Search results for: application analysis
1088 Thermo-Economic Evaluation of Sustainable Biogas Upgrading via Solid-Oxide Electrolysis
Authors: Ligang Wang, Theodoros Damartzis, Stefan Diethelm, Jan Van Herle, François Marechal
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Biogas production from anaerobic digestion of organic sludge from wastewater treatment as well as various urban and agricultural organic wastes is of great significance to achieve a sustainable society. Two upgrading approaches for cleaned biogas can be considered: (1) direct H₂ injection for catalytic CO₂ methanation and (2) CO₂ separation from biogas. The first approach usually employs electrolysis technologies to generate hydrogen and increases the biogas production rate; while the second one usually applies commercially-available highly-selective membrane technologies to efficiently extract CO₂ from the biogas with the latter being then sent afterward for compression and storage for further use. A straightforward way of utilizing the captured CO₂ is on-site catalytic CO₂ methanation. From the perspective of system complexity, the second approach may be questioned, since it introduces an additional expensive membrane component for producing the same amount of methane. However, given the circumstance that the sustainability of the produced biogas should be retained after biogas upgrading, renewable electricity should be supplied to drive the electrolyzer. Therefore, considering the intermittent nature and seasonal variation of renewable electricity supply, the second approach offers high operational flexibility. This indicates that these two approaches should be compared based on the availability and scale of the local renewable power supply and not only the technical systems themselves. Solid-oxide electrolysis generally offers high overall system efficiency, and more importantly, it can achieve simultaneous electrolysis of CO₂ and H₂O (namely, co-electrolysis), which may bring significant benefits for the case of CO₂ separation from the produced biogas. When taking co-electrolysis into account, two additional upgrading approaches can be proposed: (1) direct steam injection into the biogas with the mixture going through the SOE, and (2) CO₂ separation from biogas which can be used later for co-electrolysis. The case study of integrating SOE to a wastewater treatment plant is investigated with wind power as the renewable power. The dynamic production of biogas is provided on an hourly basis with the corresponding oxygen and heating requirements. All four approaches mentioned above are investigated and compared thermo-economically: (a) steam-electrolysis with grid power, as the base case for steam electrolysis, (b) CO₂ separation and co-electrolysis with grid power, as the base case for co-electrolysis, (c) steam-electrolysis and CO₂ separation (and storage) with wind power, and (d) co-electrolysis and CO₂ separation (and storage) with wind power. The influence of the scale of wind power supply is investigated by a sensitivity analysis. The results derived provide general understanding on the economic competitiveness of SOE for sustainable biogas upgrading, thus assisting the decision making for biogas production sites. The research leading to the presented work is funded by European Union’s Horizon 2020 under grant agreements n° 699892 (ECo, topic H2020-JTI-FCH-2015-1) and SCCER BIOSWEET.Keywords: biogas upgrading, solid-oxide electrolyzer, co-electrolysis, CO₂ utilization, energy storage
Procedia PDF Downloads 1551087 Pueblos Mágicos in Mexico: The Loss of Intangible Cultural Heritage and Cultural Tourism
Authors: Claudia Rodriguez-Espinosa, Erika Elizabeth Pérez Múzquiz
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Since the creation of the “Pueblos Mágicos” program in 2001, a series of social and cultural events had directly affected the heritage conservation of the 121 registered localities until 2018, when the federal government terminated the program. Many studies have been carried out that seek to analyze from different perspectives and disciplines the consequences that these appointments have generated in the “Pueblos Mágicos.” Multidisciplinary groups such as the one headed by Carmen Valverde and Liliana López Levi, have brought together specialists from all over the Mexican Republic to create a set of diagnoses of most of these settlements, and although each one has unique specificities, there is a constant in most of them that has to do with the loss of cultural heritage and that is related to transculturality. There are several factors identified that have fostered a cultural loss, as a direct reflection of the economic crisis that prevails in Mexico. It is important to remember that the origin of this program had as its main objective to promote the growth and development of local economies since one of the conditions for entering the program is that they have less than 20,000 inhabitants. With this goal in mind, one of the first actions that many “Pueblos Mágicos” carried out was to improve or create an infrastructure to receive both national and foreign tourists since this was practically non-existent. Creating hotels, restaurants, cafes, training certified tour guides, among other actions, have led to one of the great problems they face: globalization. Although by itself it is not bad, its impact in many cases has been negative for heritage conservation. The entry into and contact with new cultures has led to the undervaluation of cultural traditions, their transformation and even their total loss. This work seeks to present specific cases of transformation and loss of cultural heritage, as well as to reflect on the problem and propose scenarios in which the negative effects can be reversed. For this text, 36 “Pueblos Mágicos” have been selected for study, based on those settlements that are cited in volumes I and IV (the first and last of the collection) of the series produced by the multidisciplinary group led by Carmen Valverde and Liliana López Levi (researchers from UNAM and UAM Xochimilco respectively) in the project supported by CONACyT entitled “Pueblos Mágicos. An interdisciplinary vision”, of which we are part. This sample is considered representative since it forms 30% of the total of 121 “Pueblos Mágicos” existing at that moment. With this information, the elements of its intangible heritage loss or transformation have been identified in every chapter based on the texts written by the participants of that project. Finally, this text shows an analysis of the effects that this federal program, as a public policy applied to 132 populations, has had on the conservation or transformation of the intangible cultural heritage of the “Pueblos Mágicos.” Transculturality, globalization, the creation of identities and the desire to increase the flow of tourists have impacted the changes that traditions (main intangible cultural heritage) have had in the 18 years that the federal program lasted.Keywords: public policies, cultural tourism, heritage preservation, pueblos mágicos program
Procedia PDF Downloads 1901086 A Comprehensive Key Performance Indicators Dashboard for Emergency Medical Services
Authors: Giada Feletti, Daniela Tedesco, Paolo Trucco
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The present study aims to develop a dashboard of Key Performance Indicators (KPI) to enhance information and predictive capabilities in Emergency Medical Services (EMS) systems, supporting both operational and strategic decisions of different actors. The employed research methodology consists of the first phase of revision of the technical-scientific literature concerning the indicators currently used for the performance measurement of EMS systems. From this literature analysis, it emerged that current studies focus on two distinct perspectives: the ambulance service, a fundamental component of pre-hospital health treatment, and the patient care in the Emergency Department (ED). The perspective proposed by this study is to consider an integrated view of the ambulance service process and the ED process, both essential to ensure high quality of care and patient safety. Thus, the proposal focuses on the entire healthcare service process and, as such, allows considering the interconnection between the two EMS processes, the pre-hospital and hospital ones, connected by the assignment of the patient to a specific ED. In this way, it is possible to optimize the entire patient management. Therefore, attention is paid to the dependency of decisions that in current EMS management models tend to be neglected or underestimated. In particular, the integration of the two processes enables the evaluation of the advantage of an ED selection decision having visibility on EDs’ saturation status and therefore considering the distance, the available resources and the expected waiting times. Starting from a critical review of the KPIs proposed in the extant literature, the design of the dashboard was carried out: the high number of analyzed KPIs was reduced by eliminating the ones firstly not in line with the aim of the study and then the ones supporting a similar functionality. The KPIs finally selected were tested on a realistic dataset, which draws us to exclude additional indicators due to the unavailability of data required for their computation. The final dashboard, which was discussed and validated by experts in the field, includes a variety of KPIs able to support operational and planning decisions, early warning, and citizens’ awareness of EDs accessibility in real-time. By associating each KPI to the EMS phase it refers to, it was also possible to design a well-balanced dashboard covering both efficiency and effective performance of the entire EMS process. Indeed, just the initial phases related to the interconnection between ambulance service and patient’s care are covered by traditional KPIs compared to the subsequent phases taking place in the hospital ED. This could be taken into consideration for the potential future development of the dashboard. Moreover, the research could proceed by building a multi-layer dashboard composed of the first level with a minimal set of KPIs to measure the basic performance of the EMS system at an aggregate level and further levels with KPIs that can bring additional and more detailed information.Keywords: dashboard, decision support, emergency medical services, key performance indicators
Procedia PDF Downloads 1131085 Adaptability in Older People: A Mixed Methods Approach
Authors: V. Moser-Siegmeth, M. C. Gambal, M. Jelovcak, B. Prytek, I. Swietalsky, D. Würzl, C. Fida, V. Mühlegger
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Adaptability is the capacity to adjust without great difficulty to changing circumstances. Within our project, we aimed to detect whether older people living within a long-term care hospital lose the ability to adapt. Theoretical concepts are contradictory in their statements. There is also lack of evidence in the literature how the adaptability of older people changes over the time. Following research questions were generated: Are older residents of a long-term care facility able to adapt to changes within their daily routine? How long does it take for older people to adapt? The study was designed as a convergent parallel mixed method intervention study, carried out within a four-month period and took place within seven wards of a long-term care hospital. As a planned intervention, a change of meal-times was established. The inhabitants were surveyed with qualitative interviews and quantitative questionnaires and diaries before, during and after the intervention. In addition, a survey of the nursing staff was carried out in order to detect changes of the people they care for and how long it took them to adapt. Quantitative data was analysed with SPSS, qualitative data with a summarizing content analysis. The average age of the involved residents was 82 years, the average length of stay 45 months. The adaptation to new situations does not cause problems for older residents. 47% of the residents state that their everyday life has not changed by changing the meal times. 24% indicate ‘neither nor’ and only 18% respond that their daily life has changed considerably due to the changeover. The diaries of the residents, which were conducted over the entire period of investigation showed no changes with regard to increased or reduced activity. With regard to sleep quality, assessed with the Pittsburgh sleep quality index, there is little change in sleep behaviour compared to the two survey periods (pre-phase to follow-up phase) in the cross-table. The subjective sleep quality of the residents is not affected. The nursing staff points out that, with good information in advance, changes are not a problem. The ability to adapt to changes does not deteriorate with age or by moving into a long-term care facility. It only takes a few days to get used to new situations. This can be confirmed by the nursing staff. Although there are different determinants like the health status that might make an adjustment to new situations more difficult. In connection with the limitations, the small sample size of the quantitative data collection must be emphasized. Furthermore, the extent to which the quantitative and qualitative sample represents the total population, since only residents without cognitive impairments of selected units participated. The majority of the residents has cognitive impairments. It is important to discuss whether and how well the diary method is suitable for older people to examine their daily structure.Keywords: adaptability, intervention study, mixed methods, nursing home residents
Procedia PDF Downloads 1481084 Survey of the Literacy by Radio Project as an Innovation in Literacy Promotion in Nigeria
Authors: Stella Chioma Nwizu
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The National Commission for Adult and Non Formal Education (NMEC) in Nigeria is charged with the reduction of illiteracy rate through the development, monitoring, and supervision of literacy programmes in Nigeria. In spite of various efforts by NMEC to reduce illiteracy, literature still shows that the illiteracy rate is still high. According to NMEC/UNICEF, about 60 million Nigerians are non-literate, and nearly two thirds of them are women. This situation forced the government to search for innovative and better approaches to literacy promotion and delivery. The literacy by radio project was adopted as an innovative intervention to literacy delivery in Nigeria because the radio is the cheapest and most easily affordable medium for non-literates. The project aimed at widening access to literacy programmes for the non-literate marginalized and disadvantaged groups in Nigeria by taking literacy programmes to their door steps. The literacy by radio has worked perfectly well in non-literacy reduction in Cuba. This innovative intervention of literacy by radio is anchored on the diffusion of innovation theory by Rogers. The literacy by radio has been going on for fifteen years and the efficacy and contributions of this innovation need to be investigated. Thus, the purpose of this research is to review the contributions of the literacy by radio in Nigeria. The researcher adopted the survey research design for the study. The population for the study consisted of 2,706 participants and 47 facilitators of the literacy by radio programme in the 10 pilot states in Nigeria. A sample of four states made up of 302 participants and eight facilitators were used for the study. Information was collected through Focus Group Discussion (FGD), interviews and content analysis of official documents. The data were analysed qualitatively to review the contributions of literacy by radio project and determine the efficacy of this innovative approach in facilitating literacy in Nigeria. Results from the field experience showed, among others, that more non-literates have better access to literacy programmes through this innovative approach. The pilot project was 88% successful; not less than 2,110 adults were made literate through the literacy by radio project in 2017. However, lack of enthusiasm and commitment on the part of the technical committee and facilitators due to non-payment of honorarium, poor signals from radio stations, interruption of lectures with adverts, low community involvement in decision making in the project are challenges to the success rate of the project. The researcher acknowledges the need to customize all materials and broadcasts in all the dialects of the participants and the inclusion of more civil rights, environmental protection and agricultural skills into the project. The study recommends among others, improved and timely funding of the project by the Federal Government to enable NMEC to fulfill her obligations towards the greater success of the programme, setting up of independent radio stations for airing the programmes and proper monitoring and evaluation of the project by NMEC and State Agencies for greater effectiveness. In an era of the knowledge-driven economy, no one should be allowed to get saddled with the weight of illiteracy.Keywords: innovative approach, literacy, project, radio, survey
Procedia PDF Downloads 661083 On Stochastic Models for Fine-Scale Rainfall Based on Doubly Stochastic Poisson Processes
Authors: Nadarajah I. Ramesh
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Much of the research on stochastic point process models for rainfall has focused on Poisson cluster models constructed from either the Neyman-Scott or Bartlett-Lewis processes. The doubly stochastic Poisson process provides a rich class of point process models, especially for fine-scale rainfall modelling. This paper provides an account of recent development on this topic and presents the results based on some of the fine-scale rainfall models constructed from this class of stochastic point processes. Amongst the literature on stochastic models for rainfall, greater emphasis has been placed on modelling rainfall data recorded at hourly or daily aggregation levels. Stochastic models for sub-hourly rainfall are equally important, as there is a need to reproduce rainfall time series at fine temporal resolutions in some hydrological applications. For example, the study of climate change impacts on hydrology and water management initiatives requires the availability of data at fine temporal resolutions. One approach to generating such rainfall data relies on the combination of an hourly stochastic rainfall simulator, together with a disaggregator making use of downscaling techniques. Recent work on this topic adopted a different approach by developing specialist stochastic point process models for fine-scale rainfall aimed at generating synthetic precipitation time series directly from the proposed stochastic model. One strand of this approach focused on developing a class of doubly stochastic Poisson process (DSPP) models for fine-scale rainfall to analyse data collected in the form of rainfall bucket tip time series. In this context, the arrival pattern of rain gauge bucket tip times N(t) is viewed as a DSPP whose rate of occurrence varies according to an unobserved finite state irreducible Markov process X(t). Since the likelihood function of this process can be obtained, by conditioning on the underlying Markov process X(t), the models were fitted with maximum likelihood methods. The proposed models were applied directly to the raw data collected by tipping-bucket rain gauges, thus avoiding the need to convert tip-times to rainfall depths prior to fitting the models. One advantage of this approach was that the use of maximum likelihood methods enables a more straightforward estimation of parameter uncertainty and comparison of sub-models of interest. Another strand of this approach employed the DSPP model for the arrivals of rain cells and attached a pulse or a cluster of pulses to each rain cell. Different mechanisms for the pattern of the pulse process were used to construct variants of this model. We present the results of these models when they were fitted to hourly and sub-hourly rainfall data. The results of our analysis suggest that the proposed class of stochastic models is capable of reproducing the fine-scale structure of the rainfall process, and hence provides a useful tool in hydrological modelling.Keywords: fine-scale rainfall, maximum likelihood, point process, stochastic model
Procedia PDF Downloads 2781082 Antimicrobial Value of Olax subscorpioidea and Bridelia ferruginea on Micro-Organism Isolates of Dental Infection
Authors: I. C. Orabueze, A. A. Amudalat, S. A. Adesegun, A. A. Usman
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Dental and associated oral diseases are increasingly affecting a considerable portion of the population and are considered some of the major causes of tooth loss, discomfort, mouth odor and loss of confidence. This study focused on the ethnobotanical survey of medicinal plants used in oral therapy and evaluation of the antimicrobial activities of methanolic extracts of two selected plants from the survey for their efficacy against dental microorganisms. The ethnobotanical survey was carried out in six herbal markets in Lagos State, Nigeria by oral interviewing and information obtained from an old family manually complied herbal medication book. Methanolic extracts of Olax subscorpioidea (stem bark) and Bridelia ferruginea (stem bark) were assayed for their antimicrobial activities against clinical oral isolates (Aspergillus fumigatus, Candida albicans, Streptococcus spp, Staphylococcus aureus, Lactobacillus acidophilus and Pseudomonas aeruginosa). In vitro microbial technique (agar well diffusion method and minimum inhibitory concentration (MIC) assay) were employed for the assay. Chlorhexidine gluconate was used as the reference drug for comparison with the extract results. And the preliminary phytochemical screening of the constituents of the plants were done. The ethnobotanical survey produced plants (28) of diverse family. Different parts of plants (seed, fruit, leaf, root, bark) were mentioned but 60% mentioned were either the stem or the bark. O. subscorpioidea showed considerable antifungal activity with zone of inhibition ranging from 2.650 – 2.000 cm against Aspergillus fumigatus but no such encouraging inhibitory activity was observed in the other assayed organisms. B. ferruginea showed antibacterial sensitivity against Streptococcus spp, Staphylococcus aureus, Lactobacillus acidophilus and Pseudomonas aeruginosa with zone of inhibitions ranging from 3.400 - 2.500, 2.250 - 1.600, 2.700 - 1.950, 2.225 – 1.525 cm respectively. The minimum inhibitory concentration of O. subscorpioidea against Aspergillus fumigatus was 51.2 mg ml-1 while that of B. ferruginea against Streptococcus spp was 0.1mg ml-1 and for Staphylococcus aureus, Lactobacillus acidophilus and Pseudomonas aeruginosa were 25.6 mg ml-1. A phytochemical analysis reveals the presence of alkaloids, saponins, cardiac glycoside, tannins, phenols and terpenoids in both plants, with steroids only in B. ferruginea. No toxicity was observed among mice given the two methanolic extracts (1000 mg Kg-1) after 21 days. The barks of both plants exhibited antimicrobial properties against periodontal diseases causing organisms assayed, thus up-holding their folkloric use in oral disorder management. Further research could be done viewing these extracts as combination therapy, checking for possible synergistic value in toothpaste and oral rinse formulations for reducing oral bacterial flora and fungi load.Keywords: antimicrobial activities, Bridelia ferruginea, dental disinfection, methanolic extract, Olax subscorpioidea, ethnobotanical survey
Procedia PDF Downloads 2441081 Rotary Machine Sealing Oscillation Frequencies and Phase Shift Analysis
Authors: Liliia N. Butymova, Vladimir Ya Modorskii
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To ensure the gas transmittal GCU's efficient operation, leakages through the labyrinth packings (LP) should be minimized. Leakages can be minimized by decreasing the LP gap, which in turn depends on thermal processes and possible rotor vibrations and is designed to ensure absence of mechanical contact. Vibration mitigation allows to minimize the LP gap. It is advantageous to research influence of processes in the dynamic gas-structure system on LP vibrations. This paper considers influence of rotor vibrations on LP gas dynamics and influence of the latter on the rotor structure within the FSI unidirectional dynamical coupled problem. Dependences of nonstationary parameters of gas-dynamic process in LP on rotor vibrations under various gas speeds and pressures, shaft rotation speeds and vibration amplitudes, and working medium features were studied. The programmed multi-processor ANSYS CFX was chosen as a numerical computation tool. The problem was solved using PNRPU high-capacity computer complex. Deformed shaft vibrations are replaced with an unyielding profile that moves in the fixed annulus "up-and-down" according to set harmonic rule. This solves a nonstationary gas-dynamic problem and determines time dependence of total gas-dynamic force value influencing the shaft. Pressure increase from 0.1 to 10 MPa causes growth of gas-dynamic force oscillation amplitude and frequency. The phase shift angle between gas-dynamic force oscillations and those of shaft displacement decreases from 3π/4 to π/2. Damping constant has maximum value under 1 MPa pressure in the gap. Increase of shaft oscillation frequency from 50 to 150 Hz under P=10 MPa causes growth of gas-dynamic force oscillation amplitude. Damping constant has maximum value at 50 Hz equaling 1.012. Increase of shaft vibration amplitude from 20 to 80 µm under P=10 MPa causes the rise of gas-dynamic force amplitude up to 20 times. Damping constant increases from 0.092 to 0.251. Calculations for various working substances (methane, perfect gas, air at 25 ˚С) prove the minimum gas-dynamic force persistent oscillating amplitude under P=0.1 MPa being observed in methane, and maximum in the air. Frequency remains almost unchanged and the phase shift in the air changes from 3π/4 to π/2. Calculations for various working substances (methane, perfect gas, air at 25 ˚С) prove the maximum gas-dynamic force oscillating amplitude under P=10 MPa being observed in methane, and minimum in the air. Air demonstrates surging. Increase of leakage speed from 0 to 20 m/s through LP under P=0.1 MPa causes the gas-dynamic force oscillating amplitude to decrease by 3 orders and oscillation frequency and the phase shift to increase 2 times and stabilize. Increase of leakage speed from 0 to 20 m/s in LP under P=1 MPa causes gas-dynamic force oscillating amplitude to decrease by almost 4 orders. The phase shift angle increases from π/72 to π/2. Oscillations become persistent. Flow rate proved to influence greatly on pressure oscillations amplitude and a phase shift angle. Work medium influence depends on operation conditions. At pressure growth, vibrations are mostly affected in methane (of working substances list considered), and at pressure decrease, in the air at 25 ˚С.Keywords: aeroelasticity, labyrinth packings, oscillation phase shift, vibration
Procedia PDF Downloads 2961080 Study of Isoprene Emissions in Biogenic ad Anthropogenic Environment in Urban Atmosphere of Delhi: The Capital City of India
Authors: Prabhat Kashyap, Krishan Kumar
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Delhi, the capital of India, is one of the most populated and polluted city among the world. In terms of air quality, Delhi’s air is degrading day by day & becomes worst of any major city in the world. The role of biogenic volatile organic compounds (BVOCs) is not much studied in cities like Delhi as a culprit for degraded air quality. They not only play a critical role in rural areas but also determine the atmospheric chemistry of urban areas as well. Particularly, Isoprene (2-methyl 1,3-butadiene, C5H8) is the single largest emitted compound among other BVOCs globally, that influence the tropospheric ozone chemistry in urban environment as the ozone forming potential of isoprene is very high. It is mainly emitted by vegetation & a small but significant portion is also released by vehicular exhaust of petrol operated vehicles. This study investigates the spatial and temporal variations of quantitative measurements of isoprene emissions along with different traffic tracers in 2 different seasons (post-monsoon & winter) at four different locations of Delhi. For the quantification of anthropogenic and biogenic isoprene, two sites from traffic intersections (Punjabi Bagh & CRRI) and two sites from vegetative locations (JNU & Yamuna Biodiversity Park) were selected in the vicinity of isoprene emitting tree species like Ficus religiosa, Dalbergia sissoo, Eucalyptus species etc. The concentrations of traffic tracers like benzene, toluene were also determined & their robust ratios with isoprene were used to differentiate anthropogenic isoprene with biogenic portion at each site. The ozone forming potential (OFP) of all selected species along with isoprene was also estimated. For collection of intra-day samples (3 times a day) in each season, a pre-conditioned fenceline monitoring (FLM) carbopack X thermal desorption tubes were used and further analysis was done with Gas chromatography attached with mass spectrometry (GC-MS). The results of the study proposed that the ambient air isoprene is always higher in post-monsoon season as compared to winter season at all the sites because of high temperature & intense sunlight. The maximum isoprene emission flux was always observed during afternoon hours in both seasons at all sites. The maximum isoprene concentration was found to be 13.95 ppbv at Biodiversity Park during afternoon time in post monsoon season while the lower concentration was observed as low as 0.07 ppbv at the same location during morning hours in winter season. OFP of isoprene at vegetation sites is very high during post-monsoon because of high concentrations. However, OFP for other traffic tracers were high during winter seasons & at traffic locations. Furthermore, high correlation between isoprene emissions with traffic volume at traffic sites revealed that a noteworthy share of its emission also originates from road traffic.Keywords: biogenic VOCs, isoprene emission, anthropogenic isoprene, urban vegetation
Procedia PDF Downloads 1161079 Impact of Maternal Nationality on Caesarean Section Rate Variation in a High-income Country
Authors: Saheed Shittu, Lolwa Alansari, Fahed Nattouf, Tawa Olukade, Naji Abdallah, Tamara Alshdafat, Sarra Amdouni
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Cesarean sections (CS), a highly regarded surgical intervention for improving fetal-maternal outcomes and serving as an integral part of emergency obstetric services, are not without complications. Although CS has many advantages, it poses significant risks to both mother and child and increases healthcare expenditures in the long run. The escalating global prevalence of CS, coupled with variations in rates among immigrant populations, has prompted an inquiry into the correlation between CS rates and the nationalities of women undergoing deliveries at Al-Wakra Hospital (AWH), Qatar's second-largest public maternity hospital. This inquiry is motivated by the notable CS rate of 36%, deemed high in comparison to the 34% recorded across other Hamad Medical Corporation (HMC) maternity divisions This is Qatar's first comprehensive investigation of Caesarean section rates and nationalities. A retrospective cross-sectional study was conducted, and data for all births delivered in 2019 were retrieved from the hospital's electronic medical records. The CS rate, the crude rate, and adjusted risks of Caesarean delivery for mothers from each nationality were determined. The common indications for CS were analysed based on nationality. The association between nationality and Caesarean rates was examined using binomial logistic regression analysis considering Qatari women as a standard reference group. The correlation between the CS rate in the country of nationality and the observed CS rate in Qatar was also examined using Pearson's correlation. This study included 4,816 births from 69 different nationalities. CS was performed in 1767 women, equating to 36.5%. The nationalities with the highest CS rates were Egyptian (49.6%), Lebanese (45.5%), Filipino and Indian (both 42.2%). Qatari women recorded a CS rate of 33.4%. The major indication for elective CS was previous multiple CS (39.9%) and one prior CS, where the patient declined vaginal birth after the cesarean (VBAC) option (26.8%). A distinct pattern was noticed: elective CS was predominantly performed on Arab women, whereas emergency CS was common among women of Asian and Sub-Saharan African nationalities. Moreover, a significant correlation was found between the CS rates in Qatar and the women's countries of origin. Also, a high CS rate was linked to instances of previous CS. As a result of these insights, strategic interventions were successfully implemented at the facility to mitigate unwarranted CS, resulting in a notable reduction in CS rate from 36.5% in 2019 to 34% in 2022. This proves the efficacy of the meticulously researched approach. The focus has now shifted to reducing primary CS rates and facilitating well-informed decisions regarding childbirth methods.Keywords: maternal nationality, caesarean section rate variation, migrants, high-income country
Procedia PDF Downloads 701078 Entrants’ Knowledge of the Host Country’s Institutional Environments: A Critical Success Factor of International Projects in Emerging Least Developed Countries
Authors: Rameshwar Dahal, S. Ping Ho
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Although the demand for infrastructure development forms a promising market opportunity for international firms, the dominance of informal institutions over formal ones, investors are facing extraordinary institutional challenges when investing in emerging Least Developed Countries (LDCs). We believe that, in emerging LDCs, the project performance heavily depends on how well the entrants respond to the challenges exerted by the host institutional environments. Which primarily depends on how much they learn about the host institution and what strategy they apply in response. In Nepal, almost all international or global infrastructure projects are financed by international financers, so the procurement process of the infrastructure projects financed by foreign agencies is guided by the policies and regulations of the financer. Because of limited resources and the financers’ demand, contractors and consults are procured internationally. Moreover, the resources, including but not limited to construction material, manpower, and equipment, also need to be imported. Therefore, the involvement of international companies as an entrant in global infrastructure projects of LDCs is obvious. In a global project (GP), participants from different geographical and institutional environments hold different beliefs and have disparate interests. Therefore, the entrants face the challenges exerted by the host institutional environments. The entrants must either adapt to the institutions prevailing in the environment or resist the institutional pressures. It is hypothesized that, in emerging LDCs, the project performance heavily depends on how much the entrants learn about the host institutional knowledge and how well they respond to the institutional environments. While it is impossible to generalize the phenomenon and contextual conditions because of their vast diversity, this study has answered why and how participants’ level of institutional knowledge impacts the project's implementation performance. To draw that conclusion, firstly, we explored two typical GPs from Nepal. For this study, the data were collected by conducting interviews and examining the secondary data, such as the project reports published by the financers, project data provided by interviewees, and news reports. In an event analysis, firstly, we identify the sources, causes, or nature of the institutional challenges; secondly, we analyze the entrant’s responses to the exerted challenges and evaluate the impacts of the responses on the overall project performance. In this study, at first, the events occurred during the project implementation process have a causal link with the local institutions that demand the entrants’ response are extracted. Secondly, each event is scrutinized as the critical success factor of the case project. Finally, it is crucially examined whether and what institutional knowledge in these events played a critical role in project success or failure. The results also provide insights into the crucial institutional knowledge in LDCs and the subsequent strategy implications for undertaking projects in LDCs.Keywords: emerging countries, LDC, project management, project performance, institutional knowledge, institutional theory
Procedia PDF Downloads 631077 The Effects of Heavy Metal and Aromatic Hydrocarbon Pollution on Bees
Authors: Katarzyna Zięba, Hajnalka Szentgyörgyi, Paweł Miśkowiec, Agnieszka Moos-Matysik
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Bees are effective pollinators of plants using by humans. However, there is a concern about the fate different species due to their recently decline. Pollution of the environment is described in the literature as one of the causes of this phenomenon. Due to human activities, heavy metals and aromatic hydrocarbons can occur in bee organisms in high concentrations. The presented study aims to provide information on how pollution affects bee quality, taking into account, also the biological differences between various groups of bees. Understanding the consequences of environmental pollution on bees can help to create and promote bee friendly habitats and actions. The analyses were carried out using two contamination gradients with 5 sites on each. The first, mainly heavy metal polluted gradient is stretching approx. 30km from the Bukowno Zinc smelter near Olkusz in the Lesser Poland Voivodship, to the north. The second cuts through the agglomeration of Kraków up to the southern borders of the Ojców National Park. The gradient near Olkusz is a well-described pollution gradient contaminated mainly by zinc, lead, and cadmium. The second gradient cut through the agglomeration of Kraków and end below the Ojców National Park. On each gradient, two bee species were installed: red mason bees (Osmia bicornis) and honey bees (Apis mellifera). Red mason bee is a polylectic, solitary bee species, widely distributed in Poland. Honey bees are a highly social species of bees, with clearly defined casts and roles in the colony. Before installing the bees in the field, samples of imagos of red mason bees and samples of pollen and imagos from each honey bee colony were analysed for zinc, lead cadmium, polycyclic and monocyclic hydrocarbons levels. After collecting the bees from the field, samples of bees and pollen samples for each site were prepared for heavy metal, monocyclic hydrocarbon, and polycyclic hydrocarbon analysis. Analyses of aromatic hydrocarbons were performed with gas chromatography coupled with a headspace sampler (HP 7694E) and mass spectrometer (MS) as detector. Monocyclic compounds were injected into column with headspace sampler while polycyclic ones with manual injector (after solid-liquid extraction with hexane). The heavy metal content (zinc, lead and cadmium) was assessed with flame atomic absorption spectroscopy (FAAS AAnalyst 300 Perkin Elmer spectrometer) according to the methods for honey and bee products described in the literature. Pollution levels found in bee bodies and imago body masses in both species, and proportion of sex in case of red mason bees were correlated with pollution levels found in pollen for each site and colony or trap nest. An attempt to pinpoint the most important form of contamination regarding bee health was also be undertaken based on the achieved results.Keywords: heavy metals, aromatic hydrocarbons, bees, pollution
Procedia PDF Downloads 5081076 Loud Silence: A Situation Analysis of Youth Living with Hearing Impairment in Uganda
Authors: Wandera Stephen Ojumbo
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People living with hearing impairment in Uganda are one of the most excluded minority groups in the country. The Uganda National Association of the Deaf estimates that deaf people make up 3.4% of Uganda’s 43 million people. Deaf Children and youth often appear withdrawn because they face social stigma. In 2009, photojournalist Stephen Wandera Ojumbo conducted an exhibition in Kampala titled “Silent Voices with colourful Hearts” showcasing the life of deaf children at Uganda School for the Deaf, Ntinda, in order to create awareness of their plight, raising funds for the construction of a vocational centre for the deaf that didn’t continue their education due to: lack of funds, non-inclusive educational institutions, and for those who cannot read and write. These children, whose lives were exhibited in 2009, are currently youths. In Uganda, there are just five primary schools for the deaf (three of these are located in Kampala, the capital city), and barely five secondary schools for the deaf. At the moment, some deaf children only receive special needs training equivalent to primary seven levels and the majority don’t make it to secondary school education level due to the fact that English is a second language to them. There is a communication gap between speaking parents and deaf children, which leads to the breakage of family bonds. The deaf youth run away from their homes to form a community where they can communicate freely. Likewise, employment opportunities for the deaf are equally very limited. It’s for this reason that a follow-up photo exhibition was conducted to expose more about what the youthful deaf people and their guardians go through in Uganda to get jobs, live and fit in the community, how they communicate and get understood, bonding with families instead of running away to bond with fellow deaf persons. The photo exhibition under the theme “Loud Silence” was significant in showcasing the ability of deaf youths in Uganda and eliciting solutions to make a more inclusive society for the deaf. It is hoped that partners in development will join in for intervention. The methodology used included individual interviews with the deaf youth and their parents and caretakers; photography at household and community levels; document review at organizations working with the deaf; observations; and key informant interviews with relevant personnel working with the deaf. Some of the major findings include: i) Effective sign language communication is key in deaf education, family bonding, and developing a sense of belonging; ii) Love and intimacy can keep the deaf bound together; iii) Education is important; everybody should struggle even if alone; iv) Games and sports are a unifying factor and most loved among the deaf; and v) better communication skills build confidence in deaf youth. In conclusion, concerted efforts are still needed to make Uganda schools more inclusive for deaf persons. This will enable a secure future for deaf youths.Keywords: deaf, education, excluded, photo exhibition
Procedia PDF Downloads 881075 Effects of a School-based Mindfulness Intervention on Stress Levels and Emotion Regulation of Adolescent Students Enrolled in an Independent School
Authors: Tracie Catlett
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Students enrolled in high-achieving schools are under tremendous pressure to perform at high levels inside and outside the classroom. Achievement pressure is a prevalent source of stress for students enrolled in high-achieving schools, and female students, in particular, experience a higher frequency and higher levels of stress compared to their male peers. The practice of mindfulness in a school setting is one tool that has been linked to improved self-regulation of emotions, increased positive emotions, and stress reduction. A mixed methods randomized pretest-posttest no-treatment control trial evaluated the effects of a six-session mindfulness intervention taught during a regularly scheduled life skills period in an independent day school, one type of high-achieving school. Twenty-nine students in Grades 10 and 11 were randomized by class, where Grade 11 students were in the intervention group (n = 14) and Grade 10 students were in the control group (n = 15). Findings from the study produced mixed results. There was no evidence that the mindfulness program reduced participants’ stress levels and negative emotions. In fact, contrary to what was expected, students enrolled in the intervention group experienced higher levels of stress and increased negative emotions at posttreatment when compared to pretreatment. Neither the within-group nor the between-groups changes in stress level were statistically significant, p > .05, and the between-groups effect size was small, d = .2. The study found evidence that the mindfulness program may have had a positive impact on students’ ability to regulate their emotions. The within-group comparison and the between-groups comparison at posttreatment found that students in the mindfulness course experienced statistically significant improvement in the in their ability to regulate their emotions at posttreatment, p = .009 < .05 and p =. 034 < .05, respectively. The between-groups effect size was medium, d =.7, suggesting that the positive differences in emotion regulation difficulties were substantial and have practical implications. The analysis of gender differences, as they relate to stress and emotions, revealed that female students perceive higher levels of stress and report experiencing stress more often than males. There were no gender differences when analyzing sources of stress experienced by the student participants. Both females and males experience regular achievement pressures related to their school performance and worry about their future, college acceptance, grades, and parental expectations. Females reported an increased awareness of their stress and actively engaged in practicing mindfulness to manage their stress. Students in the treatment group expressed that the practice of mindfulness resulted in feelings of relaxation and calmness.Keywords: achievement pressure, adolescents, emotion regulation, emotions, high-achieving schools, independent schools, mindfulness, negative affect, positive affect, stress
Procedia PDF Downloads 611074 Assessment of Socio-Cultural Sustainability: A Comparative Analysis of Two Neighborhoods in Kolkata Metropolitan Area
Authors: Tanima Bhattacharya, Joy Sen
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To transform a space into a better livable and sustainable zone, United Nations Summit in New York 2015, has decided upon 17 sustainable development goals (SDGs) that approach directly to achieve inclusive, people-centric, sustainable developments. Though sustainability has been majorly constructed by four pillars, namely, Ecological, Economic, Social and Cultural, but it is essentially reduced to economic and ecological consideration in the context of developing countries. Therefore, in most cases planning has reduced its ambit to concentrate around the tangible infrastructure, ignoring the fundamentals of socio-cultural heritage. With the accentuating hype of infrastructural augmentation, lack of emphasis of traditional concerns like ethnicity and social connection have further diluted the situation, disintegrating cultural continuity. As cultural continuity lacks its cohesion, it’s growing absence increasingly acts as a catalyst to degrade the heritage structures, spaces around and linking these structures, and the ability of stakeholders in identifying themselves rooted in that particular space. Hence, this paper will argue that sustainability depends on the people and their interaction with their surroundings, their culture and livelihood. The interaction between people and their surroundings strengthen community building and social interaction that abides by stakeholders reverting back to their roots. To assess the socio-cultural sustainability of the city of Kolkata, two study areas are selected, namely, an old settlement from the northern part of the city of Kolkata (KMA), imbued with social connection, age-old cultural and ethnic bonding and, another cluster of new high-rises coming up in the Newtown area having portions of planned city extension on the eastern side of the city itself. Whereas, Newtown prioritizes the surging post-industrial trends of economic aspiration and ecological aspects of urban sustainability; the former settlements of northern Kolkata still continue to represent the earliest community settlement of the British-colonial-cum native era and even the pre-colonial era, permeated with socio-cultural reciprocation. Thus, to compare and assess the inlayed organizational structure of both the spaces in the two cases, selected areas have been surveyed to portray their current imageability. The argument of this paper is structured in 5parts. First, an introduction of the idea has been forwarded, Secondly, a literature review has been conducted to ground the proposed ideas, Thirdly, methodology has been discussed and appropriate case study areas have been selected, Fourthly, surveys and analyses has been forwarded and lastly, the paper has arrived at a set of conclusions by suggesting a threefold development to create happy, healthy and sustainable community.Keywords: art innovation, current scenario assessment, heritage, imageability, socio-cultural sustainability
Procedia PDF Downloads 1411073 Lifespan Assessment of the Fish Crossing System of Itaipu Power Plant (Brazil/Paraguay) Based on the Reaching of Its Sedimentological Equilibrium Computed by 3D Modeling and Churchill Trapping Efficiency
Authors: Anderson Braga Mendes, Wallington Felipe de Almeida, Cicero Medeiros da Silva
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This study aimed to assess the lifespan of the fish transposition system of the Itaipu Power Plant (Brazil/Paraguay) by using 3D hydrodynamic modeling and Churchill trapping effiency in order to identify the sedimentological equilibrium configuration in the main pond of the Piracema Channel, which is part of a 10 km hydraulic circuit that enables fish migration from downstream to upstream (and vice-versa) the Itaipu Dam, overcoming a 120 m water drop. For that, bottom data from 2002 (its opening year) and 2015 were collected and analyzed, besides bed material at 12 stations to the purpose of identifying their granulometric profiles. The Shields and Yalin and Karahan diagrams for initiation of motion of bed material were used to determine the critical bed shear stress for the sedimentological equilibrium state based on the sort of sediment (grain size) to be found at the bottom once the balance is reached. Such granulometry was inferred by analyzing the grosser material (fine and medium sands) which inflows the pond and deposits in its backwater zone, being adopted a range of diameters within the upper and lower limits of that sand stratification. The software Delft 3D was used in an attempt to compute the bed shear stress at every station under analysis. By modifying the input bathymetry of the main pond of the Piracema Channel so as to the computed bed shear stress at each station fell within the intervals of acceptable critical stresses simultaneously, it was possible to foresee the bed configuration of the main pond when the sedimentological equilibrium is reached. Under such condition, 97% of the whole pond capacity will be silted, and a shallow water course with depths ranging from 0.2 m to 1.5 m will be formed; in 2002, depths ranged from 2 m to 10 m. Out of that water path, the new bottom will be practically flat and covered by a layer of water 0.05 m thick. Thus, in the future the main pond of the Piracema Channel will lack its purpose of providing a resting place for migrating fish species, added to the fact that it may become an insurmountable barrier for medium and large sized specimens. Everything considered, it was estimated that its lifespan, from the year of its opening to the moment of the sedimentological equilibrium configuration, will be approximately 95 years–almost half of the computed lifespan of Itaipu Power Plant itself. However, it is worth mentioning that drawbacks concerning the silting in the main pond will start being noticed much earlier than such time interval owing to the reasons previously mentioned.Keywords: 3D hydrodynamic modeling, Churchill trapping efficiency, fish crossing system, Itaipu power plant, lifespan, sedimentological equilibrium
Procedia PDF Downloads 2331072 Detection of Egg Proteins in Food Matrices (2011-2021)
Authors: Daniela Manila Bianchi, Samantha Lupi, Elisa Barcucci, Sandra Fragassi, Clara Tramuta, Lucia Decastelli
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Introduction: The undeclared allergens detection in food products plays a fundamental role in the safety of the allergic consumer. The protection of allergic consumers is guaranteed, in Europe, by Regulation (EU) No 1169/2011 of the European Parliament, which governs the consumer's right to information and identifies 14 food allergens to be mandatorily indicated on food labels: among these, an egg is included. An egg can be present as an ingredient or as contamination in raw and cooked products. The main allergen egg proteins are ovomucoid, ovalbumin, lysozyme, and ovotransferrin. This study presents the results of a survey conducted in Northern Italy aimed at detecting the presence of undeclared egg proteins in food matrices in the latest ten years (2011-2021). Method: In the period January 2011 - October 2021, a total of 1205 different types of food matrices (ready-to-eat, meats, and meat products, bakery and pastry products, baby foods, food supplements, pasta, fish and fish products, preparations for soups and broths) were delivered to Food Control Laboratory of Istituto Zooprofilattico Sperimentale of Piemonte Liguria and Valle d’Aosta to be analyzed as official samples in the frame of Regional Monitoring Plan of Food Safety or in the contest of food poisoning. The laboratory is ISO 17025 accredited, and since 2019, it has represented the National Reference Centre for the detection in foods of substances causing food allergies or intolerances (CreNaRiA). All samples were stored in the laboratory according to food business operator instructions and analyzed within the expiry date for the detection of undeclared egg proteins. Analyses were performed with RIDASCREEN®FAST Ei/Egg (R-Biopharm ® Italia srl) kit: the method was internally validated and accredited with a Limit of Detection (LOD) equal to 2 ppm (mg/Kg). It is a sandwich enzyme immunoassay for the quantitative analysis of whole egg powder in foods. Results: The results obtained through this study showed that egg proteins were found in 2% (n. 28) of food matrices, including meats and meat products (n. 16), fish and fish products (n. 4), bakery and pastry products (n. 4), pasta (n. 2), preparations for soups and broths (n.1) and ready-to-eat (n. 1). In particular, in 2011 egg proteins were detected in 5% of samples, in 2012 in 4%, in 2013, 2016 and 2018 in 2%, in 2014, 2015 and 2019 in 3%. No egg protein traces were detected in 2017, 2020, and 2021. Discussion: Food allergies occur in the Western World in 2% of adults and up to 8% of children. Allergy to eggs is one of the most common food allergies in the pediatrics context. The percentage of positivity obtained from this study is, however, low. The trend over the ten years has been slightly variable, with comparable data.Keywords: allergens, food, egg proteins, immunoassay
Procedia PDF Downloads 1361071 Young People’s Perceptions of Disability: The New Generation’s View of a Public Seen as Vulnerable and Marginalized
Authors: Ulysse Lecomte, Maryline Thenot
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For a long time, disabled people lived in isolation within the family environment, with little interaction with the outside world and a high risk of social exclusion. However, in a number of countries, progress has been made thanks to changes in legislation on the social integration of disabled people, a significant change in attitudes, and the development of CSR. But the problem of their social, economic, and professional exclusion persists and has been further exacerbated by the COVID-19 pandemic. This societal phenomenon is sufficiently important to be the subject of management science research. We have therefore focused our work on society's current perception of people with disabilities and their possible integration. Our aim is to find out what levers could be put in place to bring about positive change in the situation. We have chosen to focus on the perception of young people in France, who are the new generation responsible for the future of our society and from whom tomorrow's decisionmakers, future employers, and stakeholders who can influence the living conditions of disabled people will be drawn. Our study sample corresponds to the 18-30 age group, which is the population of young adults likely to have sufficient experience and maturity. The aim of this study is not only to find out how this population currently perceives disability but also to identify the factors influencing this perception and the most effective levers for action to act positively on this phenomenon and thus promote better social integration of people with disabilities in the future. The methodology is based on theoretical and empirical research. The literature review includes a historical and etymological approach to disability, a definition of the different concepts of disability, an approach to disability as a vector of social exclusion, and the role of perception and representations in defining the social image of disability. This literature review is followed by an empirical part carried out by means of a questionnaire administered to 110 young people aged 18 to 30. Analysis of our results suggests that, despite a recent improvement, disabled people are still perceived as vulnerable and socially marginalised. The following factors stand out as having a significant influence (positive or negative) on the perception of disability: the individual's familiarity with the 'world of disability', cultural factors, the degree of 'visibility' of the disability and the empathy level of the disabled person him/herself. Others, on the other hand, such as socio-political and economic factors, have little impact on this perception. In addition, it is possible to classify the various levers of action likely to improve the social perception of disability according to their degree of effectiveness. Our study population prioritised training initiatives for the various players and stakeholders (teachers, students, disabled people themselves, companies, sports clubs, etc.). This was followed by communication, ecommunication and media campaigns in favour of disability. Lastly, the sample was judged as 'less effective' positive discrimination actions such as setting a minimum percentage for the representation of disabled people in various fields (studies, employment, politics ...).Keywords: disability, perception, social image, young people, influencing factors, levers for action
Procedia PDF Downloads 321070 Determination of Physical Properties of Crude Oil Distillates by Near-Infrared Spectroscopy and Multivariate Calibration
Authors: Ayten Ekin Meşe, Selahattin Şentürk, Melike Duvanoğlu
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Petroleum refineries are a highly complex process industry with continuous production and high operating costs. Physical separation of crude oil starts with the crude oil distillation unit, continues with various conversion and purification units, and passes through many stages until obtaining the final product. To meet the desired product specification, process parameters are strictly followed. To be able to ensure the quality of distillates, routine analyses are performed in quality control laboratories based on appropriate international standards such as American Society for Testing and Materials (ASTM) standard methods and European Standard (EN) methods. The cut point of distillates in the crude distillation unit is very crucial for the efficiency of the upcoming processes. In order to maximize the process efficiency, the determination of the quality of distillates should be as fast as possible, reliable, and cost-effective. In this sense, an alternative study was carried out on the crude oil distillation unit that serves the entire refinery process. In this work, studies were conducted with three different crude oil distillates which are Light Straight Run Naphtha (LSRN), Heavy Straight Run Naphtha (HSRN), and Kerosene. These products are named after separation by the number of carbons it contains. LSRN consists of five to six carbon-containing hydrocarbons, HSRN consist of six to ten, and kerosene consists of sixteen to twenty-two carbon-containing hydrocarbons. Physical properties of three different crude distillation unit products (LSRN, HSRN, and Kerosene) were determined using Near-Infrared Spectroscopy with multivariate calibration. The absorbance spectra of the petroleum samples were obtained in the range from 10000 cm⁻¹ to 4000 cm⁻¹, employing a quartz transmittance flow through cell with a 2 mm light path and a resolution of 2 cm⁻¹. A total of 400 samples were collected for each petroleum sample for almost four years. Several different crude oil grades were processed during sample collection times. Extended Multiplicative Signal Correction (EMSC) and Savitzky-Golay (SG) preprocessing techniques were applied to FT-NIR spectra of samples to eliminate baseline shifts and suppress unwanted variation. Two different multivariate calibration approaches (Partial Least Squares Regression, PLS and Genetic Inverse Least Squares, GILS) and an ensemble model were applied to preprocessed FT-NIR spectra. Predictive performance of each multivariate calibration technique and preprocessing techniques were compared, and the best models were chosen according to the reproducibility of ASTM reference methods. This work demonstrates the developed models can be used for routine analysis instead of conventional analytical methods with over 90% accuracy.Keywords: crude distillation unit, multivariate calibration, near infrared spectroscopy, data preprocessing, refinery
Procedia PDF Downloads 1311069 Characterization of Anisotropic Deformation in Sandstones Using Micro-Computed Tomography Technique
Authors: Seyed Mehdi Seyed Alizadeh, Christoph Arns, Shane Latham
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Geomechanical characterization of rocks in detail and its possible implications on flow properties is an important aspect of reservoir characterization workflow. In order to gain more understanding of the microstructure evolution of reservoir rocks under stress a series of axisymmetric triaxial tests were performed on two different analogue rock samples. In-situ compression tests were coupled with high resolution micro-Computed Tomography to elucidate the changes in the pore/grain network of the rocks under pressurized conditions. Two outcrop sandstones were chosen in the current study representing a various cementation status of well-consolidated and weakly-consolidated granular system respectively. High resolution images were acquired while the rocks deformed in a purpose-built compression cell. A detailed analysis of the 3D images in each series of step-wise compression tests (up to the failure point) was conducted which includes the registration of the deformed specimen images with the reference pristine dry rock image. Digital Image Correlation (DIC) technique based on the intensity of the registered 3D subsets and particle tracking are utilized to map the displacement fields in each sample. The results suggest the complex architecture of the localized shear zone in well-cemented Bentheimer sandstone whereas for the weakly-consolidated Castlegate sandstone no discernible shear band could be observed even after macroscopic failure. Post-mortem imaging a sister plug from the friable rock upon undergoing continuous compression reveals signs of a shear band pattern. This suggests that for friable sandstones at small scales loading mode may affect the pattern of deformation. Prior to mechanical failure, the continuum digital image correlation approach can reasonably capture the kinematics of deformation. As failure occurs, however, discrete image correlation (i.e. particle tracking) reveals superiority in both tracking the grains as well as quantifying their kinematics (in terms of translations/rotations) with respect to any stage of compaction. An attempt was made to quantify the displacement field in compression using continuum Digital Image Correlation which is based on the reference and secondary image intensity correlation. Such approach has only been previously applied to unconsolidated granular systems under pressure. We are applying this technique to sandstones with various degrees of consolidation. Such element of novelty will set the results of this study apart from previous attempts to characterize the deformation pattern in consolidated sands.Keywords: deformation mechanism, displacement field, shear behavior, triaxial compression, X-ray micro-CT
Procedia PDF Downloads 1901068 Hampering The 'Right to Know': Consequences of the Excessive Interpretation of the Notion of Exemption from the Right to Information
Authors: Tomasz Lewinski
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The right to know becomes gradually recognised as an increasing number of states adopts national legislations regarding access to state-held information. Laws differ from each other in the scope of the right to information (hereinafter: RTI). In all regimes of RTI, there are exceptions from the general notion of the right. States’ authorities too often use exceptions to justify refusals to requests for state-held information. This paper sets out how states hamper RTI basing on the notion of exception and by not providing an effective procedure that could redress unlawful denials. This paper bases on two selected examples of RTI incorporation into the national legal regime, United Kingdom, and South Africa. It succinctly outlines the international standard given in Article 19 of the International Covenant on Civil and Political Rights (hereinafter: ICCPR) and its influence on the RTI in selected countries. It shortly demonstrates as a background to further analysis the Human Rights Committee’s jurisprudence and standards articulated by successive Special Rapporteurs on freedom of opinion and expression. Subsequently, it presents a brief comparison of these standards with the regional standards, namely the African Charter on Human and Peoples' Rights and the European Convention on Human Rights. It critically discusses the regimes of exceptions in RTI legislations in respective national laws. It shows how excessive these regimes are, what implications they have for the transparency in general. Also, the objective is to divide exceptions enumerated in legislations of selected states in relation to exceptions provided in Article 19 of the ICCPR. Basing on the established division of exceptions by its natures, it compares both regimes of exceptions related to the principle of national security. That is to compare jurisprudence of domestic courts, and overview practices of states’ authorities applied to RTI requests. The paper evaluates remedies available in legislations, including contexts of the length and costs of the subsequent proceedings. This provides a general assessment of the given mechanisms and present potential risks of its ineffectiveness. The paper relies on examination of the national legislations, comments of the credible non-governmental organisations (e.g. The Public's Right to Know Principles on Freedom of Information Legislation by the Article 19, The Tshwane Principles on National Security and the Right to Information), academics and also the research of the relevant judgements delivered by domestic and international courts. Conclusion assesses whether selected countries’ legislations go in line with international law and trends, whether the jurisprudence of the regional courts provide appropriate benchmarks for national courts to address RTI issues effectively. Furthermore, it identifies the largest disadvantages of current legislations and to what outcomes it leads in domestic courts jurisprudences. In the end, it provides recommendations and policy arguments for states to improve transparency and support local organisations in their endeavours to establish more transparent states and societies.Keywords: access to information, freedom of information, national security, right to know, transparency
Procedia PDF Downloads 2131067 Stability in Slopes Related to Expansive Soils
Authors: Ivelise M. Strozberg, Lucas O. Vale, Maria V. V. Morais
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Expansive soils are characterized by their significant volumetric variations, tending to suffer an increase of this volume when added water in their voids and a decrease of volume when this water is removed. The parameters of resistance (especially the angle of friction, cohesion and specific weight) of expansive or non-expansive soils of the same field present differences, as found in laboratory tests. What is expected is that, through this research, demonstrate that this variation directly affects the results of the calculation of factors of safety for slope stability. The expansibility due to specific clay minerals such as montmorillonites and vermiculites is the most common form of expansion of soils or rocks, causing expansion pressures. These pressures can become an aggravating problem in regions across the globe that, when not previously studied, may present high risks to the enterprise, such as cracks, fissures, movements in structures, breaking of retaining walls, drilling of wells, among others. The study provides results based on analyzes carried out in the Slide 2018 software belonging to the Rocsience group, where the software is a two-dimensional equilibrium slope stability program that calculates the factor of safety or probability of failure of certain surfaces composed of soils or rocks (or both, depending on the situation), - through the methods of: Bishop simplified, Fellenius and Janbu corrected. This research compares the factors of safety of a homogeneous earthfill dam geometry, analysed for operation and end-of-construction situations, having a height of approximately 35 meters, with a slope of 1.5: 1 in the slope downstream and 2: 1 on the upstream slope. As the water level is 32.73m high and the water table is drawn automatically by the Slide program using the finite element method for the operating situation, considering two hypotheses for the use of materials - the first with soils with characteristics of expansion and the second with soils without expansibility. For this purpose, soil samples were collected from the region of São Bento do Una - Pernambuco, Brazil and taken to the soil mechanics laboratory to characterize and determine the percentage of expansibility. There were found 2 types of soils in that area: 1 site of expansive soils (8%) and another with non- expansive ones. Based on the results found, the analysis of the values of factors of safety indicated, both upstream and downstream slopes, the highest values were obtained in the case where there is no presence of materials with expansibility resulting, for one of the situations, values of 1.353 (Fellenius), 1,295 (Janbu corrected) and 1,409 (Bishop simplified). There is a considerable drop in safety factors in cases where soils are potentially expansive, resulting in values for the same situation of 0.859 (Fellenius), 0.809 (Janbu corrected) and 0.842 (Bishop simplified), in the case of higher expansibility (8 %). This shows that the expansibility is a determinant factor in the fall of resistance of soil, determined by the factors of cohesion and angle of friction.Keywords: dam. slope. software. swelling soil
Procedia PDF Downloads 1221066 Digital Advance Care Planning and Directives: Early Observations of Adoption Statistics and Responses from an All-Digital Consumer-Driven Approach
Authors: Robert L. Fine, Zhiyong Yang, Christy Spivey, Bonnie Boardman, Maureen Courtney
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Importance: Barriers to traditional advance care planning (ACP) and advance directive (AD) creation have limited the promise of ACP/AD for individuals and families, the healthcare team, and society. Reengineering ACP by using a web-based, consumer-driven process has recently been suggested. We report early experience with such a process. Objective: Begin to analyze the potential of the creation and use of ACP/ADs as generated by a consumer-friendly, digital process by 1) assessing the likelihood that consumers would create ACP/ADs without structured intervention by medical or legal professionals, and 2) analyzing the responses to determine if the plans can help doctors better understand a person’s goals, preferences, and priorities for their medical treatments and the naming of healthcare agents. Design: The authors chose 900 users of MyDirectives.com, a digital ACP/AD tool, solely based on their state of residence in order to achieve proportional representation of all 50 states by population size and then reviewed their responses, summarizing these through descriptive statistics including treatment preferences, demographics, and revision of preferences. Setting: General United States population. Participants: The 900 participants had an average age of 50.8 years (SD = 16.6); 84.3% of the men and 91% of the women were in self-reported good health when signing their ADs. Main measures: Preferences regarding the use of life-sustaining treatments, where to spend final days, consulting a supportive and palliative care team, attempted cardiopulmonary resuscitation (CPR), autopsy, and organ and tissue donation. Results: Nearly 85% of respondents prefer cessation of life-sustaining treatments during their final days whenever those may be, 76% prefer to spend their final days at home or in a hospice facility, and 94% wanted their future doctors to consult a supportive and palliative care team. 70% would accept attempted CPR in certain limited circumstances. Most respondents would want an autopsy under certain conditions, and 62% would like to donate their organs. Conclusions and relevance: Analysis of early experience with an all-digital web-based ACP/AD platform demonstrates that individuals from a wide range of ages and conditions can engage in an interrogatory process about values, goals, preferences, and priorities for their medical treatments by developing advance directives and easily make changes to the AD created. Online creation, storage, and retrieval of advance directives has the potential to remove barriers to ACP/AD and, thus, to further improve patient-centered end-of-life care.Keywords: Advance Care Plan, Advance Decisions, Advance Directives, Consumer; Digital, End of Life Care, Goals, Living Wills, Prefences, Universal Advance Directive, Statements
Procedia PDF Downloads 3271065 Quality of Service of Transportation Networks: A Hybrid Measurement of Travel Time and Reliability
Authors: Chin-Chia Jane
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In a transportation network, travel time refers to the transmission time from source node to destination node, whereas reliability refers to the probability of a successful connection from source node to destination node. With an increasing emphasis on quality of service (QoS), both performance indexes are significant in the design and analysis of transportation systems. In this work, we extend the well-known flow network model for transportation networks so that travel time and reliability are integrated into the QoS measurement simultaneously. In the extended model, in addition to the general arc capacities, each intermediate node has a time weight which is the travel time for per unit of commodity going through the node. Meanwhile, arcs and nodes are treated as binary random variables that switch between operation and failure with associated probabilities. For pre-specified travel time limitation and demand requirement, the QoS of a transportation network is the probability that source can successfully transport the demand requirement to destination while the total transmission time is under the travel time limitation. This work is pioneering, since existing literatures that evaluate travel time reliability via a single optimization path, the proposed QoS focuses the performance of the whole network system. To compute the QoS of transportation networks, we first transfer the extended network model into an equivalent min-cost max-flow network model. In the transferred network, each arc has a new travel time weight which takes value 0. Each intermediate node is replaced by two nodes u and v, and an arc directed from u to v. The newly generated nodes u and v are perfect nodes. The new direct arc has three weights: travel time, capacity, and operation probability. Then the universal set of state vectors is recursively decomposed into disjoint subsets of reliable, unreliable, and stochastic vectors until no stochastic vector is left. The decomposition is made possible by applying existing efficient min-cost max-flow algorithm. Because the reliable subsets are disjoint, QoS can be obtained directly by summing the probabilities of these reliable subsets. Computational experiments are conducted on a benchmark network which has 11 nodes and 21 arcs. Five travel time limitations and five demand requirements are set to compute the QoS value. To make a comparison, we test the exhaustive complete enumeration method. Computational results reveal the proposed algorithm is much more efficient than the complete enumeration method. In this work, a transportation network is analyzed by an extended flow network model where each arc has a fixed capacity, each intermediate node has a time weight, and both arcs and nodes are independent binary random variables. The quality of service of the transportation network is an integration of customer demands, travel time, and the probability of connection. We present a decomposition algorithm to compute the QoS efficiently. Computational experiments conducted on a prototype network show that the proposed algorithm is superior to existing complete enumeration methods.Keywords: quality of service, reliability, transportation network, travel time
Procedia PDF Downloads 2211064 Treatment of Onshore Petroleum Drill Cuttings via Soil Washing Process: Characterization and Optimal Conditions
Authors: T. Poyai, P. Painmanakul, N. Chawaloesphonsiya, P. Dhanasin, C. Getwech, P. Wattana
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Drilling is a key activity in oil and gas exploration and production. Drilling always requires the use of drilling mud for lubricating the drill bit and controlling the subsurface pressure. As drilling proceeds, a considerable amount of cuttings or rock fragments is generated. In general, water or Water Based Mud (WBM) serves as drilling fluid for the top hole section. The cuttings generated from this section is non-hazardous and normally applied as fill materials. On the other hand, drilling the bottom hole to reservoir section uses Synthetic Based Mud (SBM) of which synthetic oils are composed. The bottom-hole cuttings, SBM cuttings, is regarded as a hazardous waste, in accordance with the government regulations, due to the presence of hydrocarbons. Currently, the SBM cuttings are disposed of as an alternative fuel and raw material in cement kiln. Instead of burning, this work aims to propose an alternative for drill cuttings management under two ultimate goals: (1) reduction of hazardous waste volume; and (2) making use of the cleaned cuttings. Soil washing was selected as the major treatment process. The physiochemical properties of drill cuttings were analyzed, such as size fraction, pH, moisture content, and hydrocarbons. The particle size of cuttings was analyzed via light scattering method. Oil present in cuttings was quantified in terms of total petroleum hydrocarbon (TPH) through gas chromatography equipped with flame ionization detector (GC-FID). Other components were measured by the standard methods for soil analysis. Effects of different washing agents, liquid-to-solid (L/S) ratio, washing time, mixing speed, rinse-to-solid (R/S) ratio, and rinsing time were also evaluated. It was found that drill cuttings held the electrical conductivity of 3.84 dS/m, pH of 9.1, and moisture content of 7.5%. The TPH in cuttings existed in the diesel range with the concentration ranging from 20,000 to 30,000 mg/kg dry cuttings. A majority of cuttings particles held a mean diameter of 50 µm, which represented silt fraction. The results also suggested that a green solvent was considered most promising for cuttings treatment regarding occupational health, safety, and environmental benefits. The optimal washing conditions were obtained at L/S of 5, washing time of 15 min, mixing speed of 60 rpm, R/S of 10, and rinsing time of 1 min. After washing process, three fractions including clean cuttings, spent solvent, and wastewater were considered and provided with recommendations. The residual TPH less than 5,000 mg/kg was detected in clean cuttings. The treated cuttings can be then used for various purposes. The spent solvent held the calorific value of higher than 3,000 cal/g, which can be used as an alternative fuel. Otherwise, the recovery of the used solvent can be conducted using distillation or chromatography techniques. Finally, the generated wastewater can be combined with the produced water and simultaneously managed by re-injection into the reservoir.Keywords: drill cuttings, green solvent, soil washing, total petroleum hydrocarbon (TPH)
Procedia PDF Downloads 1551063 The Properties of Risk-based Approaches to Asset Allocation Using Combined Metrics of Portfolio Volatility and Kurtosis: Theoretical and Empirical Analysis
Authors: Maria Debora Braga, Luigi Riso, Maria Grazia Zoia
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Risk-based approaches to asset allocation are portfolio construction methods that do not rely on the input of expected returns for the asset classes in the investment universe and only use risk information. They include the Minimum Variance Strategy (MV strategy), the traditional (volatility-based) Risk Parity Strategy (SRP strategy), the Most Diversified Portfolio Strategy (MDP strategy) and, for many, the Equally Weighted Strategy (EW strategy). All the mentioned approaches were based on portfolio volatility as a reference risk measure but in 2023, the Kurtosis-based Risk Parity strategy (KRP strategy) and the Minimum Kurtosis strategy (MK strategy) were introduced. Understandably, they used the fourth root of the portfolio-fourth moment as a proxy for portfolio kurtosis to work with a homogeneous function of degree one. This paper contributes mainly theoretically and methodologically to the framework of risk-based asset allocation approaches with two steps forward. First, a new and more flexible objective function considering a linear combination (with positive coefficients that sum to one) of portfolio volatility and portfolio kurtosis is used to alternatively serve a risk minimization goal or a homogeneous risk distribution goal. Hence, the new basic idea consists in extending the achievement of typical risk-based approaches’ goals to a combined risk measure. To give the rationale behind operating with such a risk measure, it is worth remembering that volatility and kurtosis are expressions of uncertainty, to be read as dispersion of returns around the mean and that both preserve adherence to a symmetric framework and consideration for the entire returns distribution as well, but also that they differ from each other in that the former captures the “normal” / “ordinary” dispersion of returns, while the latter is able to catch the huge dispersion. Therefore, the combined risk metric that uses two individual metrics focused on the same phenomena but differently sensitive to its intensity allows the asset manager to express, in the context of an objective function by varying the “relevance coefficient” associated with the individual metrics, alternatively, a wide set of plausible investment goals for the portfolio construction process while serving investors differently concerned with tail risk and traditional risk. Since this is the first study that also implements risk-based approaches using a combined risk measure, it becomes of fundamental importance to investigate the portfolio effects triggered by this innovation. The paper also offers a second contribution. Until the recent advent of the MK strategy and the KRP strategy, efforts to highlight interesting properties of risk-based approaches were inevitably directed towards the traditional MV strategy and SRP strategy. Previous literature established an increasing order in terms of portfolio volatility, starting from the MV strategy, through the SRP strategy, arriving at the EQ strategy and provided the mathematical proof for the “equalization effect” concerning marginal risks when the MV strategy is considered, and concerning risk contributions when the SRP strategy is considered. Regarding the validity of similar conclusions when referring to the MK strategy and KRP strategy, the development of a theoretical demonstration is still pending. This paper fills this gap.Keywords: risk parity, portfolio kurtosis, risk diversification, asset allocation
Procedia PDF Downloads 651062 The Location-Routing Problem with Pickup Facilities and Heterogeneous Demand: Formulation and Heuristics Approach
Authors: Mao Zhaofang, Xu Yida, Fang Kan, Fu Enyuan, Zhao Zhao
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Nowadays, last-mile distribution plays an increasingly important role in the whole industrial chain delivery link and accounts for a large proportion of the whole distribution process cost. Promoting the upgrading of logistics networks and improving the layout of final distribution points has become one of the trends in the development of modern logistics. Due to the discrete and heterogeneous needs and spatial distribution of customer demand, which will lead to a higher delivery failure rate and lower vehicle utilization, last-mile delivery has become a time-consuming and uncertain process. As a result, courier companies have introduced a range of innovative parcel storage facilities, including pick-up points and lockers. The introduction of pick-up points and lockers has not only improved the users’ experience but has also helped logistics and courier companies achieve large-scale economy. Against the backdrop of the COVID-19 of the previous period, contactless delivery has become a new hotspot, which has also created new opportunities for the development of collection services. Therefore, a key issue for logistics companies is how to design/redesign their last-mile distribution network systems to create integrated logistics and distribution networks that consider pick-up points and lockers. This paper focuses on the introduction of self-pickup facilities in new logistics and distribution scenarios and the heterogeneous demands of customers. In this paper, we consider two types of demand, including ordinary products and refrigerated products, as well as corresponding transportation vehicles. We consider the constraints associated with self-pickup points and lockers and then address the location-routing problem with self-pickup facilities and heterogeneous demands (LRP-PFHD). To solve this challenging problem, we propose a mixed integer linear programming (MILP) model that aims to minimize the total cost, which includes the facility opening cost, the variable transport cost, and the fixed transport cost. Due to the NP-hardness of the problem, we propose a hybrid adaptive large-neighbourhood search algorithm to solve LRP-PFHD. We evaluate the effectiveness and efficiency of the proposed algorithm by using instances generated based on benchmark instances. The results demonstrate that the hybrid adaptive large neighbourhood search algorithm is more efficient than MILP solvers such as Gurobi for LRP-PFHD, especially for large-scale instances. In addition, we made a comprehensive analysis of some important parameters (e.g., facility opening cost and transportation cost) to explore their impacts on the results and suggested helpful managerial insights for courier companies.Keywords: city logistics, last-mile delivery, location-routing, adaptive large neighborhood search
Procedia PDF Downloads 781061 Fire Safe Medical Oxygen Delivery for Aerospace Environments
Authors: M. A. Rahman, A. T. Ohta, H. V. Trinh, J. Hyvl
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Atmospheric pressure and oxygen (O2) concentration are critical life support parameters for human-occupied aerospace vehicles and habitats. Various medical conditions may require medical O2; for example, the American Medical Association has determined that commercial air travel exposes passengers to altitude-related hypoxia and gas expansion. It may cause some passengers to experience significant symptoms and medical complications during the flight, requiring supplemental medical-grade O2 to maintain adequate tissue oxygenation and prevent hypoxemic complications. Although supplemental medical grade O2 is a successful lifesaver for respiratory and cardiac failure, O2-enriched exhaled air can contain more than 95 % O2, increasing the likelihood of a fire. In an aerospace environment, a localized high concentration O2 bubble forms around a patient being treated for hypoxia, increasing the cabin O2 beyond the safe limit. To address this problem, this work describes a medical O2 delivery system that can reduce the O2 concentration from patient-exhaled O2-rich air to safe levels while maintaining the prescribed O2 administration to the patient. The O2 delivery system is designed to be a part of the medical O2 kit. The system uses cationic multimetallic cobalt complexes to reversibly, selectively, and stoichiometrically chemisorb O2 from the exhaled air. An air-release sub-system monitors the exhaled air, and as soon the O2 percentage falls below 21%, the air is released to the room air. The O2-enriched exhaled air is channeled through a layer of porous, thin-film heaters coated with the cobalt complex. The complex absorbs O2, and when saturated, the complex is heated to 100°C using the thin-film heater. Upon heating, the complex desorbs O2 and is once again ready to absorb or remove the excess O2 from exhaled air. The O2 absorption is a sub-second process, and desorption is a multi-second process. While heating at 0.685 °C/sec, the complex desorbs ~90% O2 in 110 sec. These fast reaction times mean that a simultaneous absorb/desorb process in the O2 delivery system will create a continuous absorption of O2. Moreover, the complex can concentrate O2 by a factor of 160 times that in air and desorb over 90% of the O2 at 100°C. Over 12 cycles of thermogravimetry measurement, less than 0.1% decrease in reversibility in O2 uptake was observed. The 1 kg complex can desorb over 20L of O2, so simultaneous O2 desorption by 0.5 kg of complex and absorption by 0.5 kg of complex can potentially continuously remove 9L/min O2 (~90% desorbed at 100°C) from exhaled air. The complex is synthesized and characterized for reversible O2 absorption and efficacy. The complex changes its color from dark brown to light gray after O2 desorption. In addition to thermogravimetric analysis, the O2 absorption/desorption cycle is characterized using optical imaging, showing stable color changes over ten cycles. The complex was also tested at room temperature in a low O2 environment in its O2 desorbed state, and observed to hold the deoxygenated state under these conditions. The results show the feasibility of using the complex for reversible O2 absorption in the proposed fire safe medical O2 delivery system.Keywords: fire risk, medical oxygen, oxygen removal, reversible absorption
Procedia PDF Downloads 1041060 The Rise of Blue Water Navy and its Implication for the Region
Authors: Riddhi Chopra
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Alfred Thayer Mahan described the sea as a ‘great common,’ which would serve as a medium for communication, trade, and transport. The seas of Asia are witnessing an intriguing historical anomaly – rise of an indigenous maritime power against the backdrop of US domination over the region. As China transforms from an inward leaning economy to an outward-leaning economy, it has become increasingly dependent on the global sea; as a result, we witness an evolution in its maritime strategy from near seas defense to far seas deployment strategies. It is not only patrolling the international waters but has also built a network of civilian and military infrastructure across the disputed oceanic expanse. The paper analyses the reorientation of China from a naval power to a blue water navy in an era of extensive globalisation. The actions of the Chinese have created a zone of high alert amongst its neighbors such as Japan, Philippines, Vietnam and North Korea. These nations are trying to align themselves so as to counter China’s growing brinkmanship, but China has been pursuing claims through a carefully calibrated strategy in the region shunning any coercive measures taken by other forces. If China continues to expand its maritime boundaries, its neighbors – all smaller and weaker Asian nations would be limited to a narrow band of the sea along its coastlines. Hence it is essential for the US to intervene and support its allies to offset Chinese supremacy. The paper intends to provide a profound analysis over the disputes in South China Sea and East China Sea focusing on Philippines and Japan respectively. Moreover, the paper attempts to give an account of US involvement in the region and its alignment with its South Asian allies. The geographic dynamics is said the breed a national coalition dominating the strategic ambitions of China as well as the weak littoral states. China has conducted behind the scenes diplomacy trying to persuade its neighbors to support its position on the territorial disputes. These efforts have been successful in creating fault lines in ASEAN thereby undermining regional integrity to reach a consensus on the issue. Chinese diplomatic efforts have also forced the US to revisit its foreign policy and engage with players like Cambodia and Laos. The current scenario in the SCS points to a strong Chinese hold trying to outspace all others with no regards to International law. Chinese activities are in contrast with US principles like Freedom of Navigation thereby signaling US to take bold actions to prevent Chinese hegemony in the region. The paper ultimately seeks to explore the changing power dynamics among various claimants where a rival superpower like US can pursue the traditional policy of alliance formation play a decisive role in changing the status quo in the arena, consequently determining the future trajectory.Keywords: China, East China Sea, South China Sea, USA
Procedia PDF Downloads 2411059 2,7-Diazaindole as a Photophysical Probe for Excited State Hydrogen/Proton Transfer
Authors: Simran Baweja, Bhavika Kalal, Surajit Maity
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Photoinduced tautomerization reactions have been the centre of attention among the scientific community over the past several decades because of their significance in various biological systems. 7-azaindole (7AI) is considered a model system for DNA base pairing and to understand the role of such tautomerization reactions in mutations. To the best of our knowledge, extensive studies have been carried out on 7-azaindole and its solvent clusters exhibiting proton/ hydrogen transfer in both solution as well as gas phases. Derivatives of the above molecule, like 2,7- and 2,6-diazaindoles are proposed to have even better photophysical properties due to the presence of -aza group on the 2nd position. However, there are studies in the solution phase that suggest the relevance of these molecules, but there are no experimental studies reported in the gas phase yet. In our current investigation, we present the first gas phase spectroscopic data of 2,7-diazaindole (2,7-DAI) and its solvent cluster (2,7-DAI-H2O). In this, we have employed state-of-the-art laser spectroscopic methods such as fluorescence excitation (LIF), dispersed fluorescence (DF), resonant two-photon ionization-time of flight mass spectrometry (2C-R2PI), photoionization efficiency spectroscopy (PIE), IR-UV double resonance spectroscopy, i.e., fluorescence-dip infrared spectroscopy (FDIR) and resonant ion-dip infrared spectroscopy (IDIR) to understand the electronic structure of the molecule. The origin band corresponding to the S1 ← S0 transition of the bare 2,7-DAI is found to be positioned at 33910 cm-1, whereas the origin band corresponding to S1 ← S0 transition of the 2,7-DAI-H2O is positioned at 33074 cm-1. The red-shifted transition in the case of solvent cluster suggests the enhanced feasibility of excited state hydrogen/ proton transfer. The ionization potential for the 2,7-DAI molecule is found to be 8.92 eV which is significantly higher than the previously reported 7AI (8.11 eV) molecule, making it a comparatively complex molecule to study. The ionization potential is reduced by 0.14 eV in the case of 2,7-DAI-H2O (8.78 eV) cluster compared to that of 2,7-DAI. Moreover, on comparison with the available literature values of 7AI, we found the origin band of 2,7-DAI and 2,7-DAI-H2O to be red-shifted by -729 and -280 cm-1 respectively. The ground and excited state N-H stretching frequencies of the 27DAI molecule were determined using fluorescence-dip infrared spectra (FDIR) and resonant ion dip infrared spectroscopy (IDIR), obtained at 3523 and 3467 cm-1, respectively. The lower value of vNH in the electronically excited state of 27DAI implies the higher acidity of the group compared to the ground state. Moreover, we have done extensive computational analysis, which suggests that the energy barrier in the excited state reduces significantly as we increase the number of catalytic solvent molecules (S= H2O, NH3) as well as the polarity of solvent molecules. We found that the ammonia molecule is a better candidate for hydrogen transfer compared to water because of its higher gas-phase basicity. Further studies are underway to understand the excited state dynamics and photochemistry of such N-rich chromophores.Keywords: excited state hydrogen transfer, supersonic expansion, gas phase spectroscopy, IR-UV double resonance spectroscopy, laser induced fluorescence, photoionization efficiency spectroscopy
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