Search results for: organic pollutant degradation

Authors: Md. Hafezur Rahaman, Mohd. Maniruzzaman, Md. Shadiqul Islam, Md. Masud Rana

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With the growth of environmental awareness, enormous researches are running to develop the next generation materials based on sustainability, eco-competence, and green chemistry to preserve and protect the environment. Due to biodegradability and biocompatibility, poly (L-lactic acid) (PLLA) has a great interest in ecological and medical applications. Also, cellulose is one of the most abundant biodegradable, renewable polymers found in nature. It has several advantages such as low cost, high mechanical strength, biodegradability and so on. Recently, an immense deal of attention has been paid for the scientific and technological development of α-cellulose based composite material. PLLA could be used for grafting of cellulose to improve the compatibility prior to the composite preparation. Here it is quite difficult to form a bond between lower hydrophilic molecules like PLLA and α-cellulose. Dimmers and oligomers can easily be grafted onto the surface of the cellulose by ring opening or polycondensation method due to their low molecular weight. In this research, α-cellulose extracted from jute fiber is grafted with oligo(D-lactic acid) (ODLA) via graft polycondensation reaction in presence of para-toluene sulphonic acid and potassium persulphate in toluene at 130°C for 9 hours under 380 mmHg. Here ODLA is synthesized by ring opening polymerization of D-lactides in the presence of stannous octoate (0.03 wt% of lactide) and D-lactic acids at 140°C for 10 hours. Composites of PLLA with ODLA grafted α-cellulose are prepared by solution mixing and film casting method. Confirmation of grafting was carried out through FTIR spectroscopy and SEM analysis. A strongest carbonyl peak of FTIR spectroscopy at 1728 cm⁻¹ of ODLA grafted α-cellulose confirms the grafting of ODLA onto α-cellulose which is absent in α-cellulose. It is also observed from SEM photographs that there are some white areas (spot) on ODLA grafted α-cellulose as compared to α-cellulose may indicate the grafting of ODLA and consistent with FTIR results. Analysis of the composites is carried out by FTIR, SEM, WAXD and thermal gravimetric analyzer. Most of the FTIR characteristic absorption peak of the composites shifted to higher wave number with increasing peak area may provide a confirmation that PLLA and grafted cellulose have better compatibility in composites via intermolecular hydrogen bonding and this supports previously published results. Grafted α-cellulose distributions in composites are uniform which is observed by SEM analysis. WAXD studied show that only homo-crystalline structures of PLLA present in the composites. Thermal stability of the composites is enhanced with increasing the percentages of ODLA grafted α-cellulose in composites. As a consequence, the resultant composites have a resistance toward the thermal degradation. The effects of length of the grafted chain and biodegradability of the composites will be studied in further research.

Keywords: α-cellulose, composite, graft polycondensation, oligo(D-lactic acid), poly(L-lactic acid)

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Authors: Chetna Mohabeer, Luis Reyes, Lokmane Abdelouahed, Bechara Taouk

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In the transition to sustainability and the increasing use of renewable energy, hydrogen will play a key role as an energy carrier. Biomass has the potential to accelerate the realization of hydrogen as a major fuel of the future. Pyro-gasification allows the conversion of organic matter mainly into synthesis gas, or “syngas”, majorly constituted by CO, H2, CH4, and CO2. A second, condensable fraction of biomass pyro-gasification products are “tars”. Under certain conditions, tars may decompose into hydrogen and other light hydrocarbons. These conditions include two types of cracking: homogeneous cracking, where tars decompose under the effect of temperature ( > 1000 °C), and heterogeneous cracking, where catalysts such as olivine, dolomite or biochar are used. The latter process favors cracking of tars at temperatures close to pyro-gasification temperatures (~ 850 °C). Pyro-gasification of biomass coupled with water-gas shift is the most widely practiced process route for biomass to hydrogen today. In this work, an innovating solution will be proposed for this conversion route, in that all the pyro-gasification products, not only methane, will undergo processes that aim to optimize hydrogen production. First, a heterogeneous cracking step was included in the reaction scheme, using biochar (remaining solid from the pyro-gasification reaction) as catalyst and CO2 and H2O as gasifying agents. This process was followed by a catalytic steam methane reforming (SMR) step. For this, a Ni-based catalyst was tested under different reaction conditions to optimize H2 yield. Finally, a water-gas shift (WGS) reaction step with a Fe-based catalyst was added to optimize the H2 yield from CO. The reactor used for cracking was a fluidized bed reactor, and the one used for SMR and WGS was a fixed bed reactor. The gaseous products were analyzed continuously using a µ-GC (Fusion PN 074-594-P1F). With biochar as bed material, it was seen that more H2 was obtained with steam as a gasifying agent (32 mol. % vs. 15 mol. % with CO2 at 900 °C). CO and CH4 productions were also higher with steam than with CO2. Steam as gasifying agent and biochar as bed material were hence deemed efficient parameters for the first step. Among all parameters tested, CH4 conversions approaching 100 % were obtained from SMR reactions using Ni/γ-Al2O3 as a catalyst, 800 °C, and a steam/methane ratio of 5. This gave rise to about 45 mol % H2. Experiments about WGS reaction are currently being conducted. At the end of this phase, the four reactions are performed consecutively, and the results analyzed. The final aim is the development of a global kinetic model of the whole system in a multi-stage fluidized bed reactor that can be transferred on ASPEN PlusTM.

Keywords: multi-staged fluidized bed reactor, pyro-gasification, steam methane reforming, water-gas shift

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Authors: Keigo Ide, Toru Maruyama, Michihiro Ito, Hiroyuki Fujimura, Yoshikatu Nakano, Shoichiro Suda, Sachiyo Aburatani, Haruko Takeyama

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Understanding environmental system is one of the important tasks. In recent years, conservation of coral environments has been focused for biodiversity issues. The damage of coral reef under environmental impacts has been observed worldwide. However, the casual relationship between damage of coral and environmental impacts has not been clearly understood. On the other hand, structure/diversity of marine bacterial community may be relatively robust under the certain strength of environmental impact. To evaluate the coral environment conditions, it is necessary to investigate relationship between marine bacterial composition in coral reef and environmental factors. In this study, the Time Scale Network Analysis was developed and applied to analyze the marine environmental data for investigating the relationship among coral, bacterial community compositions and environmental factors. Seawater samples were collected fifteen times from November 2014 to May 2016 at two locations, Ishikawabaru and South of Sesoko in Sesoko Island, Okinawa. The physicochemical factors such as temperature, photosynthetic active radiation, dissolved oxygen, turbidity, pH, salinity, chlorophyll, dissolved organic matter and depth were measured at the coral reef area. Metagenome and metatranscriptome in seawater of coral reef were analyzed as the biological factors. Metagenome data was used to clarify marine bacterial community composition. In addition, functional gene composition was estimated from metatranscriptome. For speculating the relationships between physicochemical and biological factors, cross-correlation analysis was applied to time scale data. Even though cross-correlation coefficients usually include the time precedence information, it also included indirect interactions between the variables. To elucidate the direct regulations between both factors, partial correlation coefficients were combined with cross correlation. This analysis was performed against all parameters such as the bacterial composition, the functional gene composition and the physicochemical factors. As the results, time scale network analysis revealed the direct regulation of seawater temperature by photosynthetic active radiation. In addition, concentration of dissolved oxygen regulated the value of chlorophyll. Some reasonable regulatory relationships between environmental factors indicate some part of mechanisms in coral reef area.

Keywords: coral environment, marine microbiology, network analysis, omics data analysis

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Authors: Veerle Van Hoeck, Ingrid Somers, Dany Morisset

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Anti-nutritional factors such as non-starch polysaccharides (NSP) are present in viscous cereals used to feed poultry. Therefore, exogenous carbohydrases are commonly added to monogastric feed to degrade these NSP. Our hypothesis is that xylanase not only improves laying hen performance and digestibility but also induces a significant shift in microbial composition within the intestinal tract and, thereby, can cause a prebiotic effect. In this context, a better understanding of whether and how the chicken gut flora can be modulated by xylanase is needed. To do so, in the herein laying hen study, the effects of dietary supplementation of xylanase on performance, digestibility, and cecal microbiome were evaluated. A total of 96 HiSex laying hens was used in this experiment (3 diets and 16 replicates of 2 hens). Xylanase was added to the diets at concentrations of 0, 45,000 (15 g/t XygestTM HT) and 90,000 U/kg (30 g/t Xygest HT). The diets were based on wheat (~55 %), soybean, and sunflower meal. The lowest dosage, 45,000 U/kg, significantly increased average egg weight and improved feed efficiency compared to the control treatment (p < 0.05). Egg quality parameters were significantly improved in the experiment in response to the xylanase addition. For example, during the last 28 days of the trial, the 45,000 U/kg and the 90,000 U/kg treatments exhibited an increase in Haugh units and albumin heights (p < 0.05). Compared with the control, organic matter digestibility and N retention were drastically improved in the 45,000 U/kg treatment group, which implies better nutrient digestibility at this lowest recommended dosage compared to the control (p < 0.05). Furthermore, gross energy and crude fat digestibility were improved significantly for birds fed 90,000 U/kg group compared to the control. Importantly, 16S rRNA gene analysis revealed that xylanase at 45,000 U/kg dosages can exert a prebiotic effect. This conclusion was drawn based on studying the sequence variation in the 16S rRNA gene in order to characterize diverse microbial communities of the cecal content. A significant increase in beneficial bacteria (Lactobacilli spp and Enterococcus casseliflavus) was documented when adding 45,000 U/kg xylanase to the diet of laying hens. In conclusion, dietary supplementation of xylanase, even at the lowest dose of (45,000 U/kg), significantly improved laying hen performance and digestibility. Furthermore, it is generally accepted that a proper bacterial balance between the number of beneficial bacteria and pathogenic bacteria in the intestine is vital for the host. It seems that the xylanase enzyme is able to modulate the laying hen microbiome beneficially and thus exerts a prebiotic effect. This microbiome plasticity in response to the xylanase provides an attractive target for stimulating intestinal health.

Keywords: laying hen, prebiotic, XygestTM HT, xylanase

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Authors: K. Verma, v. S. Moholkar

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In developed countries, water pollution caused by industrial discharge has emerged as a significant environmental concern over the past decades. However, despite ongoing efforts, a fully effective and sustainable remediation strategy has yet to be identified. This paper describes how enzymatic and sonochemical treatments have demonstrated great promise in degrading bio-refractory pollutants. Mainly, a compelling area of interest lies in the combined technique of sono-enzymatic treatment, which has exhibited a synergistic enhancement effect surpassing that of the individual techniques. This study employed the covalent attachment method to immobilize Laccase from Trametes versicolor onto amino-functionalized magnetic Fe₃O₄ nanoparticles. To comprehensively characterize the synthesized free nanoparticles and the laccase-immobilized nanoparticles, various techniques such as X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), scanning electron microscope (SEM), vibrating sample magnetometer (VSM), and surface area through Brunauer-Emmett-Teller (BET) were employed. The size of immobilized Fe₃O₄@Laccase was found to be 60 nm, and the maximum loading of laccase was found to be 24 mg/g of nanoparticle. An investigation was conducted to study the effect of various process parameters, such as immobilized Fe₃O₄ Laccase dose, temperature, and pH, on the % Chemical oxygen demand (COD) removal as a response. The statistical design pinpointed the optimum conditions (immobilized Fe₃O₄ Laccase dose = 1.46 g/L, pH = 4.5, and temperature = 66 oC), resulting in a remarkable 65.58% COD removal within 60 minutes. An even more significant improvement (90.31% COD removal) was achieved with ultrasound-assisted enzymatic reaction utilizing a 10% duty cycle. The investigation of various kinetic models for free and immobilized laccase, such as the Haldane, Yano, and Koga, and Michaelis-Menten, showed that ultrasound application impacted the kinetic parameters Vmax and Km. Specifically, Vmax values for free and immobilized laccase were found to be 0.021 mg/L min and 0.045 mg/L min, respectively, while Km values were 147.2 mg/L for free laccase and 136.46 mg/L for immobilized laccase. The lower Km and higher Vmax for immobilized laccase indicate its enhanced affinity towards the substrate, likely due to ultrasound-induced alterations in the enzyme's confirmation and increased exposure of active sites, leading to more efficient degradation. Furthermore, the toxicity and Liquid chromatography-mass spectrometry (LC-MS) analysis revealed that after the treatment process, the wastewater exhibited 70% less toxicity than before treatment, with over 25 compounds degrading by more than 75%. At last, the prepared immobilized laccase had excellent recyclability retaining 70% activity up to 6 consecutive cycles. A straightforward manufacturing strategy and outstanding performance make the recyclable magnetic immobilized Laccase (Fe₃O₄ Laccase) an up-and-coming option for various environmental applications, particularly in water pollution control and treatment.

Keywords: kinetic, laccase enzyme, sonoenzymatic, ultrasound irradiation

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Authors: Afsheen Aman, Zainab Bibi, Shah Ali Ul Qader

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Introduction: Xylan is a heteropolysaccharide composed of xylose monomers linked together through 1,4 linkages within a complex xylan network. Owing to wide applications of xylan hydrolytic products (xylose, xylobiose and xylooligosaccharide) the researchers are focusing towards the development of various strategies for efficient xylan degradation. One of the most important strategies focused is the use of heat tolerant biocatalysts which acts as strong and specific cleaving agents. Therefore, the exploration of microbial pool from extremely diversified ecosystem is considerably vital. Microbial populations from extreme habitats are keenly explored for the isolation of thermophilic entities. These thermozymes usually demonstrate fast hydrolytic rate, can produce high yields of product and are less prone to microbial contamination. Another possibility of degrading xylan continuously is the use of immobilization technique. The current work is an effort to merge both the positive aspects of thermozyme and immobilization technique. Methodology: Geobacillus stearothermophilus was isolated from soil sample collected near the blast furnace site. This thermophile is capable of producing thermostable endo-β-1,4-xylanase which cleaves xylan effectively. In the current study, this thermozyme was immobilized within a synthetic and a non-synthetic matrice for continuous production of metabolites using entrapment technique. The kinetic parameters of the free and immobilized enzyme were studied. For this purpose calcium alginate and polyacrylamide beads were prepared. Results: For the synthesis of immobilized beads, sodium alginate (40.0 gL-1) and calcium chloride (0.4 M) was used amalgamated. The temperature (50°C) and pH (7.0) optima of immobilized enzyme remained same for xylan hydrolysis however, the enzyme-substrate catalytic reaction time raised from 5.0 to 30.0 minutes as compared to free counterpart. Diffusion limit of high molecular weight xylan (corncob) caused a decline in Vmax of immobilized enzyme from 4773 to 203.7 U min-1 whereas, Km value increased from 0.5074 to 0.5722 mg ml-1 with reference to free enzyme. Immobilized endo-β-1,4-xylanase showed its stability at high temperatures as compared to free enzyme. It retained 18% and 9% residual activity at 70°C and 80°C, respectively whereas; free enzyme completely lost its activity at both temperatures. The Immobilized thermozyme displayed sufficient recycling efficiency and can be reused up to five reaction cycles, indicating that this enzyme can be a plausible candidate in paper processing industry. Conclusion: This thermozyme showed better immobilization yield and operational stability with the purpose of hydrolyzing the high molecular weight xylan. However, the enzyme immobilization properties can be improved further by immobilizing it on different supports for industrial purpose.

Keywords: immobilization, reusability, thermozymes, xylanase

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Authors: Yonwaba Atyosi, Moses Cho, Abel Ramoelo, Nobuhle Majozi, Cecilia Masemola, Yoliswa Mkhize

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Spectroscopy has been widely used to understand the hyperspectral remote sensing of soils. Accurate and efficient measurement of soil moisture is essential for precision agriculture. The aim of this study was to understand the spectral behavior of soil at different soil water content levels and identify the significant spectral bands for soil moisture content retrieval at field-scale. The study consisted of 60 soil samples from a maize farm, divided into four different treatments representing different moisture levels. Spectral signatures were measured for each sample in laboratory under artificial light using an Analytical Spectral Device (ASD) spectrometer, covering a wavelength range from 350 nm to 2500 nm, with a spectral resolution of 1 nm. The results showed that the absorption features at 1450 nm, 1900 nm, and 2200 nm were particularly sensitive to soil moisture content and exhibited strong correlations with the water content levels. Continuum removal was developed in the R programming language to enhance the absorption features of soil moisture and to precisely understand its spectral behavior at different water content levels. Statistical analysis using partial least squares regression (PLSR) models were performed to quantify the correlation between the spectral bands and soil moisture content. This study provides insights into the spectral behavior of soil at different water content levels and identifies the significant spectral bands for soil moisture content retrieval. The findings highlight the potential of spectroscopy for non-destructive and rapid soil moisture measurement, which can be applied to various fields such as precision agriculture, hydrology, and environmental monitoring. However, it is important to note that the spectral behavior of soil can be influenced by various factors such as soil type, texture, and organic matter content, and caution should be taken when applying the results to other soil systems. The results of this study showed a good agreement between measured and predicted values of Soil Moisture Content with high R2 and low root mean square error (RMSE) values. Model validation using independent data was satisfactory for all the studied soil samples. The results has significant implications for developing high-resolution and precise field-scale soil moisture retrieval models. These models can be used to understand the spatial and temporal variation of soil moisture content in agricultural fields, which is essential for managing irrigation and optimizing crop yield.

Keywords: soil moisture content retrieval, precision agriculture, continuum removal, remote sensing, machine learning, spectroscopy

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Authors: Vasiliki Kolake, Christos Kavalaris, Sofia Megoudi, Maria Maxouri, Panagiotis A. Karas, Aris Kyparissis, Efi Levizou

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Conservation agriculture (CA), is a production system approach that can tackle the challenges of climate change mainly through facilitating carbon storage into the soil and increasing crop resilience. This is extremely important for the vulnerable Mediterranean agroecosystems, which already face adverse environmental conditions. The agronomic practices used in CA, i.e. permanent soil cover and no-tillage, result in reduced soil erosion and increased soil organic matter, preservation of water and improvement of quality and fertility of the soil in the long-term. Thus the functional characteristics and processes of the soil are considerably affected by the implementation of CA. The aim of the present work was to assess the effects of CA on soil nitrification potential and mycorrhizal colonization about the above-ground production in a wheat field. Two adjacent but independent field sites of 1.5ha each were used (Thessaly plain, Central Greece), comprising the no-till and conventional tillage treatments. The no-tillage site was covered by residues of the previous crop (cotton). Potential nitrification and the nitrate and ammonium content of the soil were measured at two different soil depths (3 and 15cm) at 20-days intervals throughout the growth period. Additionally, the leaf area index (LAI) was monitored at the same time-course. The mycorrhizal colonization was measured at the commencement and end of the experiment. At the final harvest, total yield and plant biomass were also recorded. The results indicate that wheat yield was considerably favored by CA practices, exhibiting a 42% increase compared to the conventional tillage treatment. The superior performance of the CA crop was also depicted in the above-ground plant biomass, where a 26% increase was recorded. LAI, which is considered a reliable growth index, did not show statistically significant differences between treatments throughout the growth period. On the contrary, significant differences were recorded in endomycorrhizal colonization one day before the final harvest, with CA plants exhibiting 20% colonization, while the conventional tillage plants hardly reached 1%. The on-going analyses of potential nitrification measurements, as well as nitrate and ammonium determination, will shed light on the effects of CA on key processes in the soil. These results will integrate the assessment of CA impact on certain below and above-ground processes during wheat cultivation under the Mediterranean climate.

Keywords: conservation agriculture, LAI, mycorrhizal colonization, potential nitrification, wheat, yield

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Authors: M. Nerantzaki, I. Koliakou, D. Bikiaris

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This study evaluates the hypothesis that the incorporation of fibrous hydroxyapatite nanoparticles (nHA) with high crystallinity and high aspect ratio, synthesized by hydrothermal method, into Poly(butylene succinate) (PBSu), improves the bioactivity of the aliphatic polyester and affects new bone growth inhibiting resorption and enhancing bone formation. Hydroxyapatite nanorods were synthesized using a simple hydrothermal procedure. First, the HPO42- -containing solution was added drop-wise into the Ca2+-containing solution, while the molar ratio of Ca/P was adjusted at 1.67. The HA precursor was then treated hydrothermally at 200°C for 72 h. The resulting powder was characterized using XRD, FT-IR, TEM, and EDXA. Afterwards, PBSu nanocomposites containing 2.5wt% (nHA) were prepared by in situ polymerization technique for the first time and were examined as potential scaffolds for bone engineering applications. For comparison purposes composites containing either 2.5wt% micro-Bioglass (mBG) or 2.5wt% mBG-nHA were prepared and studied, too. The composite scaffolds were characterized using SEM, FTIR, and XRD. Mechanical testing (Instron 3344) and Contact Angle measurements were also carried out. Enzymatic degradation was studied in an aqueous solution containing a mixture of R. Oryzae and P. Cepacia lipases at 37°C and pH=7.2. In vitro biomineralization test was performed by immersing all samples in simulated body fluid (SBF) for 21 days. Biocompatibility was assessed using rat Adipose Stem Cells (rASCs), genetically modified by nucleofection with DNA encoding SB100x transposase and pT2-Venus-neo transposon expression plasmids in order to attain fluorescence images. Cell proliferation and viability of cells on the scaffolds were evaluated using fluoresce microscopy and MTT (3-(4,5-dimethylthiazol-2-yl)-2,5 diphenyltetrazolium bromide) assay. Finally, osteogenic differentiation was assessed by staining rASCs with alizarine red using cetylpyridinium chloride (CPC) method. TEM image of the fibrous HAp nanoparticles, synthesized in the present study clearly showed the fibrous morphology of the synthesized powder. The addition of nHA decreased significantly the contact angle of the samples, indicating that the materials become more hydrophilic and hence they absorb more water and subsequently degrade more rapidly. In vitro biomineralization test confirmed that all samples were bioactive as mineral deposits were detected by X-ray diffractometry after incubation in SBF. Metabolic activity of rASCs on all PBSu composites was high and increased from day 1 of culture to day 14. On day 28 metabolic activity of rASCs cultured on samples enriched with bioceramics was significantly decreased due to possible differentiation of rASCs to osteoblasts. Staining rASCs with alizarin red after 28 days in culture confirmed our initial hypothesis as the presence of calcium was detected, suggesting osteogenic differentiation of rACS on PBSu/nHAp/mBG 2.5% and PBSu/mBG 2.5% composite scaffolds.

Keywords: biomaterials, hydroxyapatite nanorods, poly(butylene succinate), scaffolds

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Authors: Benjamin Castillo, Luis Pastenes, Fernando Cordova

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The pathogen growth in animal source foods is a common problem in the food industry, causing monetary losses due to the spoiling of products or food intoxication outbreaks in the community. In this sense, the quality of the product is reflected by the population of deteriorating agents present in it, which are mainly bacteria. The factors which are likely associated with freshness in animal source foods are temperature and processing, storage, and transport times. However, the level of deterioration of products depends, in turn, on the characteristics of the bacterial population, causing the decomposition or spoiling, such as pH level and toxins. Knowing the growth dynamics of the agents that are involved in product contamination allows the monitoring for more efficient processing. This means better quality and reasonable costs, along with a better estimation of necessary time and temperature intervals for transport and storage in order to preserve product quality. The objective of this project is to design a secondary model that allows measuring the impact on temperature bacterial growth and the competition for pH adequacy and release of bacteriocins in order to describe such phenomenon and, thus, estimate food product half-life with the least possible risk of deterioration or spoiling. In order to achieve this objective, the authors propose an analysis of a three-dimensional ordinary differential which includes; logistic bacterial growth extended by the inhibitory action of bacteriocins including the effect of the medium pH; change in the medium pH levels through an adaptation of the Luedeking-Piret kinetic model; Bacteriocin concentration modeled similarly to pH levels. These three dimensions are being influenced by the temperature at all times. Then, this differential system is expanded, taking into consideration the variable temperature and the concentration of pulsed bacteriocins, which represent characteristics inherent of the modeling, such as transport and storage, as well as the incorporation of substances that inhibit bacterial growth. The main results lead to the fact that temperature changes in an early stage of transport increased the bacterial population significantly more than if it had increased during the final stage. On the other hand, the incorporation of bacteriocins, as in other investigations, proved to be efficient in the short and medium-term since, although the population of bacteria decreased, once the bacteriocins were depleted or degraded over time, the bacteria eventually returned to their regular growth rate. The efficacy of the bacteriocins at low temperatures decreased slightly, which equates with the fact that their natural degradation rate also decreased. In summary, the implementation of the mathematical model allowed the simulation of a set of possible bacteria present in animal based products, along with their properties, in various transport and storage situations, which led us to state that for inhibiting bacterial growth, the optimum is complementary low constant temperatures and the initial use of bacteriocins.

Keywords: bacterial growth, bacteriocins, mathematical modelling, temperature

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Authors: Serpil Kilic, Ihsan Burak Cam, Murat Kilic, Timur Tongur

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Interest in the lead (Pb) has considerably increased due to knowledge about the potential toxic effects of this element, recently. Exposure to heavy metals above the acceptable limit affects human health. Indeed, Pb is accumulated through food chains up to toxic concentrations; therefore, it can pose an adverse potential threat to human health. A sensitive and reliable method for determination of Pb element in red pepper were improved in the present study. Samples (33 red pepper products having different brands) were purchased from different markets in Turkey. The selected method validation criteria (linearity, Limit of Detection, Limit of Quantification, recovery, and trueness) demonstrated. Recovery values close to 100% showed adequate precision and accuracy for analysis. According to the results of red pepper analysis, all of the tested lead element in the samples was determined at various concentrations. A Perkin- Elmer ELAN DRC-e model ICP-MS system was used for detection of Pb. Organic red pepper was used to obtain a matrix for all method validation studies. The certified reference material, Fapas chili powder, was digested and analyzed, together with the different sample batches. Three replicates from each sample were digested and analyzed. The results of the exposure levels of the elements were discussed considering the scientific opinions of the European Food Safety Authority (EFSA), which is the European Union’s (EU) risk assessment source associated with food safety. The Target Hazard Quotient (THQ) was described by the United States Environmental Protection Agency (USEPA) for the calculation of potential health risks associated with long-term exposure to chemical pollutants. THQ value contains intake of elements, exposure frequency and duration, body weight and the oral reference dose (RfD). If the THQ value is lower than one, it means that the exposed population is assumed to be safe and 1 < THQ < 5 means that the exposed population is in a level of concern interval. In this study, the THQ of Pb was obtained as < 1. The results of THQ calculations showed that the values were below one for all the tested, meaning the samples did not pose a health risk to the local population. This work was supported by The Scientific Research Projects Coordination Unit of Akdeniz University. Project Number: FBA-2017-2494.

Keywords: lead analyses, red pepper, risk assessment, daily exposure

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Authors: S. M. D. Y. S. A. Wijayarathna, A. C. A. Jayasundera

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Mahaweli River is the longest and largest river in Sri Lanka and it is the major drinking water source for a large portion of 2.5 million inhabitants in the Central Province. The aim of this study was to the determination of water quality and aquatic life health quality in a selected region of Mahaweli River. Six sampling locations (Site 1: 7° 16' 50" N, 80° 40' 00" E; Site 2: 7° 16' 34" N, 80° 40' 27" E; Site 3: 7° 16' 15" N, 80° 41' 28" E; Site 4: 7° 14' 06" N, 80° 44' 36" E; Site 5: 7° 14' 18" N, 80° 44' 39" E; Site 6: 7° 13' 32" N, 80° 46' 11" E) with various anthropogenic activities at bank of the river were selected for a period of three months from Tennekumbura Bridge to Victoria Reservoir. Temperature, pH, Electrical Conductivity (EC), Total Dissolved Solids (TDS), Dissolved Oxygen (DO), 5-day Biological Oxygen Demand (BOD5), Total Suspended Solids (TSS), hardness, the concentration of anions, and metal concentration were measured according to the standard methods, as physicochemical parameters. Planktons were considered as biological parameters. Using a plankton net (20 µm mesh size), surface water samples were collected into acid washed dried vials and were stored in an ice box during transportation. Diversity and abundance of planktons were identified within 4 days of sample collection using standard manuals of plankton identification under the light microscope. Almost all the measured physicochemical parameters were within the CEA standards limits for aquatic life, Sri Lanka Standards (SLS) or World Health Organization’s Guideline for drinking water. Concentration of orthophosphate ranged between 0.232 to 0.708 mg L-1, and it has exceeded the standard limit of aquatic life according to CEA guidelines (0.400 mg L-1) at Site 1 and Site 2, where there is high disturbance by cultivations and close households. According to the Pearson correlation (significant correlation at p < 0.05), it is obvious that some physicochemical parameters (temperature, DO, TDS, TSS, phosphate, sulphate, chloride fluoride, and sodium) were significantly correlated to the distribution of some plankton species such as Aulocoseira, Navicula, Synedra, Pediastrum, Fragilaria, Selenastrum, Oscillataria, Tribonema and Microcystis. Furthermore, species that appear in blooms (Aulocoseira), organic pollutants (Navicula), and phosphate high eutrophic water (Microcystis) were found, indicating deteriorated water quality in Mahaweli River due to agricultural activities, solid waste disposal, and release of domestic effluents. Therefore, it is necessary to improve environmental monitoring and management to control the further deterioration of water quality of the river.

Keywords: bio indicator, environmental variables, planktons, physicochemical parameters, water quality

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Authors: Cibele F. Oliveira, Debora P. Jaeschke, Rodrigo R. Laurino, Amanda R. Andrade, Ligia D. F. Marczak

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Raspberry is well-known as a good source of phenolic compounds, mainly anthocyanin. Some studies pointed out the importance of these bioactive compounds consumption, which is related to the decrease of the risk of cancer and cardiovascular diseases. The most consumed raspberry products are juices, yogurts, ice creams and jellies and, to ensure the safety of these products, raspberry is commonly pasteurized, for enzyme and microorganisms inactivation. Despite being efficient, the pasteurization process can lead to degradation reactions of the bioactive compounds, decreasing the products healthy benefits. Therefore, the aim of the present work was to evaluate moderate electric field (MEF) and ultrasound (US) technologies application on the pasteurization process of raspberry juice and compare the results with conventional pasteurization process. For this, phenolic compounds, anthocyanin content and physical-chemical parameters (pH, color changes, titratable acidity) of the juice were evaluated before and after the treatments. Moreover, microbiological analyses of aerobic mesophiles microorganisms, molds and yeast were performed in the samples before and after the treatments, to verify the potential of these technologies to inactivate microorganisms. All the pasteurization processes were performed in triplicate for 10 min, using a cylindrical Pyrex® vessel with a water jacket. The conventional pasteurization was performed at 90 °C using a hot water bath connected to the extraction cell. The US assisted pasteurization was performed using 423 and 508 W cm-2 (75 and 90 % of ultrasound intensity). It is important to mention that during US application the temperature was kept below 35 °C; for this, the water jacket of the extraction cell was connected to a water bath with cold water. MEF assisted pasteurization experiments were performed similarly to US experiments, using 25 and 50 V. Control experiments were performed at the maximum temperature of US and MEF experiments (35 °C) to evaluate only the effect of the aforementioned technologies on the pasteurization. The results showed that phenolic compounds concentration in the juice was not affected by US and MEF application. However, it was observed that the US assisted pasteurization, performed at the highest intensity, decreased anthocyanin content in 33 % (compared to in natura juice). This result was possibly due to the cavitation phenomena, which can lead to free radicals formation and accumulation on the medium; these radicals can react with anthocyanin decreasing the content of these antioxidant compounds in the juice. Physical-chemical parameters did not present statistical differences for samples before and after the treatments. Microbiological analyses results showed that all the pasteurization treatments decreased the microorganism content in two logarithmic cycles. However, as values were lower than 1000 CFU mL-1 it was not possible to verify the efficacy of each treatment. Thus, MEF and US were considered as potential alternative technologies for pasteurization process, once in the right conditions the application of the technologies decreased microorganism content in the juice and did not affected phenolic and anthocyanin content, as well as physical-chemical parameters. However, more studies are needed regarding the influence of MEF and US processes on microorganisms’ inactivation.

Keywords: MEF, microorganism inactivation, anthocyanin, phenolic compounds

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Authors: Khodzhaberdi Allaberdiev

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Aromaticity, one of the most important concepts in organic chemistry, has attracted considerable interest from both experimentalists and theoreticians. The geometry optimization of p-substituted o-(N-dialkyl)aminomethylphenols, o-DEAMPH XC₆ H₅CH ₂Y (X=p-OCH₃, CH₃, H, F, Cl, Br, COCH₃, COOCH₃, CHO, CN and NO₂, Y=o-N (C₂H₅)₂, o-DEAMPHs have been performed in the gas phase using the B3LYP/6-311+G(d,p) level. Aromaticities of the considered molecules were investigated using different indices included geometrical (HOMA and Bird), electronic (FLU, PDI and SA) magnetic (NICS(0), NICS(1) and NICS(1)zz indices. The linear dependencies were obtained between some aromaticity indices. The best correlation is observed between the Bird and PDI indices (R² =0.9240). However, not all types of indices or even different indices within the same type correlate well among each other. Surprisingly, for studied molecules in which geometrical and electronic cannot correctly give the aromaticity of ring, the magnetism based index successfully predicts the aromaticity of systems. 1H NMR spectra of compounds were obtained at B3LYP/6–311+G(d,p) level using the GIAO method. Excellent linear correlation (R²= 0.9996) between values the chemical shift of hydrogen atom obtained experimentally of 1H NMR and calculated using B3LYP/6–311+G(d,p) demonstrates a good assignment of the experimental values chemical shift to the calculated structures of o-DEAMPH. It is found that the best linear correlation with the Hammett substituent constants is observed for the NICS(1)zz index in comparison with the other indices: NICS(1)zz =-21.5552+1,1070 σp- (R²=0.9394). The presence intramolecular hydrogen bond in the studied molecules also revealed changes the aromatic character of substituted o-DEAMPHs. The HOMA index predicted for R=NO2 the reduction in the π-electron delocalization of 3.4% was about double that observed for p-nitrophenol. The influence intramolecular H-bonding on aromaticity of benzene ring in the ground state (S0) are described by equations between NICS(1)zz and H-bond energies: experimental, Eₑₓₚ, predicted IR spectroscopical, Eν and topological, EQTAIM with correlation coefficients R² =0.9666, R² =0.9028 and R² =0.8864, respectively. The NICS(1)zz index also correlates with usual descriptors of the hydrogen bond, while the other indices do not give any meaningful results. The influence of the intramolecular H-bonding formation on the aromaticity of some substituted o-DEAMPHs is criteria to consider the multidimensional character of aromaticity. The linear relationships as well as revealed between NICS(1)zz and both pyramidality nitrogen atom, ΣN(C₂H₅)₂ and dihedral angle, φ CAr – CAr -CCH₂ –N, to characterizing out-of-plane properties.These results demonstrated the nonplanar structure of o-DEAMPHs. Finally, when considering dependencies of NICS(1)zz, were excluded data for R=H, because the NICS(1) and NICS(1)zz values are the most negative for unsubstituted DEAMPH, indicating its highest aromaticity; that was not the case for NICS(0) index.

Keywords: aminomethylphenols, DFT, aromaticity, correlations

Procedia PDF Downloads 181

Authors: Inês N. Peça , A. Bicho, Rui Gardner, M. Margarida Cardoso

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Inorganic/organic nanocomplexes offer tremendous scope for future biomedical applications, including imaging, disease diagnosis and drug delivery. The combination of Fe3O4 with biocompatible polymers to produce smart drug delivery systems for use in pharmaceutical formulation present a powerful tool to target anti-cancer drugs to specific tumor sites through the application of an external magnetic field. In the present study, we focused on the evaluation of the effect of the magnetic field application time on the rate of drug release from iron oxide polymeric nanoparticles. Doxorubicin, an anticancer drug, was selected as the model drug loaded into the nanoparticles. Nanoparticles composed of poly(d-lactide-co-glycolide (PLGA), a biocompatible polymer already approved by FDA, containing iron oxide nanoparticles (MNP) for magnetic targeting and doxorubicin (DOX) were synthesized by the o/w solvent extraction/evaporation method and characterized by scanning electron microscopy (SEM), by dynamic light scattering (DLS), by inductively coupled plasma-atomic emission spectrometry and by Fourier transformed infrared spectroscopy. The produced particles yielded smooth surfaces and spherical shapes exhibiting a size between 400 and 600 nm. The effect of the magnetic doxorubicin loaded PLGA nanoparticles produced on cell viability was investigated in mammalian CHO cell cultures. The results showed that unloaded magnetic PLGA nanoparticles were nontoxic while the magnetic particles without polymeric coating show a high level of toxicity. Concerning the therapeutic activity doxorubicin loaded magnetic particles cause a remarkable enhancement of the cell inhibition rates compared to their non-magnetic counterpart. In vitro drug release studies performed under a non-permanent magnetic field show that the application time and the on/off cycle duration have a great influence with respect to the final amount and to the rate of drug release. In order to determine the mechanism of drug release, the data obtained from the release curves were fitted to the semi-empirical equation of the the Korsmeyer-Peppas model that may be used to describe the Fickian and non-Fickian release behaviour. Doxorubicin release mechanism has shown to be governed mainly by Fickian diffusion. The results obtained show that the rate of drug release from the produced magnetic nanoparticles can be modulated through the magnetic field time application.

Keywords: drug delivery, magnetic nanoparticles, PLGA nanoparticles, controlled release rate

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Authors: Michael T. Lobmann, Camilla Wellstein, Stefan Zerbe

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Vegetation plays an important role for the stabilization of slopes against erosion processes, such as shallow erosion and landslides. Plant roots reinforce the soil, increase soil cohesion and often cross possible shear planes. Hence, plant roots reduce the risk of slope failure. Generally, shrub and tree roots penetrate deeper into the soil vertically, while roots of forbs and grasses are concentrated horizontally in the topsoil and organic layer. Therefore, shrubs and trees have a higher potential for stabilization of slopes with deep soil layers than forbs and grasses. Consequently, research mainly focused on the vertical root effects of shrubs and trees. Nevertheless, a better understanding of the stabilizing effects of grasses and forbs is needed for better evaluation of the stability of natural and artificial slopes with herbaceous vegetation. Despite the importance of vertical root effects, field observations indicate that horizontal root effects also play an important role for slope stabilization. Not only forbs and grasses, but also some shrubs and trees form tight horizontal networks of fine and coarse roots and rhizomes in the topsoil. These root networks increase soil cohesion and horizontal tensile strength. Available methods for physical measurements, such as shear-box tests, pullout tests and singular root tensile strength measurement can only provide a detailed picture of vertical effects of roots on slope stabilization. However, the assessment of horizontal root effects is largely limited to computer modeling. Here, a method for measurement of in-situ cumulative horizontal root tensile strength is presented. A traction machine was developed that allows fixation of rectangular grass sods (max. 30x60cm) on the short ends with a 30x30cm measurement zone in the middle. On two alpine grass slopes in South Tyrol (northern Italy), 30x60cm grass sods were cut out (max. depth 20cm). Grass sods were pulled apart measuring the horizontal tensile strength over 30cm width over the time. The horizontal tensile strength of the sods was measured and compared for different soil depths, hydrological conditions, and root physiological properties. The results improve our understanding of horizontal root effects on slope stabilization and can be used for improved evaluation of grass slope stability.

Keywords: grassland, horizontal root effect, landslide, mountain, pasture, shallow erosion

Procedia PDF Downloads 166

Authors: S. Wiak, L. Szymanski, Z. Kolacinski, G. Raniszewski, L. Pietrzak, Z. Staniszewska

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The term ‘cancer’ is given to a collection of related diseases that may affect any part of the human body. It is a pathological behaviour of cells with the potential to undergo abnormal breakdown in the processes that control cell proliferation, differentiation, and death of particular cells. Although cancer is commonly considered as modern disease, there are beliefs that drastically growing number of new cases can be linked to the extensively prolonged life expectancy and enhanced techniques for cancer diagnosis. Magnetic hyperthermia therapy is a novel approach to cancer treatment, which may greatly contribute to higher efficiency of the therapy. Employing carbon nanotubes as nanocarriers for magnetic particles, it is possible to decrease toxicity and invasiveness of the treatment by surface functionalisation. Despite appearing in recent years, magnetic particle hyperthermia has already become of the highest interest in the scientific and medical environment. The reason why hyperthermia therapy brings so much hope for future treatment of cancer lays in the effect that it produces in malignant cells. Subjecting them to thermal shock results in activation of numerous degradation processes inside and outside the cell. The heating process initiates mechanisms of DNA destruction, protein denaturation and induction of cell apoptosis, which may lead to tumour shrinkage, and in some cases, it may even cause complete disappearance of cancer. The factors which have the major impact on the final efficiency of the treatment include temperatures generated inside the tissues, time of exposure to the heating process, and the character of an individual cancer cell type. The vast majority of cancer cells is characterised by lower pH, persistent hypoxia and lack of nutrients, which can be associated to abnormal microvasculature. Since in healthy tissues we cannot observe presence of these conditions, they should not be seriously affected by elevation of the temperature. The aim of this work is to investigate the influence of iron content in iron filled Carbon Nanotubes on the desired nanoparticles for cancer therapy. In the article, the development and demonstration of the method and the model device for hyperthermic selective destruction of cancer cells are presented. This method was based on the synthesis and functionalization of carbon nanotubes serving as ferromagnetic material nanocontainers. The methodology of the production carbon- ferromagnetic nanocontainers (FNCs) includes the synthesis of carbon nanotubes, chemical, and physical characterization, increasing the content of a ferromagnetic material and biochemical functionalization involving the attachment of the key addresses. The ferromagnetic nanocontainers were synthesised in CVD and microwave plasma system. The research work has been financed from the budget of science as a research project No. PBS2/A5/31/2013.

Keywords: hyperthermia, carbon nanotubes, cancer colon cells, radio frequency field

Procedia PDF Downloads 122

Authors: Sonia Amariei, Ionut Avramia, Florin Ursachi, Ancuta Chetrariu, Ancuta Petraru

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The food industry is one of the major generators of plastic waste derived from conventional synthetic petroleum-based polymers, which are non-biodegradable, used especially for packaging. These packaging materials, after the food is consumed, accumulate serious environmental concerns due to the materials but also to the organic residues that adhere to them. It is the concern of specialists, researchers to eliminate problems related to conventional materials that are not biodegradable or unnecessary plastic and replace them with biodegradable and edible materials, supporting the common effort to protect the environment. Even though environmental and health concerns will cause more consumers to switch to a plant-based diet, most people will continue to add more meat to their diet. The paper presents the possibility of replacing the polyethylene packaging from the surface of the trays for meat preparations with biodegradable packaging obtained from biopolymers. During the storage of meat products may occur deterioration by lipids oxidation and microbial spoilage, as well as the modification of the organoleptic characteristics. For this reason, different compositions of polymer mixtures and film conditions for obtaining must be studied to choose the best packaging material to achieve food safety. The compositions proposed for packaging are obtained from alginate, agar, starch, and glycerol as plasticizers. The tensile strength, elasticity, modulus of elasticity, thickness, density, microscopic images of the samples, roughness, opacity, humidity, water activity, the amount of water transferred as well as the speed of water transfer through these packaging materials were analyzed. A number of 28 samples with various compositions were analyzed, and the results showed that the sample with the highest values for hardness, density, and opacity, as well as the smallest water vapor permeability, of 1.2903E-4 ± 4.79E-6, has the ratio of components as alginate: agar: glycerol (3:1.25:0.75). The water activity of the analyzed films varied between 0.2886 and 0.3428 (aw< 0.6), demonstrating that all the compositions ensure the preservation of the products in the absence of microorganisms. All the determined parameters allow the appreciation of the quality of the packaging films in terms of mechanical resistance, its protection against the influence of light, the transfer of water through the packaging. Acknowledgments: This work was supported by a grant of the Ministry of Research, Innovation, and Digitization, CNCS/CCCDI – UEFISCDI, project number PN-III-P2-2.1-PED-2019-3863, within PNCDI III.

Keywords: meat products, alginate, agar, starch, glycerol

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Authors: Elmira Ghanbari, Jan Van Esch, Stephen J. Picken, Sahil Aggarwal

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Low-molecular-weight organogelators form gels by self-assembly into the crystalline network which immobilizes the organic solvent. For single bisamide organogelator systems, the effect of the molecular structure on the molecular interaction and their self-assembly behavior has been explored. The spatial arrangement of bisamide molecules in the gel-state is driven by a combination of hydrogen bonding and Van der Waals interactions. The hydrogen-bonding pattern between the amide groups of bisamide molecules is regulated by the number of methylene spacers; the even number of methylene spacers between two amide groups, in even-spaced bisamides, leads to the antiparallel position of amide groups within a molecule. An even-spaced bisamide molecule with antiparallel amide groups can make two pairs of hydrogen bonding with the molecules on the same plane. The odd-spaced bisamide with a parallel directionality of amide groups can form four independent hydrogen bonds with four other bisamide molecules on different planes. The arrangement of bisamide molecules in the crystalline state and the interaction of these molecules depends on the molecular structure, particularly the parity of the spacer length between the amide groups in the bisamide molecule. In this study, the directionality of amide groups has been exploited as a structural characteristic to affect the arrangement of molecules in the crystalline state and produce different binary bisamide gelators with different degrees of crystallinities. Single odd- and even-spaced single bisamides were synthesized and blended to produce binary bisamide organogelators to be characterized in order to understand the effect of the different directionality of amide groups on the molecular interaction in the crystalline state. The pattern of molecular interactions between these blended molecules, mixing or phase separation, has been monitored via differential scanning calorimetry (DSC) and crystallography techniques; X-ray powder diffraction (XRD) and Small-angle X-ray scattering (SAXS). The formation of lamellar structures for odd- and even-spaced bisamide gelators was confirmed by using SAXS and XRD techniques. DSC results have shown that binary bisamide organogelators with different parity of methylene spacers (odd-even binary blends) have a higher tendency for phase separation compared to the binary bisamides with the same parity (odd-odd or even-even binary blends). Phase separation in binary odd-even bisamides was confirmed by the presence of individual (100) reflections of odd and even lamellar structures. The structural characteristic of bisamide organogelators, the parity of spacer length in binary systems, is a promising tool to control the arrangement of molecules and their crystalline structure.

Keywords: binary bisamide organogelators, crystalline structure, phase separation, self-assembly behavior

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Authors: Louise Ödlund, Danica Djuric Ilic

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From a system perspective, there are several benefits of DH. A possibility to utilize the excess heat from waste incineration and biomass-based combined heat and power (CHP) production (e.g. possibility to utilize the excess heat from electricity production) are two examples. However, in a future sustainable society, the benefits of DH may be less obvious. Due to the climate changes and increased energy efficiency of buildings, the demand for space heating is expected to decrease. Due to the society´s development towards circular economy, a larger amount of the waste will be material recycled, and the possibility for DH production by the energy recovery through waste incineration will be reduced. Furthermore, the benefits of biomass-based CHP production will be less obvious since the marginal electricity production will no longer be linked to high greenhouse gas emissions due to an increased share of renewable electricity capacity in the electricity system. The purpose of the study is (1) to provide an overview of the possible development of other sectors which may influence the DH in the future and (2) to detect new business strategies which would enable for DH to adapt to the future conditions and remain competitive to alternative heat production in the future. A system approach was applied where DH is seen as a part of an integrated system which consists of other sectors as well. The possible future development of other sectors and the possible business strategies for DH producers were searched through a systematic literature review In order to remain competitive to the alternative heat production in the future, DH producers need to develop new business strategies. While the demand for space heating is expected to decrease, the space cooling demand will probably increase due to the climate changes, but also due to the better insulation of buildings in the cases where the home appliances are the heat sources. This opens up a possibility for applying DH-driven absorption cooling, which would increase the annual capacity utilization of the DH plants. The benefits of the DH related to the energy recovery from the waste incineration will exist in the future since there will always be a need to take care of materials and waste that cannot be recycled (e.g. waste containing organic toxins, bacteria, such as diapers and hospital waste). Furthermore, by operating central controlled heat pumps, CHP plants, and heat storage depending on the intermittent electricity production variation, the DH companies may enable an increased share of intermittent electricity production in the national electricity grid. DH producers can also enable development of local biofuel supply chains and reduce biofuel production costs by integrating biofuel and DH production in local DH systems.

Keywords: district heating, sustainable business strategies, sustainable development, system approach

Procedia PDF Downloads 84

Authors: Alice Robba, Renaud Bouchet, Celine Barchasz, Jean-Francois Colin, Erik Elkaim, Kristina Kvashnina, Gavin Vaughan, Matjaz Kavcic, Fannie Alloin

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With their high theoretical energy density (~2600 Wh.kg-1), lithium/sulfur (Li/S) batteries are highly promising, but these systems are still poorly understood due to the complex mechanisms/equilibria involved. Replacing S8 by Li2S as the active material allows the use of safer negative electrodes, like silicon, instead of lithium metal. S8 and Li2S have different conductivity and solubility properties, resulting in a profoundly changed activation process during the first cycle. Particularly, during the first charge a high polarization and a lack of reproducibility between tests are observed. Differences observed between raw Li2S material (micron-sized) and that electrochemically produced in a battery (nano-sized) may indicate that the electrochemical process depends on the particle size. Then the major focus of the presented work is to deepen the understanding of the Li2S material charge mechanism, and more precisely to characterize the effect of the initial Li2S particle size both on the mechanism and the electrode preparation process. To do so, Li2S nanoparticles were synthetized according to two ways: a liquid path synthesis and a dissolution in ethanol, allowing Li2S nanoparticles/carbon composites to be made. Preliminary chemical and electrochemical tests show that starting with Li2S nanoparticles could effectively suppress the high initial polarization but also influence the electrode slurry preparation. Indeed, it has been shown that classical formulation process - a slurry composed of Polyvinylidone Fluoride polymer dissolved in N-methyle-2-pyrrolidone - cannot be used with Li2S nanoparticles. This reveals a complete different Li2S material behavior regarding polymers and organic solvents when going at the nanometric scale. Then the coupling between two operando characterizations such as X-Ray Diffraction (XRD) and X-Ray Absorption and Emission Spectroscopy (XAS/XES) have been carried out in order to interpret the poorly understood first charge. This study discloses that initial particle size of the active material has a great impact on the working mechanism and particularly on the different equilibria involved during the first charge of the Li2S based Li-ion batteries. These results explain the electrochemical differences and particularly the polarization differences observed during the first charge between micrometric and nanometric Li2S-based electrodes. Finally, this work could lead to a better active material design and so to more efficient Li2S-based batteries.

Keywords: Li-ion/Sulfur batteries, Li2S nanoparticles effect, Operando characterizations, working mechanism

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Authors: Julia Ive, Lucia Specia

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Understanding and detecting toxicity is an important problem to support safer human interactions online. Our work focuses on the important problem of contextual toxicity detection, where automated classifiers are tasked with determining whether a short textual segment (usually a sentence) is toxic within its conversational context. We use “toxicity” as an umbrella term to denote a number of variants commonly named in the literature, including hate, abuse, offence, among others. Detecting toxicity in context is a non-trivial problem and has been addressed by very few previous studies. These previous studies have analysed the influence of conversational context in human perception of toxicity in controlled experiments and concluded that humans rarely change their judgements in the presence of context. They have also evaluated contextual detection models based on state-of-the-art Deep Learning and Natural Language Processing (NLP) techniques. Counterintuitively, they reached the general conclusion that computational models tend to suffer performance degradation in the presence of context. We challenge these empirical observations by devising better contextual predictive models that also rely on NLP data augmentation techniques to create larger and better data. In our study, we start by further analysing the human perception of toxicity in conversational data (i.e., tweets), in the absence versus presence of context, in this case, previous tweets in the same conversational thread. We observed that the conclusions of previous work on human perception are mainly due to data issues: The contextual data available does not provide sufficient evidence that context is indeed important (even for humans). The data problem is common in current toxicity datasets: cases labelled as toxic are either obviously toxic (i.e., overt toxicity with swear, racist, etc. words), and thus context does is not needed for a decision, or are ambiguous, vague or unclear even in the presence of context; in addition, the data contains labeling inconsistencies. To address this problem, we propose to automatically generate contextual samples where toxicity is not obvious (i.e., covert cases) without context or where different contexts can lead to different toxicity judgements for the same tweet. We generate toxic and non-toxic utterances conditioned on the context or on target tweets using a range of techniques for controlled text generation(e.g., Generative Adversarial Networks and steering techniques). On the contextual detection models, we posit that their poor performance is due to limitations on both of the data they are trained on (same problems stated above) and the architectures they use, which are not able to leverage context in effective ways. To improve on that, we propose text classification architectures that take the hierarchy of conversational utterances into account. In experiments benchmarking ours against previous models on existing and automatically generated data, we show that both data and architectural choices are very important. Our model achieves substantial performance improvements as compared to the baselines that are non-contextual or contextual but agnostic of the conversation structure.

Keywords: contextual toxicity detection, data augmentation, hierarchical text classification models, natural language processing

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Authors: Vanda Ferreira Ribeiro, Daiane Tomacheski, Douglas Naue Simões, Michele Pitto, Ruth Marlene Campomanes Santana

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Indoor environments, such as car cabins and public transportation vehicles are places where users are subject to air quality. Microorganisms (bacteria, fungi, yeasts) enter these environments through windows, ventilation systems and may use the organic particles present as a growth substrate. In addition, atmospheric pollutants can act as potential carbon and nitrogen sources for some microorganisms. Compounds base SEBS copolymers, poly(styrene-b-(ethylene-co-butylene)-b-styrene, are a class of thermoplastic elastomers (TPEs), fully recyclable and largely used in automotive parts. Metals, such as cooper and silver, have biocidal activities and the production of the SEBS compounds by melting blending with these agents can be a good option for producing compounds for use in plastic parts of ventilation systems and automotive air-conditioning, in order to minimize the problems caused by growth of pathogenic microorganisms. In this sense, the aim of this work was to evaluate the effect of copper microparticles as antimicrobial agent in compositions based on SEBS/PP/oil/calcite. Copper microparticles were used in weight proportion of 0%, 1%, 2% and 4%. The compounds were prepared using a co-rotating double screw extruder (L/D ratio of 40/1 and 16 mm screw diameter). The processing parameters were 300 rpm of screw rotation rate, with a temperature profile between 150 to 190°C. SEBS based TPE compounds were injection molded. The compounds emission were characterized by gravimetric fogging test. Compounds were characterized by physical (density and staining by contact), mechanical (hardness and tension properties) and rheological properties (melt volume rate – MVR). Antibacterial properties were evaluated against Staphylococcus aureus (S. aureus) and Escherichia coli (E. coli) strains. To avaluate the abilities toward the fungi have been chosen Aspergillus niger (A. niger), Candida albicans (C. albicans), Cladosporium cladosporioides (C. cladosporioides) and Penicillium chrysogenum (P. chrysogenum). The results of biological tests showed a reduction on bacteria in up to 88% in E.coli and up to 93% in S. aureus. The tests with fungi showed no conclusive results because the sample without copper also demonstrated inhibition of the development of these microorganisms. The copper addition did not cause significant variations in mechanical properties, in the MVR and the emission behavior of the compounds. The density increases with the increment of copper in compounds.

Keywords: air conditioner, antimicrobial, cooper, SEBS

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Authors: L. Asaro, M. Gratton, S. Seghar, N. Poirot, N. Ait Hocine

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Rubber waste disposal is an environmental problem. Particularly, many researches are centered in the management of discarded tires. In spite of all different ways of handling used tires, the most common is to deposit them in a landfill, creating a stock of tires. These stocks can cause fire danger and provide ambient for rodents, mosquitoes and other pests, causing health hazards and environmental problems. Because of the three-dimensional structure of the rubbers and their specific composition that include several additives, their recycling is a current technological challenge. The technique which can break down the crosslink bonds in the rubber is called devulcanization. Strictly, devulcanization can be defined as a process where poly-, di-, and mono-sulfidic bonds, formed during vulcanization, are totally or partially broken. In the recent years, super critical carbon dioxide (scCO₂) was proposed as a green devulcanization atmosphere. This is because it is chemically inactive, nontoxic, nonflammable and inexpensive. Its critical point can be easily reached (31.1 °C and 7.38 MPa), and residual scCO₂ in the devulcanized rubber can be easily and rapidly removed by releasing pressure. In this study thermomechanical devulcanization of ground tire rubber (GTR) was performed in a twin screw extruder under diverse operation conditions. Supercritical CO₂ was added in different quantities to promote the devulcanization. Temperature, screw speed and quantity of CO₂ were the parameters that were varied during the process. The devulcanized rubber was characterized by its devulcanization percent and crosslink density by swelling in toluene. Infrared spectroscopy (FTIR) and Gel permeation chromatography (GPC) were also done, and the results were related with the Mooney viscosity. The results showed that the crosslink density decreases as the extruder temperature and speed increases, and, as expected, the soluble fraction increase with both parameters. The Mooney viscosity of the devulcanized rubber decreases as the extruder temperature increases. The reached values were in good correlation (R= 0.96) with de the soluble fraction. In order to analyze if the devulcanization was caused by main chains or crosslink scission, the Horikx's theory was used. Results showed that all tests fall in the curve that corresponds to the sulfur bond scission, which indicates that the devulcanization has successfully happened without degradation of the rubber. In the spectra obtained by FTIR, it was observed that none of the characteristic peaks of the GTR were modified by the different devulcanization conditions. This was expected, because due to the low sulfur content (~1.4 phr) and the multiphasic composition of the GTR, it is very difficult to evaluate the devulcanization by this technique. The lowest crosslink density was reached with 1 cm³/min of CO₂, and the power consumed in that process was also near to the minimum. These results encourage us to do further analyses to better understand the effect of the different conditions on the devulcanization process. The analysis is currently extended to monophasic rubbers as ethylene propylene diene monomer rubber (EPDM) and natural rubber (NR).

Keywords: devulcanization, recycling, rubber, waste

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Authors: Pei-Ying Lo, Jing-Hao Ciou, Kai-Cheng Yang, Jia-Huei Zheng, Shih-Hsiang Huang, Kuen-Chan Lee, Er-Chieh Cho

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As-produced CNTs are insoluble in all organic solvents and aqueous solutions have imposed limitations to the use of CNTs. Therefore, how to debundle carbon nanotubes and to modify them for further uses is an important issue. There are several methods for the dispersion of CNTs in water using covalent attachment of hydrophilic groups to the surface of tubes. These methods, however, alter the electronic structure of the nanotubes by disrupting the network of sp2 hybridized carbons. In order to keep the nanotubes’ intrinsic mechanical and electrical properties intact, non-covalent interactions are increasingly being explored as an alternative route for dispersion. Apart from conventional surfactants such as sodium dodecylsulfate (SDS) or sodium dodecylbenzenesulfonate (SDBS) which are highly effective in dispersing CNTs, biopolymers have received much attention as dispersing agents due to the anticipated biocompatibility of the dispersed CNTs. Also, The pyrenyl group is known to interact strongly with the basal plane of graphene via π-stacking. In this study, a highly re-dispersible biopolymer is reported for the synthesis of pyrene-modified poly-L-lysine (PBPL) and poly(D-Glu, D-Lys) (PGLP). To provide the evidence of the safety of the PBPL/CNT & PGLP/CNT materials we use in this study, H1299 and HCT116 cells were incubated with PBPL/CNT & PGLP/CNT materials for toxicity analysis, MTS assays. The results from MTS assays indicated that no significant cellular toxicity was shown in H1299 and HCT116 cells. Furthermore, the fluorescence marker fluorescein isothiocyanate (FITC) was added to PBPL & PGLP dispersions. From the fluorescent measurements showed that the chemical functionalisation of the PBPL/CNT & PGLP/CNT conjugates with the fluorescence marker were successful. The fluorescent PBPL/CNT & PGLP/CNT conjugates could find application in medical imaging. In the next step, the GFP gene is immobilized onto PBPL/CNT conjugates by introducing electrostatic interaction. GFP-transfected cells that emitted fluorescence were imaged and counted under a fluorescence microscope. Due to the unique biocompatibility of PBPL modified CNTs, the GFP gene could be transported into H1299 cells without using antibodies. The applicability of such soluble and chemically functionalised polypeptide/CNT conjugates in biomedicine is currently investigated. We expect that this polypeptide/CNT system will be a safe and multi-functional nanomedical delivery platform and contribute to future medical therapy.

Keywords: carbon nanotube, nanotoxicology, GFP transfection, polypeptide/CNT hybrids

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Authors: Ratneev Kaur, Tajinder Kaur, Anupam Kaur

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Introduction: Polycystic Ovary Syndrome (PCOS) is a heterogenous disorder of endocrine system among women of reproductive age. PCOS is characterized by hyperandrogenism, anovulation, polycystic ovaries, hirsutism, obesity, and hyperinsulinemia. Several pathways are implicated in its etiology including the metabolic pathway of steroid hormone synthesis regulatory pathways. PCOS is an androgen excess disorder, genes operating in steroidogenesis may alter pathogenesis of PCOS. The cytochrome P450scc is a cholesterol side chain cleavage enzyme coded by CYP11A1 gene and catalyzes conversion of cholesterol to pregnenolone, the initial and rate-limiting step in steroid hormone synthesis. It is postulated that polymorphisms in this gene may play an important role in the regulation of CYP11A1 expression and leading to increased or decreased androgen production. The present study will be the first study from north India to best of our knowledge, to analyse the association of CYP11A1 (rs11632698) polymorphism in women suffering from PCOS. Methodology: The present study was approved by ethical committee of Guru Nanak Dev University in consistent with declaration of Helsinki. A total of 300 samples (150 PCOS cases and 150 controls) were recruited from Hartej hospital, for the present study. Venous blood sample (3ml) was withdrawn from women diagnosed with PCOS by doctor, according to Rotterdam 2003 criteria and from healthy age matched controls only after informed consent and detailed filled proforma. For molecular genetics analysis, blood was stored in EDTA vials. After DNA isolation by organic method, PCR-RFLP approach was used for genotyping and association analysis of rs11632698 polymorphism. Statistical analysis was done to check for significance of selected polymorphism with PCOS. Results: In 150 PCOS cases, the frequency of AA, AG and GG genotype was found to be 48%, 35%, and 13% compared to 62%, 27% and 8% in 150 controls. The major allele (A) and minor allele (G) frequency was 68% and 32% in cases and 78% and 22% in controls. Minor allele frequency was higher in cases as compared to controls, as well as the distribution of genotype was observed to be statistically significant (ᵡ²=6.525, p=0.038). Odds ratio in dominant, co-dominant and recessive models observed was 1.81 (p=0.013), 1.54 (p=0.012) and 1.77 (p=0.132) respectively. Conclusion: The present study showed statistically significant association of rs11632698 with PCOS (p=0.038) in North Indian women.

Keywords: polycystic ovary syndrome, CYP11A1, rs11632698, hyperandrogenism

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Authors: Nutcha Taneepanichskul, Helen C. Hailes, Mark Miodownik

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Plastic waste has emerged as a critical global environmental challenge, primarily driven by the prevalent use of conventional plastics derived from petrochemical refining and manufacturing processes in modern packaging. While these plastics serve vital functions, their persistence in the environment post-disposal poses significant threats to ecosystems. Addressing this issue necessitates approaches, one of which involves the development of biodegradable plastics designed to degrade under controlled conditions, such as industrial composting facilities. It is imperative to note that compostable plastics are engineered for degradation within specific environments and are not suited for uncontrolled settings, including natural landscapes and aquatic ecosystems. The full benefits of compostable packaging are realized when subjected to industrial composting, preventing environmental contamination and waste stream pollution. Therefore, effective sorting technologies are essential to enhance composting rates for these materials and diminish the risk of contaminating recycling streams. In this study, it leverage hyperspectral imaging technology (HSI) coupled with advanced machine learning algorithms to accurately identify various types of plastics, encompassing conventional variants like Polyethylene terephthalate (PET), Polypropylene (PP), Low density polyethylene (LDPE), High density polyethylene (HDPE) and biodegradable alternatives such as Polybutylene adipate terephthalate (PBAT), Polylactic acid (PLA), and Polyhydroxyalkanoates (PHA). The dataset is partitioned into three subsets: a training dataset comprising uncontaminated conventional and biodegradable plastics, a validation dataset encompassing contaminated plastics of both types, and a testing dataset featuring real-world packaging items in both pristine and contaminated states. Five distinct machine learning algorithms, namely Partial Least Squares Discriminant Analysis (PLS-DA), Support Vector Machine (SVM), Convolutional Neural Network (CNN), Logistic Regression, and Decision Tree Algorithm, were developed and evaluated for their classification performance. Remarkably, the Logistic Regression and CNN model exhibited the most promising outcomes, achieving a perfect accuracy rate of 100% for the training and validation datasets. Notably, the testing dataset yielded an accuracy exceeding 80%. The successful implementation of this sorting technology within recycling and composting facilities holds the potential to significantly elevate recycling and composting rates. As a result, the envisioned circular economy for plastics can be established, thereby offering a viable solution to mitigate plastic pollution.

Keywords: biodegradable plastics, sorting technology, hyperspectral imaging technology, machine learning algorithms

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Authors: Maciej Szeląg, Stanisław Fic

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The impact of elevated temperatures on the construction materials manifests in change of their physical and mechanical characteristics. Stresses and thermal deformations that occur inside the volume of the material cause its progressive degradation as temperature increase. Finally, the reactions and transformations of multiphase structure of cementitious composite cause its complete destruction. A particularly dangerous phenomenon is the impact of thermal shock – a sudden high temperature load. The thermal shock leads to a high value of the temperature gradient between the outer surface and the interior of the element in a relatively short time. The result of mentioned above process is the formation of the cracks and scratches on the material’s surface and inside the material. The article describes the use of computer image analysis techniques to identify and assess the structure of the cluster cracks on the surfaces of modified cement pastes, caused by thermal shock. Four series of specimens were tested. Two Portland cements were used (CEM I 42.5R and CEM I 52,5R). In addition, two of the series contained metakaolinite as a replacement for 10% of the cement content. Samples in each series were made in combination of three w/b (water/binder) indicators of respectively 0.4; 0.5; 0.6. Surface cracks of the samples were created by a sudden temperature load at 200°C for 4 hours. Images of the cracked surfaces were obtained via scanning at 1200 DPI; digital processing and measurements were performed using ImageJ v. 1.46r software. In order to examine the cracked surface of the cement paste as a system of closed clusters – the dispersal systems theory was used to describe the structure of cement paste. Water is used as the dispersing phase, and the binder is used as the dispersed phase – which is the initial stage of cement paste structure creation. A cluster itself is considered to be the area on the specimen surface that is limited by cracks (created by sudden temperature loading) or by the edge of the sample. To describe the structure of cracks two stereological parameters were proposed: A ̅ – the cluster average area, L ̅ – the cluster average perimeter. The goal of this study was to compare the investigated stereological parameters with the mechanical properties of the tested specimens. Compressive and tensile strength testes were carried out according to EN standards. The method used in the study allowed the quantitative determination of defects occurring in the examined modified cement pastes surfaces. Based on the results, it was found that the nature of the cracks depends mainly on the physical parameters of the cement and the intermolecular interactions on the dispersal environment. Additionally, it was noted that the A ̅/L ̅ relation of created clusters can be described as one function for all tested samples. This fact testifies about the constant geometry of the thermal cracks regardless of the presence of metakaolinite, the type of cement and the w/b ratio.

Keywords: cement paste, cluster cracks, elevated temperature, image analysis, metakaolinite, stereological parameters

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Authors: Riofrio Jonathan, Fernandez Guillermo

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Renewable energy represented around 80% of the energy matrix for power generation in Ecuador during 2020, so the deployment of current public policies is focused on taking advantage of the high presence of renewable sources to carry out several electrification projects. These projects are part of the portfolio sent to the United Nations Framework on Climate Change (UNFCCC) as a commitment to reduce greenhouse gas emissions (GHG) in the established national determined contribution (NDC). In this sense, the Ecuadorian Organic Energy Efficiency Law (LOEE) published in 2019 promotes E-mobility as one of the main milestones. In fact, it states that the new vehicles for urban and interurban usage must be E-buses since 2025. As a result, and for a successful implementation of this technological change in a national context, it is important to deploy land surveys focused on technical and geographical areas to keep the quality of services in both the electricity and transport sectors. Therefore, this research presents a technological and energy comparison between a conventional diesel bus and its equivalent E-bus. Both vehicles fulfill all the technical requirements to ride in the study-case city, which is Ambato in the province of Tungurahua-Ecuador. In addition, the analysis includes the development of a model for the energy estimation of both technologies that are especially applied in a highland city such as Ambato. The altimetry of the most important bus routes in the city varies from 2557 to 3200 m.a.s.l., respectively, for the lowest and highest points. These operation conditions provide a grade of novelty to this paper. Complementary, the technical specifications of diesel buses are defined following the common features of buses registered in Ambato. On the other hand, the specifications for E-buses come from the most common units introduced in Latin America because there is not enough evidence in similar cities at the moment. The achieved results will be good input data for decision-makers since electric demand forecast, energy savings, costs, and greenhouse gases emissions are computed. Indeed, GHG is important because it allows reporting the transparency framework that it is part of the Paris Agreement. Finally, the presented results correspond to stage I of the called project “Analysis and Prospective of Electromobility in Ecuador and Energy Mix towards 2030” supported by Deutsche Gesellschaft für Internationale Zusammenarbeit (GIZ).

Keywords: high altitude cities, energy planning, NDC, e-buses, e-mobility

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Authors: E. O. Clarke, O. J. Aderinola, O. A. Adeboyejo, M. A. Anetekhai

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Aims: The study is aimed at establishing the influence of some physical and chemical parameters on the abundance, distribution pattern and seasonal variations of the planktonic crustacean populations. Place and Duration of Study: A premier investigation into the dynamics of planktonic crustacean populations in Ologe lagoon was carried out from January 2011 to December 2012. Study Design: The study covered identification, temporal abundance, spatial distribution and diversity of the planktonic crustacea. Methodology: Standard techniques were used to collect samples from eleven stations covering five proximal satellite towns (Idoluwo, Oto, Ibiye, Obele, and Gbanko) bordering the lagoon. Data obtained were statistically analyzed using linear regression and hierarchical clustering. Results:Thirteen (13) planktonic crustacean populations were identified. Total percentage abundance was highest for Bosmina species (20%) and lowest for Polyphemus species (0.8%). The Pearson’s correlation coefficient (“r” values) between total planktonic crustacean population and some physical and chemical parameters showed that positive correlations having low level of significance occurred with salinity (r = 0.042) (sig = 0.184) and with surface water dissolved oxygen (r = 0.299) (sig = 0.155). Linear regression plots indicated that, the total population of planktonic crustacea were mainly influenced and only increased with an increase in value of surface water temperature (Rsq = 0.791) and conductivity (Rsq = 0.589). The total population of planktonic crustacea had a near neutral (zero correlation) with the surface water dissolved oxygen and thus, does not significantly change with the level of the surface water dissolved oxygen. The correlations were positive with NO3-N (midstream) at Ibiye (Rsq =0.022) and (downstream) Gbanko (Rsq =0.013), PO4-P at Ibiye (Rsq =0.258), K at Idoluwo (Rsq =0.295) and SO4-S at Oto (Rsq = 0.094) and Gbanko (Rsq = 0.457). The Berger-Parker Dominance Index (BPDI) showed that the most dominant species was Bosmina species (BPDI = 1.000), followed by Calanus species (BPDI = 1.254). Clusters by squared Euclidan distances using average linkage between groups showed proximities, transcending the borders of genera. Conclusion: The results revealed that planktonic crustacean population in Ologe lagoon undergo seasonal perturbations, were highly influenced by nutrient, metal and organic matter inputs from river Owoh, Agbara industrial estate and surrounding farmlands and were patchy in spatial distribution.

Keywords: diversity, dominance, perturbations, richness, crustacea, lagoon

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