fluid, apt for thermal energy transfer and storage applications. The present study aims to assess the stability of these nanofluids using the advanced computational modelling technique, Lagrangian particle tracking. A multi-phase solid-liquid model is used, where the motion of embedded nanoparticles in the suspended fluid is treated by an Euler-Lagrange hybrid scheme with fixed time stepping. This technique enables measurements of various multi-scale forces whose characteristic (length and timescales) are quite different. Two systems are considered, both consisting of 50 nm Al2O3 ceramic nanoparticles suspended in fluids of different density ratios. This includes both water (5 to 95 °C) and molten nitrate salt (220 to 500 °C) at various volume fractions ranging between 1% to 5%. Dynamic properties of both phases are coupled to the ambient temperature of the fluid suspension. The three-dimensional computational region consists of a 1μm cube and particles are homogeneously distributed across the domain. Periodic boundary conditions are enforced. The particle equations of motion are integrated using the fourth order Runge-Kutta algorithm with a very small time-step, Δts, set at 10-11 s. The implemented technique demonstrates the key dynamics of aggregated nanoparticles and this involves: Brownian motion, soft-sphere particle-particle collisions, and Derjaguin, Landau, Vervey, and Overbeek (DLVO) forces. These mechanisms are responsible for the predictive model of aggregation of nano-suspensions. An energy transport-based method of predicting the thermal conductivity of the nanofluids is also used to determine thermal properties of the suspension. The simulation results confirms the effectiveness of the technique. The values are in excellent agreement with the theoretical and experimental data obtained from similar studies. The predictions indicates the role of Brownian motion and DLVO force (represented by both the repulsive electric double layer and an attractive Van der Waals) and its influence in the level of nanoparticles agglomeration. As to the nano-aggregates formed that was found to play a key role in governing the thermal behavior of nanofluids at various particle concentration. The presentation will include a quantitative assessment of these forces and mechanisms, which would lead to conclusions about nanofluids, heat transfer performance and thermal characteristics and its potential application in solar thermal energy plants.

Keywords: thermal energy storage, molten salt, nano-fluids, multi-scale computational modelling

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143 Safety Considerations of Furanics for Sustainable Applications in Advanced Biorefineries

Authors: Anitha Muralidhara, Victor Engelen, Christophe Len, Pascal Pandard, Guy Marlair

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Production of bio-based chemicals and materials from lignocellulosic biomass is gaining tremendous importance in advanced bio-refineries while aiming towards progressive replacement of petroleum based chemicals in transportation fuels and commodity polymers. One such attempt has resulted in the production of key furan derivatives (FD) such as furfural, HMF, MMF etc., via acid catalyzed dehydration (ACD) of C6 and C5 sugars, which are further converted into key chemicals or intermediates (such as Furandicarboxylic acid, Furfuryl alcohol etc.,). In subsequent processes, many high potential FD are produced, that can be converted into high added value polymers or high energy density biofuels. During ACD, an unavoidable polyfuranic byproduct is generated which is called humins. The family of FD is very large with varying chemical structures and diverse physicochemical properties. Accordingly, the associated risk profiles may largely vary. Hazardous Material (Haz-mat) classification systems such as GHS (CLP in the EU) and the UN TDG Model Regulations for transport of dangerous goods are one of the preliminary requirements for all chemicals for their appropriate classification, labelling, packaging, safe storage, and transportation. Considering the growing application routes of FD, it becomes important to notice the limited access to safety related information (safety data sheets available only for famous compounds such as HMF, furfural etc.,) in these internationally recognized haz-mat classification systems. However, these classifications do not necessarily provide information about the extent of risk involved when the chemical is used in any specific application. Factors such as thermal stability, speed of combustion, chemical incompatibilities, etc., can equally influence the safety profile of a compound, that are clearly out of the scope of any haz-mat classification system. Irrespective of the bio-based origin, FD has so far received inconsistent remarks concerning their toxicity profiles. With such inconsistencies, there is a fear that, a large family of FD may also follow extreme judgmental scenarios like ionic liquids, by ranking some compounds as extremely thermally stable, non-flammable, etc., Unless clarified, these messages could lead to misleading judgements while ranking the chemical based on its hazard rating. Safety is a key aspect in any sustainable biorefinery operation/facility, which is often underscored or neglected. To fill up these existing data gaps and to address ambiguities and discrepancies, the current study focuses on giving preliminary insights on safety assessment of FD and their potential targeted by-products. With the available information in the literature and obtained experimental results, physicochemical safety, environmental safety as well as (a scenario based) fire safety profiles of key FD, as well as side streams such as humins and levulinic acid, will be considered. With this, the study focuses on defining patterns and trends that gives coherent safety related information for existing and newly synthesized FD in the market for better functionality and sustainable applications.

Keywords: furanics, humins, safety, thermal and fire hazard, toxicity

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142 Factors Affecting Early Antibiotic Delivery in Open Tibial Shaft Fractures

Authors: William Elnemer, Nauman Hussain, Samir Al-Ali, Henry Shu, Diane Ghanem, Babar Shafiq

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Introduction: The incidence of infection in open tibial shaft injuries varies depending on the severity of the injury, with rates ranging from 1.8% for Gustilo-Anderson type I to 42.9% for type IIIB fractures. The timely administration of antibiotics upon presentation to the emergency department (ED) is an essential component of fracture management, and evidence indicates that prompt delivery of antibiotics is associated with improved outcomes. The objective of this study is to identify factors that contribute to the expedient administration of antibiotics. Methods: This is a retrospective study of open tibial shaft fractures at an academic Level I trauma center. Current Procedural Terminology (CPT) codes identified all patients treated for open tibial shaft fractures between 2015 and 2021. Open fractures were identified by reviewing ED and provider notes, and with ballistic fractures were considered open. Chart reviews were performed to extract demographics, fracture characteristics, postoperative outcomes, time to operative room, time to antibiotic order, and delivery. Univariate statistical analysis compared patients who received early antibiotics (EA), which were delivered within one hour of ED presentation, and those who received late antibiotics (LA), which were delivered outside of one hour of ED presentation. A multivariate analysis was performed to investigate patient, fracture, and transport/ED characteristics contributing to faster delivery of antibiotics. The multivariate analysis included the dependent variables: ballistic fracture, activation of Delta Trauma, Gustilo-Andersen (Type III vs. Type I and II), AO-OTA Classification (Type C vs. Type A and B), arrival between 7 am and 11 pm, and arrival via Emergency Medical Services (EMS) or walk-in. Results: Seventy ED patients with open tibial shaft fractures were identified. Of these, 39 patients (55.7%) received EA, while 31 patients (44.3%) received LA. Univariate analysis shows that the arrival via EMS as opposed to walk-in (97.4% vs. 74.2%, respectively, p = 0.01) and activation of Delta Trauma (89.7% vs. 51.6%, respectively, p < 0.001) was significantly higher in the EA group vs. the LA group. Additionally, EA cases had significantly shorter intervals between the antibiotic order and delivery when compared to LA cases (0.02 hours vs. 0.35 hours, p = 0.007). No other significant differences were found in terms of postoperative outcomes or fracture characteristics. Multivariate analysis shows that a Delta Trauma Response, arrival via EMS, and presentation between 7 am and 11 pm were independent predictors of a shorter time to antibiotic administration (Odds Ratio = 11.9, 30.7, and 5.4, p = 0.001, 0.016, and 0.013, respectively). Discussion: Earlier antibiotic delivery is associated with arrival to the ED between 7 am and 11 pm, arrival via EMS, and a coordinated Delta Trauma activation. Our findings indicate that in cases where administering antibiotics is critical to achieving positive outcomes, it is advisable to employ a coordinated Delta Trauma response. Hospital personnel should be attentive to the rapid administration of antibiotics to patients with open fractures who arrive via walk-in or during late-night hours.

Keywords: antibiotics, emergency department, fracture management, open tibial shaft fractures, orthopaedic surgery, time to or, trauma fractures

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141 Ammonia Cracking: Catalysts and Process Configurations for Enhanced Performance

Authors: Frea Van Steenweghen, Lander Hollevoet, Johan A. Martens

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Compared to other hydrogen (H₂) carriers, ammonia (NH₃) is one of the most promising carriers as it contains 17.6 wt% hydrogen. It is easily liquefied at ≈ 9–10 bar pressure at ambient temperature. More importantly, NH₃ is a carbon-free hydrogen carrier with no CO₂ emission at final decomposition. Ammonia has a well-defined regulatory framework and a good track record regarding safety concerns. Furthermore, the industry already has an existing transport infrastructure consisting of pipelines, tank trucks and shipping technology, as ammonia has been manufactured and distributed around the world for over a century. While NH₃ synthesis and transportation technological solutions are at hand, a missing link in the hydrogen delivery scheme from ammonia is an energy-lean and efficient technology for cracking ammonia into H₂ and N₂. The most explored option for ammonia decomposition is thermo-catalytic cracking which is, by itself, the most energy-efficient approach compared to other technologies, such as plasma and electrolysis, as it is the most energy-lean and robust option. The decomposition reaction is favoured only at high temperatures (> 300°C) and low pressures (1 bar) as the thermocatalytic ammonia cracking process is faced with thermodynamic limitations. At 350°C, the thermodynamic equilibrium at 1 bar pressure limits the conversion to 99%. Gaining additional conversion up to e.g. 99.9% necessitates heating to ca. 530°C. However, reaching thermodynamic equilibrium is infeasible as a sufficient driving force is needed, requiring even higher temperatures. Limiting the conversion below the equilibrium composition is a more economical option. Thermocatalytic ammonia cracking is documented in scientific literature. Among the investigated metal catalysts (Ru, Co, Ni, Fe, …), ruthenium is known to be most active for ammonia decomposition with an onset of cracking activity around 350°C. For establishing > 99% conversion reaction, temperatures close to 600°C are required. Such high temperatures are likely to reduce the round-trip efficiency but also the catalyst lifetime because of the sintering of the supported metal phase. In this research, the first focus was on catalyst bed design, avoiding diffusion limitation. Experiments in our packed bed tubular reactor set-up showed that extragranular diffusion limitations occur at low concentrations of NH₃ when reaching high conversion, a phenomenon often overlooked in experimental work. A second focus was thermocatalyst development for ammonia cracking, avoiding the use of noble metals. To this aim, candidate metals and mixtures were deposited on a range of supports. Sintering resistance at high temperatures and the basicity of the support were found to be crucial catalyst properties. The catalytic activity was promoted by adding alkaline and alkaline earth metals. A third focus was studying the optimum process configuration by process simulations. A trade-off between conversion and favorable operational conditions (i.e. low pressure and high temperature) may lead to different process configurations, each with its own pros and cons. For example, high-pressure cracking would eliminate the need for post-compression but is detrimental for the thermodynamic equilibrium, leading to an optimum in cracking pressure in terms of energy cost.

Keywords: ammonia cracking, catalyst research, kinetics, process simulation, thermodynamic equilibrium

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140 Strategy of Loading by Number for Commercial Vehicles

Authors: Ramalan Musa Yerima

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The paper titled “Loading by number” explained a strategy developed recently by the Zonal Commanding Officer of the Federal Road Safety Corps of Nigeria, covering Sokoto, Kebbi and Zamfara States of Northern Nigeria. The strategy is aimed at reducing competition, which will invariably lead to a reduction in speed, reduction in dangerous driving, reduction in crash rate, reduction in injuries, reduction in property damages and reduction in death through road traffic crashes (RTC). This research paper presents a study focused on enhancing the safety of commercial vehicles. The background of this study highlights the alarming statistics related to commercial vehicle crashes in Nigeria with a focus on Sokoto, Kebbi and Zamfara States, which often result in significant damage to property, loss of lives, and economic costs. The significance and aims is to investigate and propose an effective strategy to enhance the safety of commercial vehicles. The study recognizes the pressing need for heightened safety measures in commercial transportation, as it impacts not only the well-being of drivers and passengers but also the overall public safety. To achieve the objectives, an examination of accident data, including causes and contributing factors, was performed to identify critical areas for improvement. The major finding of the study reveals that when competition comes into play within the realm of commercial driving, it has detrimental effects on road safety and resource management. Commercial drivers are pushed to complete their routes quickly and deliver goods on time, or they push themselves to arrive quickly for more passengers and new contracts. This competitive environment, fuelled by internal and external pressures such as tight deadlines, poverty and greed, often leads to sad endings. The study recommends that if a strategy called loading by number is integrated with other multiple safety measures, such as driver training programs, regulatory enforcement, and infrastructure improvements, commercial vehicle safety can be significantly enhanced. "Loading by Number” approach is designed to ensure that the sequence of departure of drivers from the motor park ‘A’ would be communicated to motor park officials of park ‘B’, which would be considered sequentially when giving them returning passengers, regardless of the first to arrive. In conclusion, this paper underscores the significance of improving the safety measures of commercial vehicles, as they are often larger and heavier than other vehicles on the road. Whenever they are involved in accidents, the consequences can be more severe. Commercial vehicles are also frequently involved in long-haul or interstate transportation, which means they cover longer distances and spend more time on the road. This increased exposure to driving conditions increases the probability of accidents occurring. By implementing the suggested measures, policymakers, transportation authorities, and industry stakeholders can work collectively toward ensuring a safer commercial transportation system.

Keywords: commercial, safety, strategy, transport

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139 Polar Bears in Antarctica: An Analysis of Treaty Barriers

Authors: Madison Hall

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The Assisted Colonization of Polar Bears to Antarctica requires a careful analysis of treaties to understand existing legal barriers to Ursus maritimus transport and movement. An absence of land-based migration routes prevent polar bears from accessing southern polar regions on their own. This lack of access is compounded by current treaties which limit human intervention and assistance to ford these physical and legal barriers. In a time of massive planetary extinctions, Assisted Colonization posits that certain endangered species may be prime candidates for relocation to hospitable environments to which they have never previously had access. By analyzing existing treaties, this paper will examine how polar bears are limited in movement by humankind’s legal barriers. International treaties may be considered codified reflections of anthropocentric values of the best knowledge and understanding of an identified problem at a set point in time, as understood through the human lens. Even as human social values and scientific insights evolve, so too must treaties evolve which specify legal frameworks and structures impacting keystone species and related biomes. Due to costs and other myriad difficulties, only a very select number of species will be given this opportunity. While some species move into new regions and are then deemed invasive, Assisted Colonization considers that some assistance may be mandated due to the nature of humankind’s role in climate change. This moral question and ethical imperative against the backdrop of escalating climate impacts, drives the question forward; what is the potential for successfully relocating a select handful of charismatic and ecologically important life forms? Is it possible to reimagine a different, but balanced Antarctic ecosystem? Listed as a threatened species under the U.S. Endangered Species Act, a result of the ongoing loss of critical habitat by melting sea ice, polar bears have limited options for long term survival in the wild. Our current regime for safeguarding animals facing extinction frequently utilizes zoos and their breeding programs, to keep alive the genetic diversity of the species until some future time when reintroduction, somewhere, may be attempted. By exploring the potential for polar bears to be relocated to Antarctica, we must analyze the complex ethical, legal, political, financial, and biological realms, which are the backdrop to framing all questions in this arena. Can we do it? Should we do it? By utilizing an environmental ethics perspective, we propose that the Ecological Commons of the Arctic and Antarctic should not be viewed solely through the lens of human resource management needs. From this perspective, polar bears do not need our permission, they need our assistance. Antarctica therefore represents a second, if imperfect chance, to buy time for polar bears, in a world where polar regimes, not yet fully understood, are themselves quickly changing as a result of climate change.

Keywords: polar bear, climate change, environmental ethics, Arctic, Antarctica, assisted colonization, treaty

Procedia PDF Downloads 386
138 Development of Alternative Fuels Technologies for Transportation

Authors: Szymon Kuczynski, Krystian Liszka, Mariusz Laciak, Andrii Oliinyk, Adam Szurlej

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Currently, in automotive transport to power vehicles, almost exclusively hydrocarbon based fuels are used. Due to increase of hydrocarbon fuels consumption, quality parameters are tightend for clean environment. At the same time efforts are undertaken for development of alternative fuels. The reasons why looking for alternative fuels for petroleum and diesel are: to increase vehicle efficiency and to reduce the environmental impact, reduction of greenhouse gases emissions and savings in consumption of limited oil resources. Significant progress was performed on development of alternative fuels such as methanol, ethanol, natural gas (CNG / LNG), LPG, dimethyl ether (DME) and biodiesel. In addition, biggest vehicle manufacturers work on fuel cell vehicles and its introduction to the market. Alcohols such as methanol and ethanol create the perfect fuel for spark-ignition engines. Their advantages are high-value antiknock which determines their application as additive (10%) to unleaded petrol and relative purity of produced exhaust gasses. Ethanol is produced in distillation process of plant products, which value as a food can be irrational. Ethanol production can be costly also for the entire economy of the country, because it requires a large complex distillation plants, large amounts of biomass and finally a significant amount of fuel to sustain the process. At the same time, the fermentation process of plants releases into the atmosphere large quantities of carbon dioxide. Natural gas cannot be directly converted into liquid fuels, although such arrangements have been proposed in the literature. Going through stage of intermediates is inevitable yet. Most popular one is conversion to methanol, which can be processed further to dimethyl ether (DME) or olefin (ethylene and propylene) for the petrochemical sector. Methanol uses natural gas as a raw material, however, requires expensive and advanced production processes. In relation to pollution emissions, the optimal vehicle fuel is LPG which is used in many countries as an engine fuel. Production of LPG is inextricably linked with production and processing of oil and gas, and which represents a small percentage. Its potential as an alternative for traditional fuels is therefore proportionately reduced. Excellent engine fuel may be biogas, however, follows to the same limitations as ethanol - the same production process is used and raw materials. Most essential fuel in the campaign of environment protection against pollution is natural gas. Natural gas as fuel may be either compressed (CNG) or liquefied (LNG). Natural gas can also be used for hydrogen production in steam reforming. Hydrogen can be used as a basic starting material for the chemical industry, an important raw material in the refinery processes, as well as a fuel vehicle transportation. Natural gas can be used as CNG which represents an excellent compromise between the availability of the technology that is proven and relatively cheap to use in many areas of the automotive industry. Natural gas can also be seen as an important bridge to other alternative sources of energy derived from fuel and harmless to the environment. For these reasons CNG as a fuel stimulates considerable interest in the worldwide.

Keywords: alternative fuels, CNG (Compressed Natural Gas), LNG (Liquefied Natural Gas), NGVs (Natural Gas Vehicles)

Procedia PDF Downloads 157
137 Heat Transfer Modeling of 'Carabao' Mango (Mangifera indica L.) during Postharvest Hot Water Treatments

Authors: Hazel James P. Agngarayngay, Arnold R. Elepaño

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Mango is the third most important export fruit in the Philippines. Despite the expanding mango trade in world market, problems on postharvest losses caused by pests and diseases are still prevalent. Many disease control and pest disinfestation methods have been studied and adopted. Heat treatment is necessary to eliminate pests and diseases to be able to pass the quarantine requirements of importing countries. During heat treatments, temperature and time are critical because fruits can easily be damaged by over-exposure to heat. Modeling the process enables researchers and engineers to study the behaviour of temperature distribution within the fruit over time. Understanding physical processes through modeling and simulation also saves time and resources because of reduced experimentation. This research aimed to simulate the heat transfer mechanism and predict the temperature distribution in ‘Carabao' mangoes during hot water treatment (HWT) and extended hot water treatment (EHWT). The simulation was performed in ANSYS CFD Software, using ANSYS CFX Solver. The simulation process involved model creation, mesh generation, defining the physics of the model, solving the problem, and visualizing the results. Boundary conditions consisted of the convective heat transfer coefficient and a constant free stream temperature. The three-dimensional energy equation for transient conditions was numerically solved to obtain heat flux and transient temperature values. The solver utilized finite volume method of discretization. To validate the simulation, actual data were obtained through experiment. The goodness of fit was evaluated using mean temperature difference (MTD). Also, t-test was used to detect significant differences between the data sets. Results showed that the simulations were able to estimate temperatures accurately with MTD of 0.50 and 0.69 °C for the HWT and EHWT, respectively. This indicates good agreement between the simulated and actual temperature values. The data included in the analysis were taken at different locations of probe punctures within the fruit. Moreover, t-tests showed no significant differences between the two data sets. Maximum heat fluxes obtained at the beginning of the treatments were 394.15 and 262.77 J.s-1 for HWT and EHWT, respectively. These values decreased abruptly at the first 10 seconds and gradual decrease was observed thereafter. Data on heat flux is necessary in the design of heaters. If underestimated, the heating component of a certain machine will not be able to provide enough heat required by certain operations. Otherwise, over-estimation will result in wasting of energy and resources. This study demonstrated that the simulation was able to estimate temperatures accurately. Thus, it can be used to evaluate the influence of various treatment conditions on the temperature-time history in mangoes. When combined with information on insect mortality and quality degradation kinetics, it could predict the efficacy of a particular treatment and guide appropriate selection of treatment conditions. The effect of various parameters on heat transfer rates, such as the boundary and initial conditions as well as the thermal properties of the material, can be systematically studied without performing experiments. Furthermore, the use of ANSYS software in modeling and simulation can be explored in modeling various systems and processes.

Keywords: heat transfer, heat treatment, mango, modeling and simulation

Procedia PDF Downloads 229
136 Thermoluminescence Investigations of Tl2Ga2Se3S Layered Single Crystals

Authors: Serdar Delice, Mehmet Isik, Nizami Hasanli, Kadir Goksen

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Researchers have donated great interest to ternary and quaternary semiconductor compounds especially with the improvement of the optoelectronic technology. The quaternary compound Tl2Ga2Se3S which was grown by Bridgman method carries the properties of ternary thallium chalcogenides group of semiconductors with layered structure. This compound can be formed from TlGaSe2 crystals replacing the one quarter of selenium atom by sulfur atom. Although Tl2Ga2Se3S crystals are not intentionally doped, some unintended defect types such as point defects, dislocations and stacking faults can occur during growth processes of crystals. These defects can cause undesirable problems in semiconductor materials especially produced for optoelectronic technology. Defects of various types in the semiconductor devices like LEDs and field effect transistor may act as a non-radiative or scattering center in electron transport. Also, quick recombination of holes with electrons without any energy transfer between charge carriers can occur due to the existence of defects. Therefore, the characterization of defects may help the researchers working in this field to produce high quality devices. Thermoluminescence (TL) is an effective experimental method to determine the kinetic parameters of trap centers due to defects in crystals. In this method, the sample is illuminated at low temperature by a light whose energy is bigger than the band gap of studied sample. Thus, charge carriers in the valence band are excited to delocalized band. Then, the charge carriers excited into conduction band are trapped. The trapped charge carriers are released by heating the sample gradually and these carriers then recombine with the opposite carriers at the recombination center. By this way, some luminescence is emitted from the samples. The emitted luminescence is converted to pulses by using an experimental setup controlled by computer program and TL spectrum is obtained. Defect characterization of Tl2Ga2Se3S single crystals has been performed by TL measurements at low temperatures between 10 and 300 K with various heating rate ranging from 0.6 to 1.0 K/s. The TL signal due to the luminescence from trap centers revealed one glow peak having maximum temperature of 36 K. Curve fitting and various heating rate methods were used for the analysis of the glow curve. The activation energy of 13 meV was found by the application of curve fitting method. This practical method established also that the trap center exhibits the characteristics of mixed (general) kinetic order. In addition, various heating rate analysis gave a compatible result (13 meV) with curve fitting as the temperature lag effect was taken into consideration. Since the studied crystals were not intentionally doped, these centers are thought to originate from stacking faults, which are quite possible in Tl2Ga2Se3S due to the weakness of the van der Waals forces between the layers. Distribution of traps was also investigated using an experimental method. A quasi-continuous distribution was attributed to the determined trap centers.

Keywords: chalcogenides, defects, thermoluminescence, trap centers

Procedia PDF Downloads 262
135 Calculation of Pressure-Varying Langmuir and Brunauer-Emmett-Teller Isotherm Adsorption Parameters

Authors: Trevor C. Brown, David J. Miron

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Gas-solid physical adsorption methods are central to the characterization and optimization of the effective surface area, pore size and porosity for applications such as heterogeneous catalysis, and gas separation and storage. Properties such as adsorption uptake, capacity, equilibrium constants and Gibbs free energy are dependent on the composition and structure of both the gas and the adsorbent. However, challenges remain, in accurately calculating these properties from experimental data. Gas adsorption experiments involve measuring the amounts of gas adsorbed over a range of pressures under isothermal conditions. Various constant-parameter models, such as Langmuir and Brunauer-Emmett-Teller (BET) theories are used to provide information on adsorbate and adsorbent properties from the isotherm data. These models typically do not provide accurate interpretations across the full range of pressures and temperatures. The Langmuir adsorption isotherm is a simple approximation for modelling equilibrium adsorption data and has been effective in estimating surface areas and catalytic rate laws, particularly for high surface area solids. The Langmuir isotherm assumes the systematic filling of identical adsorption sites to a monolayer coverage. The BET model is based on the Langmuir isotherm and allows for the formation of multiple layers. These additional layers do not interact with the first layer and the energetics are equal to the adsorbate as a bulk liquid. This BET method is widely used to measure the specific surface area of materials. Both Langmuir and BET models assume that the affinity of the gas for all adsorption sites are identical and so the calculated adsorbent uptake at the monolayer and equilibrium constant are independent of coverage and pressure. Accurate representations of adsorption data have been achieved by extending the Langmuir and BET models to include pressure-varying uptake capacities and equilibrium constants. These parameters are determined using a novel regression technique called flexible least squares for time-varying linear regression. For isothermal adsorption the adsorption parameters are assumed to vary slowly and smoothly with increasing pressure. The flexible least squares for pressure-varying linear regression (FLS-PVLR) approach assumes two distinct types of discrepancy terms, dynamic and measurement for all parameters in the linear equation used to simulate the data. Dynamic terms account for pressure variation in successive parameter vectors, and measurement terms account for differences between observed and theoretically predicted outcomes via linear regression. The resultant pressure-varying parameters are optimized by minimizing both dynamic and measurement residual squared errors. Validation of this methodology has been achieved by simulating adsorption data for n-butane and isobutane on activated carbon at 298 K, 323 K and 348 K and for nitrogen on mesoporous alumina at 77 K with pressure-varying Langmuir and BET adsorption parameters (equilibrium constants and uptake capacities). This modeling provides information on the adsorbent (accessible surface area and micropore volume), adsorbate (molecular areas and volumes) and thermodynamic (Gibbs free energies) variations of the adsorption sites.

Keywords: Langmuir adsorption isotherm, BET adsorption isotherm, pressure-varying adsorption parameters, adsorbate and adsorbent properties and energetics

Procedia PDF Downloads 199
134 An Empirical Study of Determinants Influencing Telemedicine Services Acceptance by Healthcare Professionals: Case of Selected Hospitals in Ghana

Authors: Jonathan Kissi, Baozhen Dai, Wisdom W. K. Pomegbe, Abdul-Basit Kassim

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Protecting patient’s digital information is a growing concern for healthcare institutions as people nowadays perpetually live their lives through telemedicine services. These telemedicine services have been confronted with several determinants that hinder their successful implementations, especially in developing countries. Identifying such determinants that influence the acceptance of telemedicine services is also a problem for healthcare professionals. Despite the tremendous increase in telemedicine services, its adoption, and use has been quite slow in some healthcare settings. Generally, it is accepted in today’s globalizing world that the success of telemedicine services relies on users’ satisfaction. Satisfying health professionals and patients are one of the crucial objectives of telemedicine success. This study seeks to investigate the determinants that influence health professionals’ intention to utilize telemedicine services in clinical activities in a sub-Saharan African country in West Africa (Ghana). A hybridized model comprising of health adoption models, including technology acceptance theory, diffusion of innovation theory, and protection of motivation theory, were used to investigate these quandaries. The study was carried out in four government health institutions that apply and regulate telemedicine services in their clinical activities. A structured questionnaire was developed and used for data collection. Purposive and convenience sampling methods were used in the selection of healthcare professionals from different medical fields for the study. The collected data were analyzed based on structural equation modeling (SEM) approach. All selected constructs showed a significant relationship with health professional’s behavioral intention in the direction expected from prior literature including perceived usefulness, perceived ease of use, management strategies, financial sustainability, communication channels, patients security threat, patients privacy risk, self efficacy, actual service use, user satisfaction, and telemedicine services systems securities threat. Surprisingly, user characteristics and response efficacy of health professionals were not significant in the hybridized model. The findings and insights from this research show that health professionals are pragmatic when making choices for technology applications and also their willingness to use telemedicine services. They are, however, anxious about its threats and coping appraisals. The identified significant constructs in the study may help to increase efficiency, quality of services, quality patient care delivery, and satisfactory user satisfaction among healthcare professionals. The implantation and effective utilization of telemedicine services in the selected hospitals will aid as a strategy to eradicate hardships in healthcare services delivery. The service will help attain universal health access coverage to all populace. This study contributes to empirical knowledge by identifying the vital factors influencing health professionals’ behavioral intentions to adopt telemedicine services. The study will also help stakeholders of healthcare to formulate better policies towards telemedicine service usage.

Keywords: telemedicine service, perceived usefulness, perceived ease of use, management strategies, security threats

Procedia PDF Downloads 115
133 Effects of School Culture and Curriculum on Gifted Adolescent Moral, Social, and Emotional Development: A Longitudinal Study of Urban Charter Gifted and Talented Programs

Authors: Rebekah Granger Ellis, Pat J. Austin, Marc P. Bonis, Richard B. Speaker, Jr.

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Using two psychometric instruments, this study examined social and emotional intelligence and moral judgment levels of more than 300 gifted and talented high school students enrolled in arts-integrated, academic acceleration, and creative arts charter schools in an ethnically diverse large city in the southeastern United States. Gifted and talented individuals possess distinguishable characteristics; these frequently appear as strengths, but often serious problems accompany them. Although many gifted adolescents thrive in their environments, some struggle in their school and community due to emotional intensity, motivation and achievement issues, lack of peers and isolation, identification problems, sensitivity to expectations and feelings, perfectionism, and other difficulties. These gifted students endure and survive in school rather than flourish. Gifted adolescents face special intrapersonal, interpersonal, and environmental problems. Furthermore, they experience greater levels of stress, disaffection, and isolation than non-gifted individuals due to their advanced cognitive abilities. Therefore, it is important to examine the long-term effects of participation in various gifted and talented programs on the socio-affective development of these adolescents. Numerous studies have researched moral, social, and emotional development in the areas of cognitive-developmental, psychoanalytic, and behavioral learning; however, in almost all cases, these three facets have been studied separately leading to many divergent theories. Additionally, various frameworks and models purporting to encourage the different socio-affective branches of development have been debated in curriculum theory, yet research is inconclusive on the effectiveness of these programs. Most often studied is the socio-affective domain, which includes development and regulation of emotions; empathy development; interpersonal relations and social behaviors; personal and gender identity construction; and moral development, thinking, and judgment. Examining development in these domains can provide insight into why some gifted and talented adolescents are not always successful in adulthood despite advanced IQ scores. Particularly whether emotional, social and moral capabilities of gifted and talented individuals are as advanced as their intellectual abilities and how these are related to each other. This mixed methods longitudinal study examined students in urban gifted and talented charter schools for (1) socio-affective development levels and (2) whether a particular environment encourages developmental growth. Research questions guiding the study: (1) How do academically and artistically gifted 10th and 11th grade students perform on psychological scales of social and emotional intelligence and moral judgment? Do they differ from the normative sample? Do gender differences exist among gifted students? (2) Do adolescents who attend distinctive gifted charter schools differ in developmental profiles? Students’ performances on psychometric instruments were compared over time and by program type. Assessing moral judgment (DIT-2) and socio-emotional intelligence (BarOn EQ-I: YV), participants took pre-, mid-, and post-tests during one academic school year. Quantitative differences in growth on these psychological scales (individuals and school-wide) were examined. If a school showed change, qualitative artifacts (culture, curricula, instructional methodology, stakeholder interviews) provided insight for environmental correlation.

Keywords: gifted and talented programs, moral judgment, social and emotional intelligence, socio-affective education

Procedia PDF Downloads 164
132 Energy Efficiency of Secondary Refrigeration with Phase Change Materials and Impact on Greenhouse Gases Emissions

Authors: Michel Pons, Anthony Delahaye, Laurence Fournaison

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Secondary refrigeration consists of splitting large-size direct-cooling units into volume-limited primary cooling units complemented by secondary loops for transporting and distributing cold. Such a design reduces the refrigerant leaks, which represents a source of greenhouse gases emitted into the atmosphere. However, inserting the secondary circuit between the primary unit and the ‘users’ heat exchangers (UHX) increases the energy consumption of the whole process, which induces an indirect emission of greenhouse gases. It is thus important to check whether that efficiency loss is sufficiently limited for the change to be globally beneficial to the environment. Among the likely secondary fluids, phase change slurries offer several advantages: they transport latent heat, they stabilize the heat exchange temperature, and the formerly evaporators still can be used as UHX. The temperature level can also be adapted to the desired cooling application. Herein, the slurry {ice in mono-propylene-glycol solution} (melting temperature Tₘ of 6°C) is considered for food preservation, and the slurry {mixed hydrate of CO₂ + tetra-n-butyl-phosphonium-bromide in aqueous solution of this salt + CO₂} (melting temperature Tₘ of 13°C) is considered for air conditioning. For the sake of thermodynamic consistency, the analysis encompasses the whole process, primary cooling unit plus secondary slurry loop, and the various properties of the slurries, including their non-Newtonian viscosity. The design of the whole process is optimized according to the properties of the chosen slurry and under explicit constraints. As a first constraint, all the units must deliver the same cooling power to the user. The other constraints concern the heat exchanges areas, which are prescribed, and the flow conditions, which prevent deposition of the solid particles transported in the slurry, and their agglomeration. Minimization of the total energy consumption leads to the optimal design. In addition, the results are analyzed in terms of exergy losses, which allows highlighting the couplings between the primary unit and the secondary loop. One important difference between the ice-slurry and the mixed-hydrate one is the presence of gaseous carbon dioxide in the latter case. When the mixed-hydrate crystals melt in the UHX, CO₂ vapor is generated at a rate that depends on the phase change kinetics. The flow in the UHX, and its heat and mass transfer properties are significantly modified. This effect has never been investigated before. Lastly, inserting the secondary loop between the primary unit and the users increases the temperature difference between the refrigerated space and the evaporator. This results in a loss of global energy efficiency, and therefore in an increased energy consumption. The analysis shows that this loss of efficiency is not critical in the first case (Tₘ = 6°C), while the second case leads to more ambiguous results, partially because of the higher melting temperature.The consequences in terms of greenhouse gases emissions are also analyzed.

Keywords: exergy, hydrates, optimization, phase change material, thermodynamics

Procedia PDF Downloads 109
131 Construction Port Requirements for Floating Wind Turbines

Authors: Alan Crowle, Philpp Thies

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As the floating offshore wind turbine industry continues to develop and grow, the capabilities of established port facilities need to be assessed as to their ability to support the expanding construction and installation requirements. This paper assesses current infrastructure requirements and projected changes to port facilities that may be required to support the floating offshore wind industry. Understanding the infrastructure needs of the floating offshore renewable industry will help to identify the port-related requirements. Floating Offshore Wind Turbines can be installed further out to sea and in deeper waters than traditional fixed offshore wind arrays, meaning that it can take advantage of stronger winds. Separate ports are required for substructure construction, fit-out of the turbines, moorings, subsea cables and maintenance. Large areas are required for the laydown of mooring equipment; inter-array cables, turbine blades and nacelles. The capabilities of established port facilities to support floating wind farms are assessed by evaluation of the size of substructures, the height of wind turbine with regards to the cranes for fitting of blades, distance to offshore site and offshore installation vessel characteristics. The paper will discuss the advantages and disadvantages of using large land-based cranes, inshore floating crane vessels or offshore crane vessels at the fit-out port for the installation of the turbine. Water depths requirements for import of materials and export of the completed structures will be considered. There are additional costs associated with any emerging technology. However part of the popularity of Floating Offshore Wind Turbines stems from the cost savings against permanent structures like fixed wind turbines. Floating Offshore Wind Turbine developers can benefit from lighter, more cost-effective equipment which can be assembled in port and towed to the site rather than relying on large, expensive installation vessels to transport and erect fixed bottom turbines. The ability to assemble Floating Offshore Wind Turbines equipment onshore means minimizing highly weather-dependent operations like offshore heavy lifts and assembly, saving time and costs and reducing safety risks for offshore workers. Maintenance might take place in safer onshore conditions for barges and semi-submersibles. Offshore renewables, such as floating wind, can take advantage of this wealth of experience, while oil and gas operators can deploy this experience at the same time as entering the renewables space The floating offshore wind industry is in the early stages of development and port facilities are required for substructure fabrication, turbine manufacture, turbine construction and maintenance support. The paper discusses the potential floating wind substructures as this provides a snapshot of the requirements at the present time, and potential technological developments required for commercial development. Scaling effects of demonstration-scale projects will be addressed, however, the primary focus will be on commercial-scale (30+ units) device floating wind energy farms.

Keywords: floating wind, port, marine construction, offshore renewables

Procedia PDF Downloads 257
130 Economic Valuation of Emissions from Mobile Sources in the Urban Environment of Bogotá

Authors: Dayron Camilo Bermudez Mendoza

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Road transportation is a significant source of externalities, notably in terms of environmental degradation and the emission of pollutants. These emissions adversely affect public health, attributable to criteria pollutants like particulate matter (PM2.5 and PM10) and carbon monoxide (CO), and also contribute to climate change through the release of greenhouse gases, such as carbon dioxide (CO2). It is, therefore, crucial to quantify the emissions from mobile sources and develop a methodological framework for their economic valuation, aiding in the assessment of associated costs and informing policy decisions. The forthcoming congress will shed light on the externalities of transportation in Bogotá, showcasing methodologies and findings from the construction of emission inventories and their spatial analysis within the city. This research focuses on the economic valuation of emissions from mobile sources in Bogotá, employing methods like hedonic pricing and contingent valuation. Conducted within the urban confines of Bogotá, the study leverages demographic, transportation, and emission data sourced from the Mobility Survey, official emission inventories, and tailored estimates and measurements. The use of hedonic pricing and contingent valuation methodologies facilitates the estimation of the influence of transportation emissions on real estate values and gauges the willingness of Bogotá's residents to invest in reducing these emissions. The findings are anticipated to be instrumental in the formulation and execution of public policies aimed at emission reduction and air quality enhancement. In compiling the emission inventory, innovative data sources were identified to determine activity factors, including information from automotive diagnostic centers and used vehicle sales websites. The COPERT model was utilized to ascertain emission factors, requiring diverse inputs such as data from the national transit registry (RUNT), OpenStreetMap road network details, climatological data from the IDEAM portal, and Google API for speed analysis. Spatial disaggregation employed GIS tools and publicly available official spatial data. The development of the valuation methodology involved an exhaustive systematic review, utilizing platforms like the EVRI (Environmental Valuation Reference Inventory) portal and other relevant sources. The contingent valuation method was implemented via surveys in various public settings across the city, using a referendum-style approach for a sample of 400 residents. For the hedonic price valuation, an extensive database was developed, integrating data from several official sources and basing analyses on the per-square meter property values in each city block. The upcoming conference anticipates the presentation and publication of these results, embodying a multidisciplinary knowledge integration and culminating in a master's thesis.

Keywords: economic valuation, transport economics, pollutant emissions, urban transportation, sustainable mobility

Procedia PDF Downloads 34
129 Culvert Blockage Evaluation Using Australian Rainfall And Runoff 2019

Authors: Rob Leslie, Taher Karimian

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The blockage of cross drainage structures is a risk that needs to be understood and managed or lessened through the design. A blockage is a random event, influenced by site-specific factors, which needs to be quantified for design. Under and overestimation of blockage can have major impacts on flood risk and cost associated with drainage structures. The importance of this matter is heightened for those projects located within sensitive lands. It is a particularly complex problem for large linear infrastructure projects (e.g., rail corridors) located within floodplains where blockage factors can influence flooding upstream and downstream of the infrastructure. The selection of the appropriate blockage factors for hydraulic modeling has been subject to extensive research by hydraulic engineers. This paper has been prepared to review the current Australian Rainfall and Runoff 2019 (ARR 2019) methodology for blockage assessment by applying this method to a transport corridor brownfield upgrade case study in New South Wales. The results of applying the method are also validated against asset data and maintenance records. ARR 2019 – Book 6, Chapter 6 includes advice and an approach for estimating the blockage of bridges and culverts. This paper concentrates specifically on the blockage of cross drainage structures. The method has been developed to estimate the blockage level for culverts affected by sediment or debris due to flooding. The objective of the approach is to evaluate a numerical blockage factor that can be utilized in a hydraulic assessment of cross drainage structures. The project included an assessment of over 200 cross drainage structures. In order to estimate a blockage factor for use in the hydraulic model, a process has been advanced that considers the qualitative factors (e.g., Debris type, debris availability) and site-specific hydraulic factors that influence blockage. A site rating associated with the debris potential (i.e., availability, transportability, mobility) at each crossing was completed using the method outlined in ARR 2019 guidelines. The hydraulic results inputs (i.e., flow velocity, flow depth) and qualitative factors at each crossing were developed into an advanced spreadsheet where the design blockage level for cross drainage structures were determined based on the condition relating Inlet Clear Width and L10 (average length of the longest 10% of the debris reaching the site) and the Adjusted Debris Potential. Asset data, including site photos and maintenance records, were then reviewed and compared with the blockage assessment to check the validity of the results. The results of this assessment demonstrate that the estimated blockage factors at each crossing location using ARR 2019 guidelines are well-validated with the asset data. The primary finding of the study is that the ARR 2019 methodology is a suitable approach for culvert blockage assessment that has been validated against a case study spanning a large geographical area and multiple sub-catchments. The study also found that the methodology can be effectively coded within a spreadsheet or similar analytical tool to automate its application.

Keywords: ARR 2019, blockage, culverts, methodology

Procedia PDF Downloads 311
128 Tectono-Stratigraphic Architecture, Depositional Systems and Salt Tectonics to Strike-Slip Faulting in Kribi-Campo-Cameroon Atlantic Margin with an Unsupervised Machine Learning Approach (West African Margin)

Authors: Joseph Bertrand Iboum Kissaaka, Charles Fonyuy Ngum Tchioben, Paul Gustave Fowe Kwetche, Jeannette Ngo Elogan Ntem, Joseph Binyet Njebakal, Ribert Yvan Makosso-Tchapi, François Mvondo Owono, Marie Joseph Ntamak-Nida

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Located in the Gulf of Guinea, the Kribi-Campo sub-basin belongs to the Aptian salt basins along the West African Margin. In this paper, we investigated the tectono-stratigraphic architecture of the basin, focusing on the role of salt tectonics and strike-slip faults along the Kribi Fracture Zone with implications for reservoir prediction. Using 2D seismic data and well data interpreted through sequence stratigraphy with integrated seismic attributes analysis with Python Programming and unsupervised Machine Learning, at least six second-order sequences, indicating three main stages of tectono-stratigraphic evolution, were determined: pre-salt syn-rift, post-salt rift climax and post-rift stages. The pre-salt syn-rift stage with KTS1 tectonosequence (Barremian-Aptian) reveals a transform rifting along NE-SW transfer faults associated with N-S to NNE-SSW syn-rift longitudinal faults bounding a NW-SE half-graben filled with alluvial to lacustrine-fan delta deposits. The post-salt rift-climax stage (Lower to Upper Cretaceous) includes two second-order tectonosequences (KTS2 and KTS3) associated with the salt tectonics and Campo High uplift. During the rift-climax stage, the growth of salt diapirs developed syncline withdrawal basins filled by early forced regression, mid transgressive and late normal regressive systems tracts. The early rift climax underlines some fine-grained hangingwall fans or delta deposits and coarse-grained fans from the footwall of fault scarps. The post-rift stage (Paleogene to Neogene) contains at least three main tectonosequences KTS4, KTS5 and KTS6-7. The first one developed some turbiditic lobe complexes considered as mass transport complexes and feeder channel-lobe complexes cutting the unstable shelf edge of the Campo High. The last two developed submarine Channel Complexes associated with lobes towards the southern part and braided delta to tidal channels towards the northern part of the Kribi-Campo sub-basin. The reservoir distribution in the Kribi-Campo sub-basin reveals some channels, fan lobes reservoirs and stacked channels reaching up to the polygonal fault systems.

Keywords: tectono-stratigraphic architecture, Kribi-Campo sub-basin, machine learning, pre-salt sequences, post-salt sequences

Procedia PDF Downloads 25
127 Flourishing in Marriage among Arab Couples in Israel: The Impact of Capitalization Support and Accommodation on Positive and Negative Affect

Authors: Niveen Hassan-Abbas, Tammie Ronen-Rosenbaum

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Background and purpose: 'Flourishing in marriage' is a concept refers to married individuals’ high positivity ratio regarding their marriage, namely greater reported positive than negative emotions. The study proposes a different approach to marriage which emphasizes the place of the individual himself as largely responsible for his personal flourishing within marriage. Accordingly, the individual's desire to preserve and strengthen his marriage largely determines the marital behavior in a way that will contribute to his marriage success (Actor Effect), regardless the contribution of his or her partner to his marriage success (Partner Effect). Another assumption was that flourishing in marriage could be achieved by two separate processes, where capitalization support increases the positive marriage's evaluations and accommodation decreases the negative one. A theoretical model was constructed, whereby individuals who were committed to their marriage were hypothesized as employing self-control skills by way of two dynamic processes. First, individual’s higher degree of 'capitalization supportive responses' - supportive responses to the partner's sharing of positive personal experiences - was hypothesized as increasing one’s positive evaluations of marriage and thereby one’s positivity ratio. Second, individual’s higher degree of 'accommodation' responses - the ability during conflict situations to control the impulse to respond destructively and instead to respond constructively - was hypothesized as decreasing one’s negative evaluations of marriage and thereby increasing one’s positivity ratio. Methods: Participants were 156 heterosexual Arab couples from different regions of Israel. The mean period of marriage was 10.19 (SD=7.83), ages were 31.53 years for women (SD=8.12) and 36.80 years for men (SD=8.07). Years of education were 13.87 for women (SD=2.84) and 13.23 years for men (SD=3.45). Each participant completed seven questionnaires: socio-demographic, self-control skills, commitment, capitalization support, accommodation, marital quality, positive and negative affect. Using statistical analyses adapted to dyadic research design, firstly descriptive statistics were calculated and preliminary tests were performed. Next, dyadic model based on the Actor-Partner Interdependence Model (APIM) were tested using structural equation modeling (SEM). Results: The assumption according to which flourishing in marriage can be achieved by two processes was confirmed. All of the Actor Effect hypotheses were confirmed. Participants with higher self-control used more capitalization support and accommodation responses. Among husbands, unlike wives, these correlations were stronger when the individual's commitment level was higher. More capitalization supportive responses were found to increase positive evaluations of marriage, and greater spousal accommodation was found to decrease negative evaluations of marriage. High positive evaluations and low negative evaluations were found to increase positivity ratio. Not according to expectation, four partner effect paths were found significant. Conclusions and Implications: The present findings coincide with the positive psychology approach that emphasizes human strengths. The uniqueness of this study is its proposal that individuals are largely responsible for their personal flourishing in marriage. This study demonstrated that marital flourishing can be achieved by two processes, where capitalization increases the positive and accommodation decreases the negative. Practical implications include the need to construct interventions that enhance self-control skills for employment of capitalizing responsiveness and accommodation processes.

Keywords: accommodation, capitalization support, commitment, flourishing in marriage, positivity ratio, self-control skills

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126 Hydraulic Headloss in Plastic Drainage Pipes at Full and Partially Full Flow

Authors: Velitchko G. Tzatchkov, Petronilo E. Cortes-Mejia, J. Manuel Rodriguez-Varela, Jesus Figueroa-Vazquez

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Hydraulic headloss, expressed by the values of friction factor f and Manning’s coefficient n, is an important parameter in designing drainage pipes. Their values normally are taken from manufacturer recommendations, many times without sufficient experimental support. To our knowledge, currently there is no standard procedure for hydraulically testing such pipes. As a result of research carried out at the Mexican Institute of Water Technology, a laboratory testing procedure was proposed and applied on 6 and 12 inches diameter polyvinyl chloride (PVC) and high-density dual wall polyethylene pipe (HDPE) drainage pipes. While the PVC pipe is characterized by naturally smooth interior and exterior walls, the dual wall HDPE pipe has corrugated exterior wall and, although considered smooth, a slightly wavy interior wall. The pipes were tested at full and partially full pipe flow conditions. The tests for full pipe flow were carried out on a 31.47 m long pipe at flow velocities between 0.11 and 4.61 m/s. Water was supplied by gravity from a 10 m-high tank in some of the tests, and from a 3.20 m-high tank in the rest of the tests. Pressure was measured independently with piezometer readings and pressure transducers. The flow rate was measured by an ultrasonic meter. For the partially full pipe flow the pipe was placed inside an existing 49.63 m long zero slope (horizontal) channel. The flow depth was measured by piezometers located along the pipe, for flow rates between 2.84 and 35.65 L/s, measured by a rectangular weir. The observed flow profiles were then compared to computer generated theoretical gradually varied flow profiles for different Manning’s n values. It was found that Manning’s n, that normally is assumed constant for a given pipe material, is in fact dependent on flow velocity and pipe diameter for full pipe flow, and on flow depth for partially full pipe flow. Contrary to the expected higher values of n and f for the HDPE pipe, virtually the same values were obtained for the smooth interior wall PVC pipe and the slightly wavy interior wall HDPE pipe. The explanation of this fact was found in Henry Morris’ theory for smooth turbulent conduit flow over isolated roughness elements. Following Morris, three categories of the flow regimes are possible in a rough conduit: isolated roughness (or semi smooth turbulent) flow, wake interference (or hyper turbulent) flow, and skimming (or quasi-smooth) flow. Isolated roughness flow is characterized by friction drag turbulence over the wall between the roughness elements, independent vortex generation, and dissipation around each roughness element. In this regime, the wake and vortex generation zones at each element develop and dissipate before attaining the next element. The longitudinal spacing of the roughness elements and their height are important influencing agents. Given the slightly wavy form of the HDPE pipe interior wall, the flow for this type of pipe belongs to this category. Based on that theory, an equation for the hydraulic friction factor was obtained. The obtained coefficient values are going to be used in the Mexican design standards.

Keywords: drainage plastic pipes, hydraulic headloss, hydraulic friction factor, Manning’s n

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125 Innovative Technologies of Distant Spectral Temperature Control

Authors: Leonid Zhukov, Dmytro Petrenko

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Optical thermometry has no alternative in many cases of industrial most effective continuous temperature control. Classical optical thermometry technologies can be used on available for pyrometers controlled objects with stable radiation characteristics and transmissivity of the intermediate medium. Without using temperature corrections, it is possible in the case of a “black” body for energy pyrometry and the cases of “black” and “grey” bodies for spectral ratio pyrometry or with using corrections – for any colored bodies. Consequently, with increasing the number of operating waves, optical thermometry possibilities to reduce methodical errors significantly expand. That is why, in recent 25-30 years, research works have been reoriented on more perfect spectral (multicolor) thermometry technologies. There are two physical material substances, i.e., substance (controlled object) and electromagnetic field (thermal radiation), to be operated in optical thermometry. Heat is transferred by radiation; therefore, radiation has the energy, entropy, and temperature. Optical thermometry was originating simultaneously with the developing of thermal radiation theory when the concept and the term "radiation temperature" was not used, and therefore concepts and terms "conditional temperatures" or "pseudo temperature" of controlled objects were introduced. They do not correspond to the physical sense and definitions of temperature in thermodynamics, molecular-kinetic theory, and statistical physics. Launched by the scientific thermometric society, discussion about the possibilities of temperature measurements of objects, including colored bodies, using the temperatures of their radiation is not finished. Are the information about controlled objects transferred by their radiation enough for temperature measurements? The positive and negative answers on this fundamental question divided experts into two opposite camps. Recent achievements of spectral thermometry develop events in her favour and don’t leave any hope for skeptics. This article presents the results of investigations and developments in the field of spectral thermometry carried out by the authors in the Department of Thermometry and Physics-Chemical Investigations. The authors have many-year’s of experience in the field of modern optical thermometry technologies. Innovative technologies of optical continuous temperature control have been developed: symmetric-wave, two-color compensative, and based on obtained nonlinearity equation of spectral emissivity distribution linear, two-range, and parabolic. Тhe technologies are based on direct measurements of physically substantiated and proposed by Prof. L. Zhukov, radiation temperatures with the next calculation of the controlled object temperature using this radiation temperatures and corresponding mathematical models. Тhe technologies significantly increase metrological characteristics of continuous contactless and light-guide temperature control in energy, metallurgical, ceramic, glassy, and other productions. For example, under the same conditions, the methodical errors of proposed technologies are less than the errors of known spectral and classical technologies in 2 and 3-13 times, respectively. Innovative technologies provide quality products obtaining at the lowest possible resource-including energy costs. More than 600 publications have been published on the completed developments, including more than 100 domestic patents, as well as 34 patents in Australia, Bulgaria, Germany, France, Canada, the USA, Sweden, and Japan. The developments have been implemented in the enterprises of USA, as well as Western Europe and Asia, including Germany and Japan.

Keywords: emissivity, radiation temperature, object temperature, spectral thermometry

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124 Horizontal Stress Magnitudes Using Poroelastic Model in Upper Assam Basin, India

Authors: Jenifer Alam, Rima Chatterjee

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Upper Assam sedimentary basin is one of the oldest commercially producing basins of India. Being in a tectonically active zone, estimation of tectonic strain and stress magnitudes has vast application in hydrocarbon exploration and exploitation. This East North East –West South West trending shelf-slope basin encompasses the Bramhaputra valley extending from Mikir Hills in the southwest to the Naga foothills in the northeast. Assam Shelf lying between the Main Boundary Thrust (MBT) and Naga Thrust area is comparatively free from thrust tectonics and depicts normal faulting mechanism. The study area is bounded by the MBT and Main Central Thrust in the northwest. The Belt of Schuppen in the southeast, is bordered by Naga and Disang thrust marking the lower limit of the study area. The entire Assam basin shows low-level seismicity compared to other regions of northeast India. Pore pressure (PP), vertical stress magnitude (SV) and horizontal stress magnitudes have been estimated from two wells - N1 and T1 located in Upper Assam. N1 is located in the Assam gap below the Bramhaputra river while T1, lies in the Belt of Schuppen. N1 penetrates geological formations from top Alluvial through Dhekiajuli, Girujan, Tipam, Barail, Kopili, Sylhet and Langpur to the granitic basement while T1 in trusted zone crosses through Girujan Suprathrust, Tipam Suprathrust, Barail Suprathrust to reach Naga Thrust. Normal compaction trend is drawn through shale points through both wells for estimation of PP using the conventional Eaton sonic equation with an exponent of 1.0 which is validated with Modular Dynamic Tester and mud weight. Observed pore pressure gradient ranges from 10.3 MPa/km to 11.1 MPa/km. The SV has a gradient from 22.20 to 23.80 MPa/km. Minimum and maximum horizontal principal stress (Sh and SH) magnitudes under isotropic conditions are determined using poroelastic model. This approach determines biaxial tectonic strain utilizing static Young’s Modulus, Poisson’s Ratio, SV, PP, leak off test (LOT) and SH derived from breakouts using prior information on unconfined compressive strength. Breakout derived SH information is used for obtaining tectonic strain due to lack of measured SH data from minifrac or hydrofracturing. Tectonic strain varies from 0.00055 to 0.00096 along x direction and from -0.0010 to 0.00042 along y direction. After obtaining tectonic strains at each well, the principal horizontal stress magnitudes are calculated from linear poroelastic model. The magnitude of Sh and SH gradient in normal faulting region are 12.5 and 16.0 MPa/km while in thrust faulted region the gradients are 17.4 and 20.2 MPa/km respectively. Model predicted Sh and SH matches well with the LOT data and breakout derived SH data in both wells. It is observed from this study that the stresses SV>SH>Sh prevailing in the shelf region while near the Naga foothills the regime changes to SH≈SV>Sh area corresponds to normal faulting regime. Hence this model is a reliable tool for predicting stress magnitudes from well logs under active tectonic regime in Upper Assam Basin.

Keywords: Eaton, strain, stress, poroelastic model

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123 Correlation Analysis of Reactivity in the Oxidation of Para and Meta-Substituted Benzyl Alcohols by Benzimidazolium Dichromate in Non-Aqueous Media: A Kinetic and Mechanistic Aspects

Authors: Seema Kothari, Dinesh Panday

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An observed correlation of the reaction rates with the changes in the nature of substituent present on one of the reactants often reveals the nature of transition state. Selective oxidation of organic compounds under non-aqueous media is an important transformation in synthetic organic chemistry. Inorganic chromates and dichromates being drastic oxidant and are generally insoluble in most organic solvents, a number of different chromium (VI) derivatives have been synthesized. Benzimidazolium dichromate (BIDC) is one of the recently reported Cr(VI) reagents which is neither hygroscopic nor light sensitive being, therefore, much stable. Not many reports on the kinetics of the oxidations by BIDC are seemed to be available in the literature. In the present investigation, the kinetics and mechanism of benzyl alcohol (BA) and a number of para- and meta-substituted benzyl alcohols by benzimidazolium dichromate (BIDC), in dimethyl sulphoxide, is reported. The reactions were followed spectrophotometrically at 364 nm by monitoring the decrease in [BIDC] for up to 85-90% reaction, the temperature being constant. The observed oxidation product is the corresponding benzaldehyde. The reactions were of first order with respect to each the alcohol and BIDC. The reactions are catalyzed by proton, and the dependence is of the form: kobs = a + b[H+]. The reactions thus follow both, an acid-dependent and acid-independent paths. The oxidation of [1,1 2H2]benzyl alcohol exhibited the presence of a substantial kinetic isotope effect ( kH/kD = 6.20 at 298 K ). This indicated the cleavage of a α-C-H bond in the rate-determining step. An analysis of the temperature dependence of the deuterium isotope effect showed that the loss of hydrogen proceeds through a concerted cyclic process. The rate of oxidation of BA was determined in 19 organic solvents. An analysis of the solvent effect by Swain’s equation indicated that though both the anion and cation-solvating powers of the solvent contribute to the observed solvent effect, the role of cation-solvation is major. The rates of the para and meta compounds, at 298 K, failed to exhibit a significant correlation in terms of Hammett or Brown's substituent constants. The rates were then subjected to analyses in terms of dual substituent parameter (DSP) equations. The rates of oxidation of the para-substituted benzyl alcohols show an excellent correlation with Taft's σI and σRBA values. However, the rates for the meta-substituted benzyl alcohols show an excellent correlation with σI and σR0. The polar reaction constants are negative indicating an electron-deficient transition state. Hence the overall mechanism is proposed to involve the formation of a chromate ester in a fast pre-equilibrium and then a decomposition of the ester in a subsequent slow step via a cyclic concerted symmetrical transition state, involving hydride-ion transfer, leading to the product. The first order dependence on alcohol may be accounted in terms of the small value of the formation constant of the ester intermediate. An another reaction mechanism accounting the acid-catalysis involve the formation of a protonated BIDC prior to formation of an ester intermediate which subsequently decomposes in a slow step leading to the product.

Keywords: benzimidazolium dichromate, benzyl alcohols, correlation analysis, kinetics, oxidation

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122 Electronic Raman Scattering Calibration for Quantitative Surface-Enhanced Raman Spectroscopy and Improved Biostatistical Analysis

Authors: Wonil Nam, Xiang Ren, Inyoung Kim, Masoud Agah, Wei Zhou

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Despite its ultrasensitive detection capability, surface-enhanced Raman spectroscopy (SERS) faces challenges as a quantitative biochemical analysis tool due to the significant dependence of local field intensity in hotspots on nanoscale geometric variations of plasmonic nanostructures. Therefore, despite enormous progress in plasmonic nanoengineering of high-performance SERS devices, it is still challenging to quantitatively correlate the measured SERS signals with the actual molecule concentrations at hotspots. A significant effort has been devoted to developing SERS calibration methods by introducing internal standards. It has been achieved by placing Raman tags at plasmonic hotspots. Raman tags undergo similar SERS enhancement at the same hotspots, and ratiometric SERS signals for analytes of interest can be generated with reduced dependence on geometrical variations. However, using Raman tags still faces challenges for real-world applications, including spatial competition between the analyte and tags in hotspots, spectral interference, laser-induced degradation/desorption due to plasmon-enhanced photochemical/photothermal effects. We show that electronic Raman scattering (ERS) signals from metallic nanostructures at hotspots can serve as the internal calibration standard to enable quantitative SERS analysis and improve biostatistical analysis. We perform SERS with Au-SiO₂ multilayered metal-insulator-metal nano laminated plasmonic nanostructures. Since the ERS signal is proportional to the volume density of electron-hole occupation in hotspots, the ERS signals exponentially increase when the wavenumber is approaching the zero value. By a long-pass filter, generally used in backscattered SERS configurations, to chop the ERS background continuum, we can observe an ERS pseudo-peak, IERS. Both ERS and SERS processes experience the |E|⁴ local enhancements during the excitation and inelastic scattering transitions. We calibrated IMRS of 10 μM Rhodamine 6G in solution by IERS. The results show that ERS calibration generates a new analytical value, ISERS/IERS, insensitive to variations from different hotspots and thus can quantitatively reflect the molecular concentration information. Given the calibration capability of ERS signals, we performed label-free SERS analysis of living biological systems using four different breast normal and cancer cell lines cultured on nano-laminated SERS devices. 2D Raman mapping over 100 μm × 100 μm, containing several cells, was conducted. The SERS spectra were subsequently analyzed by multivariate analysis using partial least square discriminant analysis. Remarkably, after ERS calibration, MCF-10A and MCF-7 cells are further separated while the two triple-negative breast cancer cells (MDA-MB-231 and HCC-1806) are more overlapped, in good agreement with the well-known cancer categorization regarding the degree of malignancy. To assess the strength of ERS calibration, we further carried out a drug efficacy study using MDA-MB-231 and different concentrations of anti-cancer drug paclitaxel (PTX). After ERS calibration, we can more clearly segregate the control/low-dosage groups (0 and 1.5 nM), the middle-dosage group (5 nM), and the group treated with half-maximal inhibitory concentration (IC50, 15 nM). Therefore, we envision that ERS calibrated SERS can find crucial opportunities in label-free molecular profiling of complicated biological systems.

Keywords: cancer cell drug efficacy, plasmonics, surface-enhanced Raman spectroscopy (SERS), SERS calibration

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121 A Digital Clone of an Irrigation Network Based on Hardware/Software Simulation

Authors: Pierre-Andre Mudry, Jean Decaix, Jeremy Schmid, Cesar Papilloud, Cecile Munch-Alligne

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In most of the Swiss Alpine regions, the availability of water resources is usually adequate even in times of drought, as evidenced by the 2003 and 2018 summers. Indeed, important natural stocks are for the moment available in the form of snow and ice, but the situation is likely to change in the future due to global and regional climate change. In addition, alpine mountain regions are areas where climate change will be felt very rapidly and with high intensity. For instance, the ice regime of these regions has already been affected in recent years with a modification of the monthly availability and extreme events of precipitations. The current research, focusing on the municipality of Val de Bagnes, located in the canton of Valais, Switzerland, is part of a project led by the Altis company and achieved in collaboration with WSL, BlueArk Entremont, and HES-SO Valais-Wallis. In this region, water occupies a key position notably for winter and summer tourism. Thus, multiple actors want to apprehend the future needs and availabilities of water, on both the 2050 and 2100 horizons, in order to plan the modifications to the water supply and distribution networks. For those changes to be salient and efficient, a good knowledge of the current water distribution networks is of most importance. In the current case, the water drinking network is well documented, but this is not the case for the irrigation one. Since the water consumption for irrigation is ten times higher than for drinking water, data acquisition on the irrigation network is a major point to determine future scenarios. This paper first presents the instrumentation and simulation of the irrigation network using custom-designed IoT devices, which are coupled with a digital clone simulated to reduce the number of measuring locations. The developed IoT ad-hoc devices are energy-autonomous and can measure flows and pressures using industrial sensors such as calorimetric water flow meters. Measurements are periodically transmitted using the LoRaWAN protocol over a dedicated infrastructure deployed in the municipality. The gathered values can then be visualized in real-time on a dashboard, which also provides historical data for analysis. In a second phase, a digital clone of the irrigation network was modeled using EPANET, a software for water distribution systems that performs extended-period simulations of flows and pressures in pressurized networks composed of reservoirs, pipes, junctions, and sinks. As a preliminary work, only a part of the irrigation network was modelled and validated by comparisons with the measurements. The simulations are carried out by imposing the consumption of water at several locations. The validation is performed by comparing the simulated pressures are different nodes with the measured ones. An accuracy of +/- 15% is observed on most of the nodes, which is acceptable for the operator of the network and demonstrates the validity of the approach. Future steps will focus on the deployment of the measurement devices on the whole network and the complete modelling of the network. Then, scenarios of future consumption will be investigated. Acknowledgment— The authors would like to thank the Swiss Federal Office for Environment (FOEN), the Swiss Federal Office for Agriculture (OFAG) for their financial supports, and ALTIS for the technical support, this project being part of the Swiss Pilot program 'Adaptation aux changements climatiques'.

Keywords: hydraulic digital clone, IoT water monitoring, LoRaWAN water measurements, EPANET, irrigation network

Procedia PDF Downloads 116