Search results for: carbon nickel

Authors: Feng Wang, Vladislav Vasilyev

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Ferrocene (Fe(C5H5)2, i.e., di-cyclopentadienyle iron (FeCp2) or Fc) is a unique example of ‘wrong but seminal’ in chemistry history. It has significant applications in a number of areas such as homogeneous catalysis, polymer chemistry, molecular sensing, and nonlinear optical materials. However, the ‘molecular carousel’ has been a ‘notoriously difficult example’ and subject to long debate for its conformation and properties. Ferrocene is a dynamic molecule. As a result, understanding of the dynamical properties of ferrocene is very important to understand the conformational properties of Fc. In the present study, molecular dynamic (MD) simulations are performed. In the simulation, we use 5 geometrical parameters to define the overall conformation of Fc and all the rest is a thermal noise. The five parameters are defined as: three parameters d---the distance between two Cp planes, α and δ to define the relative positions of the Cp planes, in which α is the angle of the Cp tilt and δ the angle the two Cp plane rotation like a carousel. Two parameters to position the Fe atom between two Cps, i.e., d1 for Fe-Cp1 and d2 for Fe-Cp2 distances. Our preliminary MD simulation discovered the five parameters behave differently. Distances of Fe to the Cp planes show that they are independent, practically identical without correlation. The relative position of two Cp rings, α, indicates that the two Cp planes are most likely not in a parallel position, rather, they tilt in a small angle α≠ 0°. The mean plane dihedral angle δ ≠ 0°. Moreover, δ is neither 0° nor 36°, indicating under those conditions, Fc is neither in a perfect eclipsed structure nor a perfect staggered structure. The simulations show that when the temperature is above 80K, the conformers are virtually in free rotations, A very interesting result from the MD simulation is the five C-Fe bond distances from the same Cp ring. They are surprisingly not identical but in three groups of 2, 2 and 1. We describe the pentagon formed by five carbon atoms as ‘turtle swimming’ for the motion of the Cp rings of Fc as shown in their dynamical animation video. The Fe- C(1) and Fe-C(2) which are identical as ‘the turtle back legs’, Fe-C(3) and Fe-C(4) which are also identical as turtle front paws’, and Fe-C(5) ---’the turtle head’. Such as ‘turtle swimming’ analog may be able to explain the single substituted derivatives of Fc. Again, the mean Fe-C distance obtained from MD simulation is larger than the quantum mechanically calculated Fe-C distances for eclipsed and staggered Fc, with larger deviation with respect to the eclipsed Fc than the staggered Fc. The same trend is obtained for the five Fe-C-H angles from same Cp ring of Fc. The simulated mean IR spectrum at 7K shows split spectral peaks at approximately 470 cm-1 and 488 cm-1, in excellent agreement with quantum mechanically calculated gas phase IR spectrum for eclipsed Fc. As the temperature increases over 80K, the clearly splitting IR spectrum become a very board single peak. Preliminary MD results will be presented.

Keywords: ferrocene conformation, molecular dynamics simulation, conformer orientation, eclipsed and staggered ferrocene

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Authors: Catalina Iticescu, Lucian P. Georgescu, Mihaela Timofti, Gabriel Murariu

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Since the accumulation of large quantities of sewage sludge is producing serious environmental problems, numerous environmental specialists are looking for solutions to solve this problem. The sewage sludge obtained by treatment of municipal wastewater may be used as fertiliser on agricultural soils because such sludge contains large amounts of nitrogen, phosphorus and organic matter. In many countries, sewage sludge is used instead of chemical fertilizers in agriculture, this being the most feasible method to reduce the increasingly larger quantities of sludge. The use of sewage sludge on agricultural soils is allowed only with a strict monitoring of their physical and chemical parameters, because heavy metals exist in varying amounts in sewage sludge. Exceeding maximum permitted quantities of harmful substances may lead to pollution of agricultural soil and may cause their removal aside because the plants may take up the heavy metals existing in soil and these metals will most probably be found in humans and animals through food. The sewage sludge analyzed for the present paper was extracted from the Wastewater Treatment Station (WWTP) Galati, Romania. The physico-chemical parameters determined were: pH (upH), total organic carbon (TOC) (mg L⁻¹), N-total (mg L⁻¹), P-total (mg L⁻¹), N-NH₄ (mg L⁻¹), N-NO₂ (mg L⁻¹), N-NO₃ (mg L⁻¹), Fe-total (mg L⁻¹), Cr-total (mg L⁻¹), Cu (mg L⁻¹), Zn (mg L⁻¹), Cd (mg L⁻¹), Pb (mg L⁻¹), Ni (mg L⁻¹). The determination methods were electrometrical (pH, C, TSD) - with a portable HI 9828 HANNA electrodes committed multiparameter and spectrophotometric - with a Spectroquant NOVA 60 - Merck spectrophotometer and with specific Merck parameter kits. The tests made pointed out the fact that the sludge analysed is low heavy metal falling within the legal limits, the quantities of metals measured being much lower than the maximum allowed. The results of the tests made to determine the content of nutrients in the sewage sludge have shown that the existing nutrients may be used to increase the fertility of agricultural soils. Other tests were carried out on lands where sewage sludge was applied in order to establish the maximum quantity of sludge that may be used so as not to constitute a source of pollution. The tests were made on three plots: a first batch with no mud and no chemical fertilizers applied, a second batch on which only sewage sludge was applied, and a third batch on which small amounts of chemical fertilizers were applied in addition to sewage sludge. The results showed that the production increases when the soil is treated with sludge and small amounts of chemical fertilizers. Based on the results of the present research, a fertilization plan has been suggested. This plan should be reconsidered each year based on the crops planned, the yields proposed, the agrochemical indications, the sludge analysis, etc.

Keywords: agricultural use, crops, physico–chemical parameters, sewage sludge

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Authors: Frederic Barth, Wouter Vanhoudt, Marc Londo, Jaap C. Jansen, Karine Veum, Javier Castro, Klaus Nürnberger, Matthias Altmann

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Hydrogen is expected to play a key role in the transition towards a low-carbon economy, especially within the transport sector, the energy sector and the (petro)chemical industry sector. However, the production and use of hydrogen only make sense if the production and transportation are carried out with minimal impact on natural resources, and if greenhouse gas emissions are reduced in comparison to conventional hydrogen or conventional fuels. The CertifHy project, supported by a wide range of key European industry leaders (gas companies, chemical industry, energy utilities, green hydrogen technology developers and automobile manufacturers, as well as other leading industrial players) therefore aims to: 1. Define a widely acceptable definition of green hydrogen. 2. Determine how a robust Guarantee of Origin (GoO) scheme for green hydrogen should be designed and implemented throughout the EU. It is divided into the following work packages (WPs). 1. Generic market outlook for green hydrogen: Evidence of existing industrial markets and the potential development of new energy related markets for green hydrogen in the EU, overview of the segments and their future trends, drivers and market outlook (WP1). 2. Definition of “green” hydrogen: step-by-step consultation approach leading to a consensus on the definition of green hydrogen within the EU (WP2). 3. Review of existing platforms and interactions between existing GoO and green hydrogen: Lessons learnt and mapping of interactions (WP3). 4. Definition of a framework of guarantees of origin for “green” hydrogen: Technical specifications, rules and obligations for the GoO, impact analysis (WP4). 5. Roadmap for the implementation of an EU-wide GoO scheme for green hydrogen: the project implementation plan will be presented to the FCH JU and the European Commission as the key outcome of the project and shared with stakeholders before finalisation (WP5 and 6). Definition of Green Hydrogen: CertifHy Green hydrogen is hydrogen from renewable sources that is also CertifHy Low-GHG-emissions hydrogen. Hydrogen from renewable sources is hydrogen belonging to the share of production equal to the share of renewable energy sources (as defined in the EU RES directive) in energy consumption for hydrogen production, excluding ancillary functions. CertifHy Low-GHG hydrogen is hydrogen with emissions lower than the defined CertifHy Low-GHG-emissions threshold, i.e. 36.4 gCO2eq/MJ, produced in a plant where the average emissions intensity of the non-CertifHy Low-GHG hydrogen production (based on an LCA approach), since sign-up or in the past 12 months, does not exceed the emissions intensity of the benchmark process (SMR of natural gas), i.e. 91.0 gCO2eq/MJ.

Keywords: green hydrogen, cross-cutting, guarantee of origin, certificate, DG energy, bankability

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Authors: Xiang Zheng, Zhaoping Zhong

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In this study, Aspen Plus was used to simulate the whole process of biomass conversion to liquid fuel in different ways, and the main results of material and energy flow were obtained. The process optimization and evaluation were carried out on the four routes of cellulosic biomass pyrolysis gasification low-carbon olefin synthesis olefin oligomerization, biomass water pyrolysis and polymerization to jet fuel, biomass fermentation to ethanol, and biomass pyrolysis to liquid fuel. The environmental impacts of three biomass species (poplar wood, corn stover, and rice husk) were compared by the gasification synthesis pathway. The global warming potential, acidification potential, and eutrophication potential of the three biomasses were the same as those of rice husk > poplar wood > corn stover. In terms of human health hazard potential and solid waste potential, the results were poplar > rice husk > corn stover. In the popular pathway, 100 kg of poplar biomass was input to obtain 11.9 kg of aviation coal fraction and 6.3 kg of gasoline fraction. The energy conversion rate of the system was 31.6% when the output product energy included only the aviation coal product. In the basic process of hydrothermal depolymerization process, 14.41 kg aviation kerosene was produced per 100 kg biomass. The energy conversion rate of the basic process was 33.09%, which can be increased to 38.47% after the optimal utilization of lignin gasification and steam reforming for hydrogen production. The total exergy efficiency of the system increased from 30.48% to 34.43% after optimization, and the exergy loss mainly came from the concentration of precursor dilute solution. Global warming potential in environmental impact is mostly affected by the production process. Poplar wood was used as raw material in the process of ethanol production from cellulosic biomass. The simulation results showed that 827.4 kg of pretreatment mixture, 450.6 kg of fermentation broth, and 24.8 kg of ethanol were produced per 100 kg of biomass. The power output of boiler combustion reached 94.1 MJ, the unit power consumption in the process was 174.9 MJ, and the energy conversion rate was 33.5%. The environmental impact was mainly concentrated in the production process and agricultural processes. On the basis of the original biomass pyrolysis to liquid fuel, the enzymatic hydrolysis lignin residue produced by cellulose fermentation to produce ethanol was used as the pyrolysis raw material, and the fermentation and pyrolysis processes were coupled. In the coupled process, 24.8 kg ethanol and 4.78 kg upgraded liquid fuel were produced per 100 kg biomass with an energy conversion rate of 35.13%.

Keywords: biomass conversion, biofuel, process optimization, life cycle assessment

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Authors: Gaweł Magdalena, Lipkowska Anna, Olbert Magdalena, Frąckiewicz Ewelina, Librowski Tadeusz, Nowak Gabriel, Pilc Andrzej

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Heme oxygenase-1 (HO-1), also known as heat shock protein 32 (HSP32), has been shown to be implicated in cytoprotection in various organs. Its activation plays a significant role in acute and chronic inflammation, protecting cells from oxidative injury and apoptosis. This inducible isoform of HO catalyzes the first and rate-limiting step in heme degradation to produce equimolar quantities of biologically active products: carbon monoxide (CO), free iron and biliverdin. CO has been reported to possess anti-apoptotic properties. Moreover, it inhibits the production of proinflammatory cytokines and stimulates the synthesis of the anti-inflammatory interleukin-10 (IL-10), as well as promotes vasodilatation at sites of inflammation. The second product of catalytic HO-1 activity, free cytotoxic iron, is promptly sequestered into the iron storage protein ferritin, which lowers the pro-oxidant state of the cell. The third product, biliverdin, is subsequently converted by biliverdin reductase into the bile pigment bilirubin, the most potent endogenous antioxidant among the constituents of human serum, which modulates immune effector functions and suppresses inflammatory response. Furthermore, being one of the so-called stress proteins, HO-1 adaptively responds to different stressors, such as reactive oxygen species (ROS), inflammatory cytokines and heavy metals and thus protects cells against such conditions as ischemia, hemorrhagic shock, heat shock or hypoxia. It is suggested that pharmacologic modulation of HO-1 may represent an effective strategy for prevention of stress and drug-induced gastrointestinal toxicity. HO-1 is constitutively expressed in normal gastric, intestinal and colonic mucosa and up-regulated during inflammation. It has been proven that HO-1 up-regulated by hemin, heme and cobalt-protoporphyrin ameliorates experimental colitis. In addition, the up-regulation of HO-1 partially explains the mechanism of action of 5-aminosalicylic acid (5-ASA), which is used clinically as an anti-colitis agent. In 2009 Ueda et al. has reported for the first time that mucosal protection by Polaprezinc, a chelate compound of zinc and L-carnosine used as an anti-ulcer drug in Japan, is also attributed to induction of HO-1 in the stomach. Since then, inducers of HO-1 are desired subject of research, as they may constitute therapeutically effective anti-ulcer drugs.

Keywords: heme oxygenase-1, gastric lesions, gastroprotection, Polaprezinc

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Authors: Jos Olijve

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Introduction and Purpose: Endotoxins are found in the outer membrane of gram-negative bacteria and have profound in vitro and in vivo responses. They can trigger strong immune responses and negatively affect various cellar activities particular cells expressing toll-like receptors. They are therefore unwanted contaminants of biomaterials sourced from natural raw materials, and their activity must be as low as possible. Collagen and gelatin are natural extracellular matrix components and have, due to their low allergenic potential, suitable biological properties, and tunable physical characteristics, high potential in biomedical applications. The purpose of this study was to determine the influence of autoclave sterilization of gelatin on physical properties and endotoxin level compared to surfactant purified gelatin. Methods: Type A gelatin from Sigma-Aldrich (G1890) with endotoxin level of 35000 endotoxin units (EU) per gram gelatin and type A gelatins from Rousselot Gent with endotoxin activity of 30000 EU per gram were used. A 10 w/w% G1890 gelatin solution was autoclave sterilized during 30 minutes at 121°C and 1 bar over pressure. The physical properties and the endotoxin level of the sterilized G1890 gelatin were compared to a type A gelatin from Rousselot purified with Triton X100 surfactant. The Triton X100 was added to a concentration of 0.5 w/w% which is above the critical micellar concentration. The gelatin surfactant mixtures were kept for 30-45 minutes under constant stirring at 55-60°C. The Triton X100 was removed by active carbon filtration. The endotoxin levels of the gelatins were measured using the Endozyme recombinant factor C method from Hyglos GmbH (Germany). Results and Discussion: Autoclave sterilization significantly affect the physical properties of gelatin. Molecular weight of G1890 decreased from 140 to 50kDa, and gel strength decreased from 300 to 40g. The endotoxin level of the gelatin reduced after sterilization from 35000 EU/g to levels of 400-500 EU/g. These endotoxin levels are however still far above the upper endotoxin level of 0.05 EU/ml, which resembles 5 EU/g gelatin based on a 1% gelatin solution, to avoid cell proliferation alteration. Molecular weight and gel strength of Rousselot gelatin was not altered after Triton X100 purification and remained 150kDa and 300g respectively. The endotoxin levels of Triton X100 purified Rousselot gelatin was < 5EU/g gelatin. Conclusion: Autoclave sterilization of gelatin is, in comparison to Triton X100 purification, not efficient to inactivate endotoxin levels in gelatin to levels below the upper limit to avoid cell proliferation alteration. Autoclave sterilization gave a significant decrease in molecular weight and gel strength which makes autoclave sterilized gelatin, in comparison to Triton X100 purified gelatin, not suitable for 3D printing.

Keywords: endotoxin, gelatin, molecular weight, sterilization, Triton X100

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Authors: Alexander J. Severinsky

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Radiative forces of greenhouse gases (GHG) increase the temperature of the Earth's surface, more on land, and less in oceans, due to their thermal capacities. Given this inertia, the temperature increase is delayed over time. Air temperature, however, is not delayed as air thermal capacity is much lower. In this study, through analysis and synthesis of multidisciplinary science and data, an estimate of atmospheric temperature increase is made. Then, this estimate is used to shed light on current observations of ice and snow loss, desertification and forest fires, and increased extreme air disturbances. The reason for this inquiry is due to the author’s skepticism that current changes cannot be explained by a "~1 ^oC" global average surface temperature rise within the last 50-60 years. The only other plausible cause to explore for understanding is that of atmospheric temperature rise. The study utilizes an analysis of air temperature rise from three different scientific disciplines: thermodynamics, climate science experiments, and climactic historical studies. The results coming from these diverse disciplines are nearly the same, within ± 1.6%. The direct radiative force of GHGs with a high level of scientific understanding is near 4.7 W/m² on average over the Earth’s entire surface in 2018, as compared to one in pre-Industrial time in the mid-1700s. The additional radiative force of fast feedbacks coming from various forms of water gives approximately an additional ~15 W/m². In 2018, these radiative forces heated the atmosphere by approximately 5.1 ^oC, which will create a thermal equilibrium average ground surface temperature increase of 4.6 ^oC to 4.8 ^oC by the end of this century. After 2018, the temperature will continue to rise without any additional increases in the concentration of the GHGs, primarily of carbon dioxide and methane. These findings of the radiative force of GHGs in 2018 were applied to estimates of effects on major Earth ecosystems. This additional force of nearly 20 W/m² causes an increase in ice melting by an additional rate of over 90 cm/year, green leaves temperature increase by nearly 5 ^oC, and a work energy increase of air by approximately 40 Joules/mole. This explains the observed high rates of ice melting at all altitudes and latitudes, the spread of deserts and increases in forest fires, as well as increased energy of tornadoes, typhoons, hurricanes, and extreme weather, much more plausibly than the 1.5 ^oC increase in average global surface temperature in the same time interval. Planned mitigation and adaptation measures might prove to be much more effective when directed toward the reduction of existing GHGs in the atmosphere.

Keywords: greenhouse radiative force, greenhouse air temperature, greenhouse thermodynamics, greenhouse historical, greenhouse radiative force on ice, greenhouse radiative force on plants, greenhouse radiative force in air

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Authors: Natalia Alzate-Carvajal, Diego A. Acevedo-Guzman, Victor Meza-Laguna, Mario H. Farias, Luis A. Perez-Rey, Edgar Abarca-Morales, Victor A. Garcia-Ramirez, Vladimir A. Basiuk, Elena V. Basiuk

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Direct covalent functionalization of prefabricated free-standing graphene oxide paper (GOP) is considered as the only approach suitable for systematic tuning of thermal, mechanical and electronic characteristics of this important class of carbon nanomaterials. At the same time, the traditional liquid-phase functionalization protocols can compromise physical integrity of the paper-like material up to its total disintegration. To avoid such undesirable effects, we explored the possibility of employing an alternative, solvent-free strategy for facile and nondestructive functionalization of GOP with two representative aliphatic amines, 1-octadecylamine (ODA) and 1,12-diaminododecane (DAD), as well as with two aromatic amines, 1-aminopyrene (AP) and 1,5-diaminonaphthalene (DAN). The functionalization was performed under moderate heating at 150-180 °C in vacuum. Under such conditions, it proceeds through both amidation and epoxy ring opening reactions. Comparative characterization of pristine and amine-functionalized GOP mats was carried out by using Fourier-transform infrared, Raman, and X-ray photoelectron spectroscopy (XPS), thermogravimetric (TGA) and differential thermal analysis, scanning electron and atomic force microscopy (SEM and AFM, respectively). Besides that, we compared the stability in water, wettability, electrical conductivity and elastic (Young's) modulus of GOP mats before and after amine functionalization. The highest content of organic species was obtained in the case of GOP-ODA, followed by GOP-DAD, GOP-AP and GOP-DAN samples. The covalent functionalization increased mechanical and thermal stability of GOP, as well as its electrical conductivity. The magnitude of each effect depends on the particular chemical structure of amine employed, which allows for tuning a given GOP property. Morphological characterization by using SEM showed that, compared to pristine graphene oxide paper, amine-modified GOP mats become relatively ordered layered assemblies, in which individual GO sheets are organized in a near-parallel pattern. Financial support from the National Autonomous University of Mexico (grants DGAPA-IN101118 and IN200516) and from the National Council of Science and Technology of Mexico (CONACYT, grant 250655) is greatly appreciated. The authors also thank David A. Domínguez (CNyN of UNAM) for XPS measurements and Dr. Edgar Alvarez-Zauco (Faculty of Science of UNAM) for the opportunity to use TGA equipment.

Keywords: amines, covalent functionalization, gas-phase, graphene oxide paper

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Authors: Hyuk Sung Yoon, In-Lee Choi, Mohammad Zahirul Islam, Jun Pill Baek, Ho-Min Kang

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The strawberry ‘Maehyang’ cultivated in South Korea has been increased to export to Southeast Asia. The degradation of quality often occurs in strawberries during short export period. Botrytis cinerea has been known to cause major damage to the export strawberries and the disease was caused during shipping and distribution. This study was conducted to find out the sterilized effect of chlorine dioxide(ClO2) gas and high concentration of CO2 gas injection for ‘Maehyang’ strawberry and it was packaged with oxygen transmission rate (OTR) films. The strawberry was harvested at 80% color changed stage and packaged with OTR film and perforated film (control). The treatments were a MAP used by with 20,000 cc·m-2·day·atm OTR film and gas injection in packages. The gas type of ClO2 and CO2 were injected into OTR film packages, and treatments were 6 mg/L ClO2, 15% CO2, and they were combined. The treated strawberries were stored at 3℃ for 30 days. Fresh weight loss rate was less than 1% in all OTR film packages but it was more than 15% in a perforated film treatment that showed severe deterioration of visual quality during storage. Carbon dioxide concentration within a package showed approximately 15% of the maximum CO2 concentration in all treatments except control until the 21st day, it was the tolerated range of maximum CO2 concentration of strawberry in recommended CA or MA conditions. But, it increased to almost 50% on the 30th day. Oxygen concentration showed a decrease down to approximately 0% in all treatments except control for 25 days. Ethylene concentration was shown to be steady until the 17th day, but it quickly increased on the 17th day and dropped down on the final storage day (30th day). All treatments did not show any significant differences in gas treatments. Firmness increased in CO2 (15%) and ClO2 (6mg/L) + CO2 (15%) treatments during storage. It might be the effect of high concentration CO2 known by reducing decay and cell wall degradation. The soluble solid decreased in all treatments during storage. These results were caused to use up the sugar by the increase of respiration during storage. The titratable acidity showed a similarity in all treatments. Incidence of fungi was 0% in CO2 (15%) and ClO2 (6mg/L)+ CO2 (15%), but was more than 20% in a perforated film treatment. Consequently, The result indicates that Chloride Dioxide(ClO2) and high concentration of CO2 inhibited fungi growth. Due to the fact that fresh weight loss rate and incidence of fungi were lower, the ClO2(6mg/L)+ CO2(15%) prove to be most efficient in sterilization. These results suggest that Chloride Dioxide (ClO2) and high concentration of CO2 gas injection treatments were an effective decontamination technique for improving the safety of strawberries.

Keywords: chloride dioxide, high concentration of CO2, modified atmosphere condition, oxygen transmission rate films

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Authors: Mariam Dianat Sabet Gilani, Lars M. Blank, Birgitta E. Ebert

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Plant-derived lupane-type, pentacyclic triterpenoids are biologically active compounds that are highly interesting for applications in medical, pharmaceutical, and cosmetic industries. Due to the low abundance of these valuable compounds in their natural sources, and the environmentally harmful downstream process, alternative production methods, such as microbial cell factories, are investigated. Engineered Saccharomyces cerevisiae strains, harboring the heterologous genes for betulinic acid synthesis, can produce up to 2 g L-1 triterpenoids, showing high potential for large-scale production of triterpenoids. One limitation of the microbial synthesis is the intracellular product accumulation. It not only makes cell disruption a necessary step in the downstream processing but also limits productivity and product yield per cell. To overcome these restrictions, the aim of this study is to develop an in-situ extraction method, which extracts triterpenoids into a second organic phase. Such a continuous or sequential product removal from the biomass keeps the cells in an active state and enables extended production time or biomass recycling. After screening of twelve different solvents, selected based on product solubility, biocompatibility, as well as environmental and health impact, isopropyl myristate (IPM) was chosen as a suitable solvent for in-situ product removal from S. cerevisiae. Impedance-based single-cell analysis and off-gas measurement of carbon dioxide emission showed that cell viability and physiology were not affected by the presence of IPM. Initial experiments demonstrated that after the addition of 20 vol % IPM to cultures in the stationary phase, 40 % of the total produced triterpenoids were extracted from the cells into the organic phase. In future experiments, the application of IPM in a repeated batch process will be tested, where IPM is added at the end of each batch run to remove triterpenoids from the cells, allowing the same biocatalysts to be used in several sequential batch steps. Due to its high biocompatibility, the amount of IPM added to the culture can also be increased to more than 20 vol % to extract more than 40 % triterpenoids in the organic phase, allowing the cells to produce more triterpenoids. This highlights the potential for the development of a continuous large-scale process, which allows biocatalysts to produce intracellular products continuously without the necessity of cell disruption and without limitation of the cell capacity.

Keywords: betulinic acid, biocompatible solvent, in-situ extraction, isopropyl myristate, process development, secondary metabolites, triterpenoids, yeast

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Authors: Mahadehe Hassan

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In most countries manufacturing, trading and distribution of gasoline and diesel fuels belongs to the most important sectors of national economy. For Bangladesh, a robust, well-functioning, secure and smartly managed national fuel distribution chain is an essential precondition for achieving Government top priorities in development and modernization of transportation infrastructure, protection of national environment and population health as well as, very importantly, securing due tax revenue for the State Budget. Bangladesh is a developing country with complex fuel supply network, high fuel taxes incidence and – till now - limited possibilities in application of modern, automated technologies for Government national fuel market control. Such environment allows dishonest physical and legal persons and organized criminals to build and profit from illegal fuel distribution schemes and fuel illicit trade. As a result, the market transparency and the country attractiveness for foreign investments, law-abiding economic operators, national consumers, State Budget and the Government ability to finance development projects, and the country at large suffer significantly. Research shows that over 50% of retail petrol stations in major agglomerations of Bangladesh sell adulterated fuels and/or cheat customers on the real volume of the fuel pumped into their vehicles. Other forms of detected fuel illicit trade practices include misdeclaration of fuel quantitative and qualitative parameters during internal transit and selling of non-declared and smuggled fuels. The aim of the study is to recommend the implementation of a National Fuel Distribution Integrity Program (FDIP) in Bangladesh to address and resolve fuel adulteration and illicit trade problems. The program should be customized according to the specific needs of the country and implemented in partnership with providers of advanced technologies. FDIP should enable and further enhance capacity of respective Bangladesh Government authorities in identification and elimination of all forms of fuel illicit trade swiftly and resolutely. FDIP high-technology, IT and automation systems and secure infrastructures should be aimed at the following areas (1) fuel adulteration, misdeclaration and non-declaration; (2) fuel quality and; (3) fuel volume manipulation at retail level. Furthermore, overall concept of FDIP delivery and its interaction with the reporting and management systems used by the Government shall be aligned with and support objectives of the Vision 2041 and Smart Bangladesh Government programs.

Keywords: fuel adulteration, octane, kerosene, diesel, petrol, pollution, carbon emissions

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Authors: Vojtěch Svěrák

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Climate change ethics have recently shifted away from individualistic paradigms towards concepts of shared or collective responsibility. Despite this evolving trend, a noticeable gap remains: a lack of research exclusively addressing the moral responsibility of specific unorganized social groups. The primary objective of the article is to fill this gap. The article employs the structuralist methodological approach proposed by some feminist philosophers, utilizing structural analysis to explain the existence of social groups. The argument is made for the integration of this framework with the so-called forward-looking Social Connection Model (SCM) of responsibility, which ascribes responsibilities to individuals based on their participation in social structures. The article offers an extension of this model to justify the responsibility of unorganized social groups. The major finding of the study is that although members of unorganized groups are loosely connected, collectively they instantiate specific external social structures, share social positioning, and the notion of responsibility could be based on that. Specifically, if the structure produces harm or perpetuates injustices, and the group both benefits from and possesses the capacity to significantly influence the structure, a greater degree of responsibility should be attributed to the group as a whole. This thesis is applied and justified within the context of climate change, based on the asymmetrical positioning of different social groups. Climate change creates a triple inequality: in contribution, vulnerability, and mitigation. The study posits that different degrees of group responsibility could be drawn from these inequalities. Two social groups serve as a case study for the article: first, the Pakistan lower class, consisting of people living below the national poverty line, with a low greenhouse gas emissions rate, severe climate change-related vulnerability due to the lack of adaptation measures, and with very limited options to participate in the mitigation of climate change. Second, the so-called polluter elite, defined by members' investments in polluting companies and high-carbon lifestyles, thus with an interest in the continuation of structures leading to climate change. The first identified group cannot be held responsible for climate change, but their group interest lies in structural change and should be collectively maintained. On the other hand, the responsibility of the second identified group is significant and can be fulfilled by a justified demand for some political changes. The proposed approach of group responsibility is suggested to help navigate climate justice discourse and environmental policies, thus helping with the sustainability transition.

Keywords: collective responsibility, climate justice, climate change ethics, group responsibility, social ontology, structural analysis

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Authors: Weiliang Gong, Lissa Gomes, Lucile Raymond, Hui Xu, Werner Lutze, Ian L. Pegg

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Alkali-activated materials, particularly geopolymers, have attracted much interest in academia. Commercial applications are on the rise, as well. Geopolymers are produced typically by a reaction of one or two aluminosilicates with an alkaline solution at room temperature. Fly ash is an important aluminosilicate source. However, using low-Ca fly ash, the byproduct of burning hard or black coal reacts and sets slowly at room temperature. The development of mechanical durability, e.g., compressive strength, is slow as well. The use of fly ashes with relatively high contents ( > 6%) of unburned carbon, i.e., high loss on ignition (LOI), is particularly disadvantageous as well. This paper will show to what extent these impediments can be mitigated by mixing the fly ash with one or two more aluminosilicate sources. The fly ash used here is generated at the Orlando power plant (Florida, USA). It is low in Ca ( < 1.5% CaO) and has a high LOI of > 6%. The additional aluminosilicate sources are metakaolin and blast furnace slag. Binary fly ash-metakaolin and ternary fly ash-metakaolin-slag geopolymers were prepared. Properties of geopolymer pastes before and after setting have been measured. Fresh mixtures of aluminosilicates with an alkaline solution were studied by Vicat needle penetration, rheology, and isothermal calorimetry up to initial setting and beyond. The hardened geopolymers were investigated by SEM/EDS and the compressive strength was measured. Initial setting (fluid to solid transition) was indicated by a rapid increase in yield stress and plastic viscosity. The rheological times of setting were always smaller than the Vicat times of setting. Both times of setting decreased with increasing replacement of fly ash with blast furnace slag in a ternary fly ash-metakaolin-slag geopolymer system. As expected, setting with only Orlando fly ash was the slowest. Replacing 20% fly ash with metakaolin shortened the set time. Replacing increasing fractions of fly ash in the binary system by blast furnace slag (up to 30%) shortened the time of setting even further. The 28-day compressive strength increased drastically from < 20 MPa to 90 MPa. The most interesting finding relates to the calorimetric measurements. The use of two or three aluminosilicates generated significantly more heat (20 to 65%) than the calculated from the weighted sum of the individual aluminosilicates. This synergetic heat contributes or may be responsible for most of the increase of compressive strength of our binary and ternary geopolymers. The synergetic heat effect may be also related to increased incorporation of calcium in sodium aluminosilicate hydrate to form a hybrid (N,C)A-S-H) gel. The time of setting will be correlated with heat release and maximum heat flow.

Keywords: alkali-activated materials, binary and ternary geopolymers, blends of fly ash, metakaolin and blast furnace slag, rheology, synergetic heats

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Authors: Chrislaura Carmo, Luca Deiana, Mafalda Laranjo, Abilio Sobral, Armando Cordova

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Photodynamic therapy (PDT) is currently used for the treatment of malignancies and premalignant tumors. It is based on the capture of a photosensitizing molecule (PS) which, when excited by light at a certain wavelength, reacts with oxygen and generates oxidizing species (radicals, singlet oxygen, triplet species) in target tissues, leading to cell death. BODIPY (4,4-difluoro-4-bora-3a,4a-diaza-s-indaceno) derivatives are emerging as important candidates for photosensitizer in photodynamic therapy of cancer cells due to their high triplet quantum yield. Today these dyes are relevant molecules in photovoltaic materials and fluorescent sensors. In this study, it will be demonstrated the possibility that BODIPY can be covalently linked to thioglycolic acid through the click reaction. Thiol−ene click chemistry has become a powerful synthesis method in materials science and surface modification. The design of biobased allyl-terminated precursors with high renewable carbon content for the construction of the thiol-ene polymer networks is essential for sustainable development and green chemistry. The work aims to synthesize the BODIPY (10-(4-(allyloxy) phenyl)-2,8-diethyl-5,5-difluoro-1,3,7,9-tetramethyl-5H-dipyrrolo[1,2-c:2',1'-f] [1,3,2] diazaborinin-4-ium-5-uide) and to click reaction with Thioglycolic acid. BODIPY was synthesized by the condensation reaction between aldehyde and pyrrole in dichloromethane, followed by in situ complexation with BF3·OEt2 in the presence of the base. Then it was functionalized with allyl bromide to achieve the double bond and thus be able to carry out the click reaction. The thiol−ene click was performed using DMPA (2,2-Dimethoxy-2-phenylacetophenone) as a photo-initiator in the presence of UV light (320–500 nm) in DMF at room temperature for 24 hours. Compounds were characterized by standard analytical techniques, including UV-Vis Spectroscopy, 1H, 13C, 19F NMR and mass spectroscopy. The results of this study will be important to link BODIPY to polymers through the thiol group offering a diversity of applications and functionalization. This new molecule can be tested as third-generation photosensitizers, in which the dye is targeted by antibodies or nanocarriers by cells, mainly in cancer cells, PDT and Photodynamic Antimicrobial Chemotherapy (PACT). According to our studies, it was possible to visualize a click reaction between allyl BODIPY and thioglycolic acid. Our team will also test the reaction with other thiol groups for comparison. Further, we will do the click reaction of BODIPY with a natural polymer linked with a thiol group. The results of the above compounds will be tested in PDT assays on various lung cancer cell lines.

Keywords: bodipy, click reaction, thioglycolic acid, allyl, thiol-ene click

Procedia PDF Downloads 132

Authors: Daniel Manaye Kabtamu, Anteneh Wodaje Bayeh

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With the development and utilization of new energy technology, people’s demand for large-scale energy storage system has become increasingly urgent. Vanadium redox flow battery (VRFB) is one of the most promising technologies for grid-scale energy storage applications because of numerous attractive features, such as long cycle life, high safety, and flexible design. However, the relatively low energy efficiency and high production cost of the VRFB still limit its practical implementations. It is of great attention to enhance its energy efficiency and reduce its cost. One of the main components of VRFB that can impressively impact the efficiency and final cost is the electrode materials, which provide the reactions sites for redox couples (V₂₊/V³⁺ and VO²⁺/VO₂⁺). Graphite felt (GF) is a typical carbon-based material commonly employed as electrode for VRFB due to low-cost, good chemical and mechanical stability. However, pristine GF exhibits insufficient wettability, low specific surface area, and poor kinetics reversibility, leading to low energy efficiency of the battery. Therefore, it is crucial to further modify the GF electrode to improve its electrochemical performance towards VRFB by employing active electrocatalysts, such as less expensive metal oxides. This study successfully fabricates low-cost plate-like bismuth vanadate (BiVO₄) material through a simple one-step hydrothermal route, employed as an electrocatalyst to adorn the GF for use as the negative electrode in VRFB. The experimental results show that BiVO₄-3h exhibits the optimal electrocatalytic activity and reversibility for the vanadium redox couples among all samples. The energy efficiency of the VRFB cell assembled with BiVO₄-decorated GF as the negative electrode is found to be 75.42% at 100 mA cm−2, which is about 10.24% more efficient than that of the cell assembled with heat-treated graphite felt (HT-GF) electrode. The possible reasons for the activity enhancement can be ascribed to the existence of oxygen vacancies in the BiVO₄ lattice structure and the relatively high surface area of BiVO₄, which provide more active sites for facilitating the vanadium redox reactions. Furthermore, the BiVO₄-GF electrode obstructs the competitive irreversible hydrogen evolution reaction on the negative side of the cell, and it also has better wettability. Impressively, BiVO₄-GF as the negative electrode shows good stability over 100 cycles. Thus, BiVO₄-GF is a promising negative electrode candidate for practical VRFB applications.

Keywords: BiVO₄ electrocatalyst, electrochemical energy storage, graphite felt, vanadium redox flow battery

Procedia PDF Downloads 1573

Authors: El Khaddam Safaa, Soulaymani Abdelmajid, Mokhtari Abdelghani, Ouammi Lahcen, Rachida Soulaymani-Beincheikh

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The poisonings represent a problem of health in the world and Morocco, The exact dimensions of this phenomenon are still poorly recorded that we see the lack of exhaustive statistical data. The objective of this retrospective study of a series of cases of the poisonings declared at the level of the region of Tadla-Azilal and collected by the Moroccan Poison Control and Pharmacovigilance Center. An epidemiological profile of the poisonings was to raise, to determine the risk factors influencing the vital preview of the poisoned And to follow the evolution of the incidence, the lethality, and the mortality. During the period of study, we collected and analyzed 9303 cases of poisonings by different incriminated toxic products with the exception of the scorpion poisonings. These poisonings drove to 99 deaths. The epidemiological profile which we raised, showed that the poisoned were of any age with an average of 24.62±16.61 years, The sex-ratio (woman/man) was 1.36 in favor of the women. The difference between both sexes is highly significant (χ2 = 210.5; p<0,001). Most of the poisoned which declared to be of urban origin (60.5 %) (χ2=210.5; p<0,001). Carbon monoxide was the most incriminated among the cases of poisonings (24.15 %), them putting in head, followed by some pesticides and farm produces (21.44 %) and food (19.95 %). The analysis of the risk factors showed that the grown-up patients whose age is between 20 and 74 years have twice more risk of evolving towards the death (RR=1,57; IC95 % = 1,03-2,38) than the other age brackets, so the male genital organ was the most exposed (explained) to the death that the female genital organ (RR=1,59; IC95 % = 1,07-2,38) The patients of rural origin had presented 5 times more risk (RR=4,713; IC95 % = 2,543-8,742). Poisoned by the mineral products had presented the maximum of risk on the vital preview death (RR=23,19, IC95 % = 2,39-224,1). The poisonings by pesticides produce a risk of 9 (RR=9,31; IC95 % = 6,10-14,18). The incidence was 3,3 cases of 10000 inhabitants, and the mortality was 0,004 cases of 1000 inhabitants (that is 4 cases by 1000 000 inhabitants). The rate of lethality registered annually was 10.6 %. The evolution of the indicators of health according to the years showed that the rate of statement measured by the incidence increased by a significant way. We also noted an improvement in the coverage which (who) ended up with a decrease in the rate of the lethality and the mortality during last years. The fight anti-toxic is a work of length time. He asks for a lot of work various levels. It is necessary to attack the delay accumulated by our country on the various legal, institutional and technical aspects. The ideal solution is to develop and to set up a national strategy.

Keywords: epidemiology, poisoning, risk factors, indicators of health, Tadla-Azilal grated by anti-toxic fight

Procedia PDF Downloads 365

Authors: E. Salem

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Combustion has been used for a long time as a means of energy extraction. However, in recent years, there has been a further increase in air pollution, through pollutants such as nitrogen oxides, acid etc. In order to solve this problem, there is a need to reduce carbon and nitrogen oxides through learn burning modifying combustors and fuel dilution. A numerical investigation has been done to investigate the effectiveness of several reduced mechanisms in terms of computational time and accuracy, for the combustion of the hydrocarbons/air or diluted with hydrogen in a micro combustor. The simulations were carried out using the ANSYS Fluent 19.1. To validate the results “PREMIX and CHEMKIN” codes were used to calculate 1D premixed flame based on the temperature, composition of burned and unburned gas mixtures. Numerical calculations were carried for several hydrocarbons by changing the equivalence ratios and adding small amounts of hydrogen into the fuel blends then analyzing the flammable limit, the reduction in NOx and CO emissions, then comparing it to experimental data. By solving the conservations equations, several global reduced mechanisms (2-9-12) were obtained. These reduced mechanisms were simulated on a 2D cylindrical tube with dimensions of 40 cm in length and 2.5 cm diameter. The mesh of the model included a proper fine quad mesh, within the first 7 cm of the tube and around the walls. By developing a proper boundary layer, several simulations were performed on hydrocarbon/air blends to visualize the flame characteristics than were compared with experimental data. Once the results were within acceptable range, the geometry of the combustor was modified through changing the length, diameter, adding hydrogen by volume, and changing the equivalence ratios from lean to rich in the fuel blends, the results on flame temperature, shape, velocity and concentrations of radicals and emissions were observed. It was determined that the reduced mechanisms provided results within an acceptable range. The variation of the inlet velocity and geometry of the tube lead to an increase of the temperature and CO2 emissions, highest temperatures were obtained in lean conditions (0.5-0.9) equivalence ratio. Addition of hydrogen blends into combustor fuel blends resulted in; reduction in CO and NOx emissions, expansion of the flammable limit, under the condition of having same laminar flow, and varying equivalence ratio with hydrogen additions. The production of NO is reduced because the combustion happens in a leaner state and helps in solving environmental problems.

Keywords: combustor, equivalence-ratio, hydrogenation, premixed flames

Procedia PDF Downloads 114

Authors: Benukar Biswas, S. Banerjee, P. K. Bandhyopadhyaya, S. K. Patra, S. Sarkar

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Jute can be sown as relay crop in between the lines of 15-20 days old green gram for additional pulse yield without reducing the yield of jute. The main problem of this system is water use efficiency (WUE). The increase in water productivity and reduction in production cost were reported in the zero-tilled crop. The hydrogel can hold water up to 400 times of its weight and can release 95 % of the retained water. The present field study was carried out during 2015-16 at BCKV (tropical sub-humid, 1560 mm annual rainfall, 22058/ N, 88051/ E, 9.75 m AMSL, sandy loam soil, aeric Haplaquept, pH 6.75, organic carbon 5.4 g kg-1, available N 85 kg ha-1, P2O5 15.3 kg ha-1 and K2O 40 kg ha-1) with four levels of irrigation regimes: no irrigation - RF, cumulative pan evaporation 250mm (CPE250), CPE125 and CPE83 and three levels of hydrogel: no hydrogel (H0), 2.5 kg ha-1 (H2.5) and 5 kg ha-1 (H5). Throughout the crop growing period a linear positive relationship remained between Leaf Area Index (LAI) and evapotranspiration rate. The strength of the relationship between ETa and LAI started increasing and reached its peak at 7 WAS (R2=0.78) when green gram was at its maturity, and both the crops covered the nearly entire base area. This relation starts weakening from 13 WAS due to jute leaf shading. A linear relationship between system yield and ET was also obtained in the present study. The variation in system yield might be predicted 75% with ET alone. Effective rainfall was reduced with increasing irrigation frequency due to enhanced water supply in contrast to hydrogel application due to the difference in water storage capacity. Irrigation contributed a major source of variability of ET. Higher irrigation frequency resulted in higher ET loss ranging from 574 mm in RF to 764 mm in CPE83. Hydrogel application also increased water storage on a sustained basis and supplied to crops resulting higher ET from 639 mm in H0 to 671mm in H5. WUE ranged between 0.4 kg m-3 (RF) to 0.63 kg m-3 (CPE83 H5). WUE increased with increased application of irrigation water from 0.42 kg m-3 in RF to 0.57 kg m-3 in CPE 83. Hydrogel application significantly improves the WUE from 0.45 kg m-3 in H0 to 0.50 in H2.5 and 0.54 in H5. Under relatively dry root zone (RF), both evaporation and transpiration remain at suboptimal level resulting in lower ET as well as lower system yield. Green gram – jute relay system can be water use efficient with 38% higher yield with application of hydrogel @ 2.5 kg ha-1 under deficit irrigation regime of CPE 125 over rainfed system without application of the gel. Application of gel conditioner improved water storage, checked excess water loss from the system, and mitigated ET demand of the relay system for a longer time. Hence, irrigation frequency was reduced from five times at CPE 83 to only three times in CPE 125.

Keywords: zero tillage, deficit irrigation, hydrogel, relay system

Procedia PDF Downloads 233

Authors: Seyed Ali Mohammad, Modarres Sanavy, Hamed Keshavarz, Ali Mokhtassi-Bidgoli

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One of the biggest challenges for the current and future generations is to produce sufficient food for the world population with the existing limited available water resources. Peppermint is a specialty crop used for food and medicinal purposes. Its main component is menthol. It is used predominantly for oral hygiene, pharmaceuticals, and foods. Although drought stress is considered as a negative factor in agriculture, being responsible for severe yield losses; medicinal plants grown under semi-arid conditions usually produce higher concentrations of active substances than same species grown under moderate climates. Nitrogen (N) fertilizer management is central to the profitability and sustainability of forage crop production. Sub-optimal N supply will result in poor yields, and excess N application can lead to nitrate leaching and environmental pollution. In order to determine the response of peppermint to drought stress and different fertilizer treatments, a field experiment with peppermint was conducted in a sandy loam soil at a site of the Tarbiat Modares University, Agriculture Faculty, Tehran, Iran. The experiment used a complete randomized block design, with six rates of fertilizer strategies (F1: control, F2: Urea, F3: 75% urea + 25% vermicompost, F4: 50% urea + 50% vermicompost, F5: 25% urea + 75% vermicompost and F6: vermicompost) and three irrigation regime (S1: 45%, S2: 60% and S3: 75% FC) with three replication. The traits such as nitrogen, chlorophyll, carotenoids, anthocyanin, flavonoid and fresh biomass were studied. The results showed that the treatments had a significant effect on the studied traits as drought stress reduced photosynthetic pigment concentration. Also, drought stress reduced fresh yield of peppermint. Non stress condition had the greater amount of chlorophyll and fresh yield more than other irrigation treatments. The highest concentration of chlorophyll and the fresh biomass was obtained in F2 fertilizing treatments. Sever water stress (S1) produced decreased photosynthetic pigment content fresh yield of peppermint. Supply of N could improve photosynthetic capacity by enhancing photosynthetic pigment content. Perhaps application of vermicompost significantly improved the organic carbon, available N, P and K content in soil over urea fertilization alone. To get sustainable production of peppermint, application of vermicompost along with N through synthetic fertilizer is recommended for light textured sandy loam soils.

Keywords: fresh yield, peppermint, synthetic nitrogen, vermicompost, water stress

Procedia PDF Downloads 217

Authors: Adam Majczak, Grzegorz Barański, Marcin Szlachetka

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Environmental considerations necessitate the search for new energy sources. One of the available solutions is a partial replacement of diesel fuel by compressed natural gas (CNG) in the compression ignition engines. This type of the engines is used mainly in vans and trucks. These units are also gaining more and more popularity in the passenger car market. In Europe, this part of the market share reaches 50%. Diesel engines are also used in industry in such vehicles as ship or locomotives. Diesel engines have higher emissions of nitrogen oxides in comparison to spark ignition engines. This can be currently limited by optimizing the combustion process and the use of additional systems such as exhaust gas recirculation or AdBlue technology. As a result of the combustion process of diesel fuel also particulate matter (PM) that are harmful to the human health are emitted. Their emission is limited by the use of a particulate filter. One of the method for toxic components emission reduction may be the use of liquid gas fuel such as propane and butane (LPG) or compressed natural gas (CNG). In addition to the environmental aspects, there are also economic reasons for the use of gaseous fuels to power diesel engines. A total or partial replacement of diesel gas is possible. Depending on the used technology and the percentage of diesel fuel replacement, it is possible to reduce the content of nitrogen oxides in the exhaust gas even by 30%, particulate matter (PM) by 95 % carbon monoxide and by 20%, in relation to original diesel fuel. The research object is prototype gas injector designed for direct injection of compressed natural gas (CNG) in compression ignition engines. The construction of the injector allows for it positioning in the glow plug socket, so that the gas is injected directly into the combustion chamber. The cycle analysis of the four-cylinder Andoria ADCR engine with a capacity of 2.6 dm3 for different crankshaft rotational speeds allowed to determine the necessary time for fuel injection. Because of that, it was possible to determine the required mass flow rate of the injector, for replacing as much of the original fuel by gaseous fuel. To ensure a high value of flow inside the injector, supply pressure equal to 1 MPa was applied. High gas supply pressure requires high value of valve opening forces. For this purpose, an injector with hydraulic control system, using a liquid under pressure for the opening process was designed. On the basis of air pressure measurements in the flow line after the injector, the analysis of opening and closing of the valve was made. Measurements of outflow mass of the injector were also carried out. The results showed that the designed injector meets the requirements necessary to supply ADCR engine by the CNG fuel.

Keywords: CNG, diesel engine, gas flow, gas injector

Procedia PDF Downloads 493

Authors: Matthew E. Potter, Daniel J. Stewart, Lindsay M. Armstrong, Pier J. A. Sazio, Robert R. Raja

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Rising CO₂ levels in the atmosphere means that CO₂ is a highly desirable feedstock. This requires specific catalysts to be designed to activate this inert molecule, combining a catalytic site tailored for CO₂ transformations with a support that can readily adsorb CO₂. Metal organic frameworks (MOFs) are regularly used as CO₂ sorbents. The organic nature of the linker molecules, connecting the metal nodes, offers many post-synthesis modifications to introduce catalytic active sites into the frameworks. However, the metal nodes may be coordinatively unsaturated, allowing them to bind to organic moieties. Imidazoles have shown promise catalyzing the formation of cyclic carbonates from epoxides with CO₂. Typically, this synthesis route employs toxic reagents such as phosgene, liberating HCl. Therefore an alternative route with CO₂ is highly appealing. In this work we design active sites for CO₂ activation, by tethering substituted-imidazole organocatalytic species to the available Cr3+ metal nodes of a Cr-MIL-101 MOF, for the first time, to create a tailored species for carbon capture utilization applications. Our tailored design strategy combining a CO₂ sorbent, Cr-MIL-101, with an anchored imidazole results in a highly active and selective multifunctional catalyst, achieving turnover frequencies of over 750 hr-1. These findings demonstrate the synergy between the MOF framework and imidazoles for CO₂ utilization applications. Further, the effect of substrate variation has been explored yielding mechanistic insights into this process. Through characterization, we show that the structural and compositional integrity of the Cr-MIL-101 has been preserved on functionalizing the imidazoles. Further, we show the binding of the imidazoles to the Cr3+ metal nodes. This can be seen through our EPR study, where the distortion of the Cr3+ on binding to the imidazole shows the CO₂ binding site is close to the active imidazole. This has a synergistic effect, improving catalytic performance. We believe the combination of MOF support and organocatalyst allows many possibilities to generate new multifunctional catalysts for CO₂ utilisation. In conclusion, we have validated our design procedure, combining a known CO₂ sorbent, with an active imidazole species to create a unique tailored multifunctional catalyst for CO₂ utilization. This species achieves high activity and selectivity for the formation of cyclic carbonates and offers a sustainable alternative to traditional synthesis methods. This work represents a unique design strategy for CO₂ utilization while offering exciting possibilities for further work in characterization, computational modelling, and post-synthesis modification.

Keywords: carbonate, catalysis, MOF, utilisation

Procedia PDF Downloads 180

Authors: Anjali Vanpariya, Priyanka Marathey, Sakshum Khanna, Roma Patel, Indrajit Mukhopadhyay

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Silicon (Si) is a promising negative electrode material for lithium-ion batteries (LiBs) due to its low cost, non-toxicity, and a high theoretical capacity of 4200 mAhg⁻¹. The primary challenge of the application of Si-based LiBs is large volume expansion (~ 300%) during the charge-discharge process. Incorporation of graphene, carbon nanotubes (CNTs), morphological control, and nanoparticles was utilized as effective strategies to tackle volume expansion issues. However, molten salt methods can resolve the issue, but high-temperature requirement limits its application. For sustainable and practical approach, room temperature (RT) based methods are essentially required. Use of ionic liquids (ILs) for electrodeposition of Si nanostructures can possibly resolve the issue of temperature as well as greener media. In this work, electrodeposition of Si nanoparticles on gold substrate was successfully carried out in the presence of ILs media, 1-butyl-3-methylimidazolium-bis (trifluoromethyl sulfonyl) imide (BMImTf₂N) at room temperature. Cyclic voltammetry (CV) suggests the sequential reduction of Si⁴⁺ to Si²⁺ and then Si nanoparticles (SiNs). The structure and morphology of the electrodeposited SiNs were investigated by FE-SEM and observed interconnected Si nanoparticles of average particle size ⁓100-200 nm. XRD and XPS data confirm the deposition of Si on Au (111). The first discharge-charge capacity of Si anode material has been found to be 1857 and 422 mAhg⁻¹, respectively, at current density 7.8 Ag⁻¹. The irreversible capacity of the first discharge-charge process can be attributed to the solid electrolyte interface (SEI) formation via electrolyte decomposition, and trapped Li⁺ inserted into the inner pores of Si. Pulverization of SiNs results in the creation of a new active site, which facilitates the formation of new SEI in the subsequent cycles leading to fading in a specific capacity. After 20 cycles, charge-discharge profiles have been stabilized, and a reversible capacity of 150 mAhg⁻¹ is retained. Electrochemical impedance spectroscopy (EIS) data shows the decrease in Rct value from 94.7 to 47.6 kΩ after 50 cycles of charge-discharge, which demonstrates the improvements of the interfacial charge transfer kinetics. The decrease in the Warburg impedance after 50 cycles of charge-discharge measurements indicates facile diffusion in fragmented and smaller Si nanoparticles. In summary, Si nanoparticles deposited on gold substrate using ILs as media and characterized well with different analytical techniques. Synthesized material was successfully utilized for LiBs application, which is well supported by CV and EIS data.

Keywords: silicon nanoparticles, ionic liquid, electrodeposition, cyclic voltammetry, Li-ion battery

Procedia PDF Downloads 125

Authors: Derek Wardle, Tarik Al-Shemmeri, Neil Packer

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This paper presents a small tube/wire type electrostatic precipitator (ESP). In the ESPs present form, particle charging and collecting voltages and airflow rates were individually varied throughout 200 ambient temperature test runs ranging from 10 to 30 kV in increments on 5 kV and 0.5 m/s to 1.5 m/s, respectively. It was repeatedly observed that, at input air velocities of between 0.5 and 0.9 m/s and voltage settings of 20 kV to 30 kV, the collection efficiency remained above 95%. The outcomes of preliminary tests at combustion flue temperatures are, at present, inconclusive although indications are that there is little or no drop in comparable performance during ideal test conditions. A limited set of similar tests was carried out during which the collecting electrode was grounded, having been disconnected from the static generator. The collecting efficiency fell significantly, and for that reason, this approach was not pursued further. The collecting efficiencies during ambient temperature tests were determined by mass balance between incoming and outgoing dry PM. The efficiencies of combustion temperature runs are determined by analysing the difference in opacity of the flue gas at inlet and outlet compared to a reference light source. In addition, an array of Leit tabs (carbon coated, electrically conductive adhesive discs) was placed at inlet and outlet for a number of four-day continuous ambient temperature runs. Analysis of the discs’ contamination was carried out using scanning electron microscopy and ImageJ computer software that confirmed collection efficiencies of over 99% which gave unequivocal support to all the previous tests. The average efficiency for these runs was 99.409%. Emissions collected from a woody biomass combustion unit, classified to a diameter of 100 µm, were used in all ambient temperature trials test runs apart from two which collected airborne dust from within the laboratory. Sawdust and wood pellets were chosen for laboratory and field combustion trials. Video recordings were made of three ambient temperature test runs in which the smoke from a wood smoke generator was drawn through the precipitator. Although these runs were visual indicators only, with no objective other than to display, they provided a strong argument for the device’s claimed efficiency, as no emissions were visible at exit when energised.  The theoretical performance of ESPs, when applied to the geometry and configuration of the tested model, was compared to the actual performance and was shown to be in good agreement with it.

Keywords: electrostatic precipitators, air quality, particulates emissions, electron microscopy, image j

Procedia PDF Downloads 253

Authors: Aloke Bapli, Debabrata Seth

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Graphene oxide (GO) is the two-dimensional (2D) nanoscale allotrope of carbon having several physiochemical properties such as high mechanical strength, high surface area, strong thermal and electrical conductivity makes it an important candidate in various modern applications such as drug delivery, supercapacitors, sensors etc. GO has been used in the photothermal treatment of cancers and Alzheimer’s disease etc. The main idea to choose GO in our work is that it is a surface active molecule, it has a large number of hydrophilic functional groups such as carboxylic acid, hydroxyl, epoxide on its surface and in basal plane. So it can easily interact with organic fluorophores through hydrogen bonding or any other kind of interaction and easily modulate the photophysics of the probe molecules. We have used different spectroscopic techniques for our work. The Ground-state absorption spectra and steady-state fluorescence emission spectra were measured by using UV-Vis spectrophotometer from Shimadzu (model-UV-2550) and spectrofluorometer from Horiba Jobin Yvon (model-Fluoromax 4P) respectively. All the fluorescence lifetime and anisotropy decays were collected by using time-correlated single photon counting (TCSPC) setup from Edinburgh instrument (model: LifeSpec-II, U.K.). Herein, we described the photophysics of a hydrophilic molecule 7-(n,n׀-diethylamino) coumarin-3-carboxylic acid (7-DCCA) in the reverse micelles containing GO. It was observed that photophysics of dye is modulated in the presence of GO compared to photophysics of dye in the absence of GO inside the reverse micelles. Here we have reported the solvent relaxation and rotational relaxation time in GO containing reverse micelle and compare our work with normal reverse micelle system by using 7-DCCA molecule. Normal reverse micelle means reverse micelle in the absence of GO. The absorption maxima of 7-DCCA were blue shifted and emission maxima were red shifted in GO containing reverse micelle compared to normal reverse micelle. The rotational relaxation time in GO containing reverse micelle is always faster compare to normal reverse micelle. Solvent relaxation time, at lower w₀ values, is always slower in GO containing reverse micelle compare to normal reverse micelle and at higher w₀ solvent relaxation time of GO containing reverse micelle becomes almost equal to normal reverse micelle. Here emission maximum of 7-DCCA exhibit bathochromic shift in GO containing reverse micelles compared to that in normal reverse micelles because in presence of GO the polarity of the system increases, as polarity increases the emission maxima was red shifted an average decay time of GO containing reverse micelle is less than that of the normal reverse micelle. In GO containing reverse micelle quantum yield, decay time, rotational relaxation time, solvent relaxation time at λₑₓ=375 nm is always higher than λₑₓ=405 nm, shows the excitation wavelength dependent photophysics of 7-DCCA in GO containing reverse micelles.

Keywords: photophysics, reverse micelle, rotational relaxation, solvent relaxation

Procedia PDF Downloads 155

Authors: Turin Datta, Kisor K. Sahu

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Structural materials used in today’s oil and gas exploration and drilling of both onshore and offshore oil and gas wells must possess superior tensile properties, excellent resistance to corrosive degradation that includes general, localized (pitting and crevice) and environment assisted cracking such as stress corrosion cracking and hydrogen embrittlement. The High Pressure and High Temperature (HPHT) wells are typically operated at temperature and pressure that can exceed 300-3500F and 10,000psi (69MPa) respectively which necessitates the use of exotic materials in these exotic sources of natural resources. This research investigation is focussed on the evaluation of tensile properties and corrosion behavior of AISI 4140 High-Strength Low Alloy Steel (HSLA) possessing tempered martensitic microstructure and Duplex 2205 Stainless Steel (DSS) having austenitic and ferritic phase. The selection of this two alloys are primarily based on economic considerations as 4140 HSLA is cheaper when compared to DSS 2205. Due to the harsh aggressive chemical species encountered in deep oil and gas wells like chloride ions (Cl-), carbon dioxide (CO2), hydrogen sulphide (H2S) along with other mineral organic acids, DSS 2205, having a dual-phase microstructure can mitigate the degradation resulting from the presence of both chloride ions (Cl-) and hydrogen simultaneously. Tensile properties evaluation indicates a ductile failure of DSS 2205 whereas 4140 HSLA exhibit quasi-cleavage fracture due to the phenomenon of ‘tempered martensitic embrittlement’. From the potentiodynamic polarization testing, it is observed that DSS 2205 has higher corrosion resistance than 4140 HSLA; the former exhibits passivity signifying resistance to localized corrosion while the latter exhibits active dissolution in all the environmental parameters space that was tested. From the Scanning Electron Microscopy (SEM) evaluation, it is understood that stable pits appear in DSS 2205 only when the temperature exceeds the critical pitting temperature (CPT). SEM observation of the corroded 4140 HSLA specimen tested in aqueous 3.5 wt.% NaCl solution reveals intergranular cracking which appears due to the adsorption and diffusion of hydrogen during polarization, thus, causing hydrogen-induced cracking/hydrogen embrittlement. General corrosion testing of DSS 2205 in acidic brine (pH~3.0) solution at ambient temperature using coupons indicate no weight loss even after three months whereas the corrosion rate of AISI 4140 HSLA is significantly higher after one month of testing.

Keywords: DSS 2205, polarization, pitting, SEM

Procedia PDF Downloads 264

Authors: Danish Laidin, Peter Gostomski, Aaron Marshall, Carlo Carere

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Groundwater contamination of nitrate (NO3-) is becoming more prevalent in regions of intensive and extensive agricultural activities. Household nitrate removal involves using ion exchange membranes and reverse osmosis (RO) systems, whereas industrial nitrate removal may use organic carbon substrates (e.g. methanol) for heterotrophic microbial denitrification. However, these approaches both require high capital investment and operating costs. In this study, denitrification was demonstrated using bio-electrochemical systems (BESs) inoculated from sediments and microbial enrichment cultures. The BES reactors were operated continuously as microbial electrolytic cells (MECs) with a poised potential of -0.7V and -1.1V vs Ag/AgCl. Three parallel MECs were inoculated using hydrogen-driven denitrifying enrichments, stream sediments, and biofilm harvested from a denitrifying biotrickling filter, respectively. These reactors were continuously operated for over a year as various operating conditions were investigated to determine the optimal conditions for electroactive denitrification. The mass loading rate of nitrate was varied between 10 – 70 mg NO3-/d, and the maximum observed nitrate removal rate was 22 mg NO3- /(cm2∙d) with a current of 2.1 mA. For volumetric load experiments, the dilution rate of 1 mM NO3- feed was varied between 0.01 – 0.1 hr-1 to achieve a nitrate loading rate similar to the mass loading rate experiments. Under these conditions, the maximum rate of denitrification observed was 15.8 mg NO3- /(cm2∙d) with a current of 1.7mA. Hydrogen (H2) was supplied intermittently to investigate the hydrogenotrophic potential of the denitrifying biofilm electrodes. H2 supplementation at 0.1 mL/min resulted in an increase of nitrate removal from 0.3 mg NO3- /(cm2∙d) to 3.4 mg NO3- /(cm2∙d) in the hydrogenotrophically subcultured reactor but had no impact on the reactors which exhibited direct electron transfer properties. Results from this study depict the denitrification performance of the immobilized biofilm electrodes, either by direct electron transfer or hydrogen-driven denitrification, and the contribution of the planktonic cells present in the growth medium. Other results will include the microbial community analysis via 16s rDNA amplicon sequencing, varying the effect of poising cathodic potential from 0.7V to 1.3V vs Ag/AgCl, investigating the potential of using in-situ electrochemically produced hydrogen for autotrophic denitrification and adjusting the conductivity of the feed solution to mimic groundwater conditions. These findings highlight the overall performance of sediment inoculated MECs in removing nitrate and will be used for the future development of sustainable solutions for the treatment of nitrate polluted groundwater.

Keywords: bio-electrochemical systems, groundwater, electroactive denitrification, microbial electrolytic cell

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Authors: Lana Damaj, Vincent Laur, Azar Maalouf, Alexis Chevalier

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Matched termination is an important part of the passive waveguide components. It is typically used at the end of a waveguide transmission line to prevent reflections and improve signal quality. Waveguide terminations (loads) are commonly used in microwave and RF applications. In traditional microwave architectures, usually, waveguide termination consists of a standard rectangular waveguide made by a lossy resistive material, and ended by shorting metallic plate. These types of terminations are used, to dissipate the energy as heat. However, these terminations may increase the size and the weight of the overall system. New alternative solution consists in developing terminations based on 3D-printing of materials. Designing such terminations is very challenging since it should meet the requirements imposed by the system. These requirements include many parameters such as the absorption, the power handling capability in addition to the cost, the size and the weight that have to be minimized. 3D-printing is a shaping process that enables the production of complex geometries. It allows to find best compromise between requirements. In this paper, a comparison study has been made between different existing and new shapes of waveguide terminations. Indeed, 3D printing of absorbers makes it possible to study not only standard shapes (wedge, pyramid, tongue) but also more complex topologies such as exponential ones. These shapes have been designed and simulated using CST MWS®. The loads have been printed using the carbon-filled PolyLactic Acid, conductive PLA from ProtoPasta. Since the terminations has been characterized in the X-band (from 8GHz to 12GHz), the rectangular waveguide standard WR-90 has been selected. The classical wedge shape has been used as a reference. First, all loads have been simulated with the same length and two parameters have been compared: the absorption level (level of |S11|) and the dissipated power density. This study shows that the concave exponential pyramidal shape has the better absorption level and the convex exponential pyramidal shape has the better dissipated power density level. These two loads have been printed in order to measure their properties. A good agreement between the simulated and measured reflection coefficient has been obtained. Furthermore, a study of material structuring based on the honeycomb hexagonal structure has been investigated in order to vary the effective properties. In the final paper, the detailed methodology and the simulated and measured results will be presented in order to show how 3D-printing can allow controlling mass, weight, absorption level and power behaviour.

Keywords: additive manufacturing, electromagnetic composite materials, microwave measurements, passive components, power handling capacity (PHC), 3D-printing

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Authors: Alejandro Ruiz-Olivares, M. del Carmen González-Chávez, Rogelio Carrillo-González, Martha Reyes-Ramos, Javier Suárez Espinosa

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Use of automobiles has increased and proportionally, the demand for batteries to impulse them. When the device is aged, all the battery materials are reused through lead acid battery recycling (LABR). Importation of used lead acid batteries in Mexico has increased in the last years since many recycling factories have been settled in the country. Inadequate disposal of lead-acid battery recycling (LABR) wastes left soil severely polluted with Pb, Cu, and salts (Na+, SO2− 4, PO3− 4). Soil organic amendments may contribute with essential nutrients and sequester (scavenger compounds) metals to allow plant establishment. The objective of this research was to revegetate a former lead-acid battery recycling site aided with organic amendments. Seven tree species (Acacia farnesiana, Casuarina equisetifolia, Cupressus lusitanica, Eucalyptus obliqua, Fraxinus excelsior, Prosopis laevigata and Pinus greggii) and two organic amendments (vermicompost and vermicompost + sawdust mixture) were tested for phytoremediation of a defunct LABR site. Plants were irrigated during the dry season. Monitoring of the soils was carried out during the experiment: Available metals, salts concentrations and their spatial pattern in soil were analyzed. Plant species and amendments were compared through analysis of covariance and longitudinal analysis. High concentrations of extractable (DTPA-TEA-CaCl₂) metals (up to 15,685 mg kg⁻¹ and 478 mg kg⁻¹ for Pb and Cu) and soluble salts (292 mg kg-1 and 23,578 mg kg-1 for PO3− 4and SO2− 4) were found in the soil after three and six months of setting up the experiment. Lead and Cu concentrations were depleted in the rhizosphere after amendments addition. Spatial pattern of PO3− 4, SO2− 4 and DTPA-extractable Pb and Cu changed slightly through time. In spite of extreme soil conditions the plant species planted: A. farnesiana, E. obliqua, C. equisetifolia and F. excelsior had 100% of survival. Available metals and salts differently affected each species. In addition, negative effect on growth due to Pb accumulated in shoots was observed only in C. lusitanica. Many specimens accumulated high concentrations of Pb ( > 1000 mg kg-1) in shoots. C. equisetifolia and C. lusitanica had the best rate of growth. Based on the results, all the evaluated species may be useful for revegetation of Pb-polluted soils. Besides their use in phytoremediation, some ecosystem services can be obtained from the woodland such as encourage wildlife, wood production, and carbon sequestration. Further research should be conducted to analyze these services.

Keywords: heavy metals, inadequate disposal, organic amendments, phytoremediation with trees

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Authors: Samson Obiene, Khamati Shilabukha, Geoffrey Muga, James Kairo

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Mangroves play a vital role in the achievement of multiple goals of global sustainable development (SDG’s), particularly SDG SDG 14 (life under water). Their management, however, is faced with several shortcomings arising from inadequate knowledge on the perceptions of their ecosystem services, hence a need to map mangrove goods and services within SDGs while interrogating the disaggregated perceptions. This study therefore aimed at exploring the parities and disparities in attitudes and perceptions of mangrove ecosystem services among community members of Vanga and the link of the ecosystem services (ESs) to specific SDG targets. The study was based at the Kenya-Tanzania transboundary area in Vanga; where a carbon-offset project on mangroves is being up scaled. Mixed methods approach employing surveys, focus group discussions (FGDs) and reviews of secondary data were used in the study. A two stage cluster samplings was used to select the study population and the sample size. FGDs were conducted purposively selecting active participants in mangrove related activities with distinct socio-demographic characteristics. Sampled respondents comprised of males and females of different occupations and age groups. Secondary data review was used to select specific SDG targets against which mangrove ecosystem services identified through a value chain analysis were mapped. In Vanga, 20 ecosystem services were identified and categorized under supporting, cultural and aesthetic, provisioning and regulating services. According to the findings of this study, 63.9% (95% ci 56.6-69.3) perceived of the ESs as very important for economic development, 10.3% (95% ci 0-21.3) viewed them as important for environmental and ecological development while 25.8% (95% ci 2.2-32.8) were not sure of any role they play in development. In the social-economic disaggregation, ecosystem service values were found to vary with the level of interaction with the ecosystem which depended on gender and other social-economic classes within the study area. The youths, low income earners, women and those with low education levels were also identified as the primary beneficiaries of mangrove ecosystem services. The study also found that of the 17 SDGs, mangroves have a potential of influencing the achievement 12, including, SDGs 1, 2, 3, 4, 6, 8 10, 12, 13, 14, 15 and 17 either directly or indirectly. Generally therefore, the local community is aware of the critical importance mangroves for enhanced livelihood and ecological services but challenges in sustainability still occur as a result the diverse values and of the services and the contradicting interests of the different actors around the ecosystem. It is therefore important to consider parities in values and perception to avoid a ‘tragedy of the commons’ while striving to enhance sustainability of the Mangrove ecosystem.

Keywords: sustainable development, community values, socio-demographics, Vanga, mangrove ecosystem services

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Authors: Steven Hidalgo, Patricio Neumann

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The growth of societies has increased the consumption of raw materials and food obtained from nature. This has influenced the services offered by ecosystems to humans, mainly supply and regulation services. One of the indicators used to evaluate these services is Net Primary Productivity (NPP), which is understood as the energy stored in the form of biomass by primary organisms through the process of photosynthesis and respiration. The variation of NPP by defined area produces changes in the properties of terrestrial and aquatic ecosystems, which alter factors such as biodiversity, nutrient cycling, carbon storage and water quality. The analysis of NPP to evaluate variations in ecosystem services includes harvested NPP (understood as provisioning services), which is the raw material from agricultural systems used by humans as a source of energy and food, and the remaining NPP (expressed as a regulating service) or the amount of biomass that remains in ecosystems after the harvesting process, which is mainly related to factors such as biodiversity. Given that agriculture is a fundamental pillar of Chile's integral development, the purpose of this study is to evaluate provisioning and regulating ecosystem services in the agricultural sector, specifically in cereal production, in the communes of the central-southern regions of Chile through a conceptual framework based on the quantification of the fraction of Human Appropriation of Net Primary Productivity (HANPP) and the fraction remaining in the ecosystems (NPP remaining). A total of 161 communes were analyzed in the regions of O'Higgins, Maule, Ñuble, Bio-Bío, La Araucanía and Los Lagos, which are characterized by having the largest areas planted with cereals. It was observed that the region of La Araucanía produces the greatest amount of dry matter, understood as provisioning service, where Victoria is the commune with the highest cereal production in the country. In addition, the maximum value of HANPP was in the O'Higgins region, highlighting the communes of Coltauco, Quinta de Tilcoco, Placilla and Rengo. On the other hand, the communes of Futrono, Pinto, Lago Ranco and Pemuco, whose cereal production was important during the study, had the highest values of remaining NPP as a regulating service. Finally, an inverse correlation was observed between the provisioning and regulating ecosystem services, i.e., the higher the cereal or dry matter production in a defined area, the lower the net primary production remaining in the ecosystems. Based on this study, future research will focus on the evaluation of ecosystem services associated with other crops, such as forestry plantations, whose activity is an important part of the country's productive sector.

Keywords: provisioning services, regulating services, net primary productivity, agriculture

Procedia PDF Downloads 97