Search results for: oxidation of hydrocarbons and alcohols

Authors: S. Shanthi

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Catalyzed oxidation processes show extraordinary guarantee for application in numerous wastewater treatment ranges. Advanced oxidation processes are emerging innovation that might be utilized for particular objectives in wastewater treatment. This research work provides a solution for removal a refractory organic compound 2,4-dichlorophenoxyaceticacid a common water pollutant. All studies were done in batch mode in a constantly stirred reactor. Alternative ozonation processes catalysed by transition metals or granular activated carbon have been investigated for degradation of organics. Catalytic ozonation under study are homogeneous catalytic ozonation, which is based on ozone activation by transition metal ions present in aqueous solution, and secondly as heterogeneous catalytic ozonation in the presence of Granular Activated Carbon (GAC). The present studies reveal that heterogeneous catalytic ozonation using GAC favour the ozonation of 2,4-dichlorophenoxyaceticacid by increasing the rate of ozonation and a much higher degradation of substrates were obtained in a given time. Be that it may, Fe2+and Fe3+ ions decreased the rate of degradation of 2,4-dichlorophenoxyaceticacid indicating that it acts as a negative catalyst. In case of heterogeneous catalytic ozonation using GAC catalyst it was found that during the initial 5 minutes of contact solution concentration decreased significantly as the pollutants were adsorbed initially. Thereafter the substrate started getting oxidized and ozonation became a dominates the treatment process. The exhausted GAC was found to be regenerated in situ. The percentage reduction of the substrate was maximum achieved in minimum possible time when GAC catalyst is employed.

Keywords: ozonation, homogeneous catalysis, heterogeneous catalysis, granular activated carbon

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Authors: I. Berger, N. Machour, F. Portet-Koltalo

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Polycyclic aromatic hydrocarbons (PAHs) are toxic and carcinogenic pollutants produced in majority by incomplete combustion processes in industrialized and urbanized areas. After being emitted in atmosphere, these persistent contaminants are deposited to soils or sediments. Even if persistent, some can be partially degraded (photodegradation, biodegradation, chemical oxidation) and they lead to oxygenated metabolites (oxy-PAHs) which can be more toxic than their parent PAH. Oxy-PAHs are less measured than PAHs in sediments and this study aims to compare different analytical tools in order to extract and quantify a mixture of four hydroxylated PAHs (OH-PAHs) and four carbonyl PAHs (quinones) in sediments. Methodologies: Two analytical systems – HPLC with on-line UV and fluorescence detectors (HPLC-UV-FLD) and GC coupled to a mass spectrometer (GC-MS) – were compared to separate and quantify oxy-PAHs. Microwave assisted extraction (MAE) was optimized to extract oxy-PAHs from sediments. Results: First OH-PAHs and quinones were analyzed in HPLC with on-line UV and fluorimetric detectors. OH-PAHs were detected with the sensitive FLD, but the non-fluorescent quinones were detected with UV. The limits of detection (LOD)s obtained were in the range (2-3)×10-4 mg/L for OH-PAHs and (2-3)×10-3 mg/L for quinones. Second, even if GC-MS is not well adapted to the analysis of the thermodegradable OH-PAHs and quinones without any derivatization step, it was used because of the advantages of the detector in terms of identification and of GC in terms of efficiency. Without derivatization, only two of the four quinones were detected in the range 1-10 mg/L (LODs=0.3-1.2 mg/L) and LODs were neither very satisfying for the four OH-PAHs (0.18-0.6 mg/L). So two derivatization processes were optimized, comparing to literature: one for silylation of OH-PAHs, one for acetylation of quinones. Silylation using BSTFA/TCMS 99/1 was enhanced using a mixture of catalyst solvents (pyridine/ethyle acetate) and finding the appropriate reaction duration (5-60 minutes). Acetylation was optimized at different steps of the process, including the initial volume of compounds to derivatize, the added amounts of Zn (0.1-0.25 g), the nature of the derivatization product (acetic anhydride, heptafluorobutyric acid…) and the liquid/liquid extraction at the end of the process. After derivatization, LODs were decreased by a factor 3 for OH-PAHs and by a factor 4 for quinones, all the quinones being now detected. Thereafter, quinones and OH-PAHs were extracted from spiked sediments using microwave assisted extraction (MAE) followed by GC-MS analysis. Several mixtures of solvents of different volumes (10-25 mL) and using different extraction temperatures (80-120°C) were tested to obtain the best recovery yields. Satisfactory recoveries could be obtained for quinones (70-96%) and for OH-PAHs (70-104%). Temperature was a critical factor which had to be controlled to avoid oxy-PAHs degradation during the MAE extraction process. Conclusion: Even if MAE-GC-MS was satisfactory to analyze these oxy-PAHs, MAE optimization has to be carried on to obtain a most appropriate extraction solvent mixture, allowing a direct injection in the HPLC-UV-FLD system, which is more sensitive than GC-MS and does not necessitate a previous long derivatization step.

Keywords: derivatizations for GC-MS, microwave assisted extraction, on-line HPLC-UV-FLD, oxygenated PAHs, polluted sediments

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Authors: Maria Trimintziou, Michael Sakellariou, Prodromos Psarropoulos

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Nowadays, the exploitation of hydrocarbons reserves in deep seas and oceans, in combination with the need to transport hydrocarbons among countries, has made the design, construction and operation of offshore pipelines very significant. Under this perspective, it is evident that many more offshore pipelines are expected to be constructed in the near future. Since offshore pipelines are usually crossing extended areas, they may face a variety of geohazards that impose substantial permanent ground deformations (PGDs) to the pipeline and potentially threaten its integrity. In case of a geohazard area, there exist three options to proceed. The first option is to avoid the problematic area through rerouting, which is usually regarded as an unfavorable solution due to its high cost. The second is to apply (if possible) mitigation/protection measures in order to eliminate the geohazard itself. Finally, the last appealing option is to allow the pipeline crossing through the geohazard area, provided that the pipeline will have been verified against the expected PGDs. In areas with moderate or high seismicity the design of an offshore pipeline is more demanding due to the earthquake-related geohazards, such as landslides, soil liquefaction phenomena, and active faults. It is worthy to mention that although worldwide there is a great experience in offshore geotechnics and pipeline design, the experience in seismic design of offshore pipelines is rather limited due to the fact that most of the pipelines have been constructed in non-seismic regions (e.g. North Sea, West Australia, Gulf of Mexico, etc.). The current study focuses on the seismic design of offshore pipelines against active faults. After an extensive literature review of the provisions of the seismic norms worldwide and of the available analytical methods, the study simulates numerically (through finite-element modeling and strain-based criteria) the distress of offshore pipelines subjected to PGDs induced by active seismic faults at the seabed. Factors, such as the geometrical properties of the fault, the mechanical properties of the ruptured soil formations, and the pipeline characteristics, are examined. After some interesting conclusions regarding the seismic vulnerability of offshore pipelines, potential cost-effective mitigation measures are proposed taking into account constructability issues.

Keywords: offhore pipelines, seismic design, active faults, permanent ground deformations (PGDs)

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Authors: S. Mousavian, A. Abedianpour, A. Khanmohammadi, S. Hematian, Gh. Eidi Veisi

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Ionic liquids are finding a wide range of applications from reaction media to separations and materials processing. In these applications, Vapor–Liquid equilibrium (VLE) is the most important one. VLE for six systems at 353 K and activity coefficients at infinite dilution 〖(γ〗_i^∞) for various solutes (alkanes, alkenes, cycloalkanes, cycloalkenes, aromatics, alcohols, ketones, esters, ethers, and water) in the ionic liquids (1-ethyl-3-methylimidazolium bis (trifluoromethylsulfonyl)imide [EMIM][BTI], 1-hexyl-3-methyl imidazolium bis (trifluoromethylsulfonyl) imide [HMIM][BTI], 1-octyl-3-methylimidazolium bis(trifluoromethylsulfonyl) imide [OMIM][BTI], and 1-butyl-1-methylpyrrolidinium bis (trifluoromethylsulfonyl) imide [BMPYR][BTI]) have been used to train neural networks in the temperature range from (303 to 333) K. Densities of the ionic liquids, Hildebrant constant of substances, and temperature were selected as input of neural networks. The networks with different hidden layers were examined. Networks with seven neurons in one hidden layer have minimum error and good agreement with experimental data.

Keywords: ionic liquid, neural networks, VLE, dilute solution

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Authors: H. Boukhatem, L. Djouadi, H. Khalaf, R. M. Navarro, F. V. Ganzalez

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Synthetic organic dyes are used in various industries, such as textile industry, leather tanning industry, paper production, hair dye production, etc. Wastewaters containing these dyes may be harmful to the environment and living organisms. Therefore, it is very important to remove or degrade these dyes before discharging them into the environment. In addition to standard technologies for the degradation and/or removal of dyes, several new specific technologies, the so-called advanced oxidation processes (AOPs), have been developed to eliminate dangerous compounds from polluted waters. AOPs are all characterized by the same chemical feature: production of radicals (•OH) through a multistep process, although different reaction systems are used. These radicals show little selectivity of attack and are able to oxidize various organic pollutants due to their high oxidative capacity (reduction potential of HO• Eo = 2.8 V). Heterogeneous photocatalysis, as one of the AOPs, could be effective in the oxidation/degradation of organic dyes. A major advantage of using heterogeneous photocatalysis for this purpose is the total mineralization of organic dyes, which results in CO2, H2O and corresponding mineral acids. In this study, nanomaterials based on montmorillonite and CuxCd1-xS with different Cu concentration (0.3 < x < 0.7) were utilized for the degradation of the commercial cationic textile dye Methylene blue (MB), used as a model pollutant. The synthesized nanomaterials were characterized by fourier transform infrared (FTIR) and thermogravimetric-differential thermal analysis (TG–DTA). Test results of photocatalysis of methylene blue under UV-Visible irradiation show that the photoactivity of nanomaterials montmorillonite/ CuxCd1-xS increases with the increasing of Cu concentration. The kinetics of the degradation of the MB dye was described with the Langmuir–Hinshelwood (L–H) kinetic model.

Keywords: heterogeneous photocatalysis, methylene blue, montmorillonite, nanomaterial

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Authors: Y. S. Shen, B. H. Liao

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This study aimed to develop the design equation of a laminar-falling-film-slurry (LFFS) type photoreactor for the treatment of organic wastewaters containing isopropyl alcohol (IPA) by VUV-based advanced oxidation processes (AOPs). The photoreactor design equations were established by combining with the chemical kinetics of the photocatalytic system, light absorption model within the photoreactor, and was used to predict the decomposition of IPA in aqueous solutions in the photoreactors of different geometries at various operating conditions (volumetric flow rate, oxidants, catalysts, solution pH values, UV light intensities, and initial concentration of pollutants) to verify its rationality and feasibility. By the treatment of the LFFS-VUV only process, it was found that the decomposition rates of IPA in aqueous solutions increased with the increase of volumetric flow rate, VUV light intensity, dosages of TiO2 and H2O2. The removal efficiencies of IPA by photooxidation processes were in the order: VUV/H2O2>VUV/TiO2/H2O2>VUV/TiO2>VUV only. In VUV, VUV/H2O2, VUV/TiO2/H2O2 processes, integrating with the reaction kinetic equations of IPA, the mass conservation equation and the linear light source model, the photoreactor design equation can reasonably to predict reaction behaviors of IPA at various operating conditions and to describe the concentration distribution profiles of IPA within photoreactors.The results of this research can be useful basis for the future application of the homogeneous and heterogeneous VUV-based advanced oxidation processes.

Keywords: isopropyl alcohol, photoreactor design, VUV, AOPs

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Authors: N. Jirukkakul, J. Sodtipinta

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Tomatoes are widely consumed as fresh and processed products through the manufacturing industry. Therefore, tomato pomace is generated as a by-product accounting for about 5-13% of the whole tomato. Antioxidants still remain in tomato pomace and extraction of tomato oil may useful in edible film production. The edible film solution was prepared by mixing gelatin (2, 4 and 6%) with the distilled water and heating at 40oC for 30 min. Effect of tomato pomace oil was evaluated at 0, 0.5 and 1%. Film solution was poured in plate and dried overnight at 40oC before determining the physical properties, which are tensile strength, moisture content, color, solubility, and swelling power. The results showed that an increase gelatin concentration caused increasing of tensile strength, moisture content, solubility and swelling power. The edible film with tomato pomace oil extract appeared as the rough film with oil droplet dispersion. The addition of tomato pomace oil extract caused an increase in lightness, redness and yellowness, while tensile strength, moisture content, and solubility were decreased. Film with tomato pomace oil extract at 0.5 and 1% exhibited antioxidant properties but those properties were not significantly different (p<0.05) between film incorporated with tomato pomace oil extract 0.5 and 1%. The suitable condition for film production in this study, 4% of gelatin and 0.5% of tomato pomace oil extract, was selected for protecting oxidation of palm oil. At 15 days of the storage period, the palm oil which covered by gelatin film with tomato pomace oil extract had 22.45 milliequivalents/kg of peroxide value (PV), while, the palm oil which covered by polypropylene film and control had 24.79 and 26.67 milliequivalents/kg, respectively. Therefore, incorporation of tomato pomace oil extract in gelatin film was able to protect the oxidation of food products with high fat content.

Keywords: antioxidant, gelatin films, physical properties, tomato oil extract

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Authors: Ageliki I. Katsarou, Andriana C. Kaliora, Antonia Chiou, Apostolos Papalois, Nick Kalogeropoulos, Nikolaos K. Andrikopoulos

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Oxidative stress is a major mechanism underlying CVDs while inflammation, an intertwined process with oxidative stress, is also linked to CVDs. Extra virgin olive oil (EVOO) is widely known to play a pivotal role in CVD prevention and CVD reduction. However, in most studies, olive oil constituents are evaluated individually and not as part of the native food, hence potential synergistic effects as drivers of EVOO beneficial properties may be underestimated. In this study, EVOO lipidic and polar phenolics fractions were evaluated for their effect on inflammatory (TNF-alpha) and oxidation (malondialdehyde/MDA) markers, in cholesterol-fed rats. Thereat, oils with discernible lipidic profile and polar phenolic content were used. Wistar rats were fed on either a high-cholesterol diet (HCD) or a HCD supplemented with oils, either commercially available, i.e. EVOO, sunflower oil (SO), or modified as to their polar phenol content, i.e. phenolics deprived-EVOO (EVOOd), SO enriched with the EVOO phenolics (SOe). After 9 weeks of dietary intervention, heart and blood samples were collected. HCD induced dylipidemia shown by increase in serum total cholesterol, low-density lipoprotein cholesterol (LDL-c) and triacylglycerols. Heart tissue has been affected by dyslipidemia; oxidation was indicated by increase in MDA in cholesterol-fed rats and inflammation by increase in TNF-alpha. In both cases, this augmentation was attenuated in EVOO and SOe diets. With respect to oxidation, SO enrichment with the EVOO phenolics brought its lipid peroxidation levels as low as in EVOO-fed rats. This suggests that phenolic compounds may act as antioxidant agents in rat heart. A possible mechanism underlying this activity may be the protective effect of phenolics in mitochondrial membrane against oxidative damage. This was further supported by EVOO/EVOOd comparison with the former presenting lower heart MDA content. As for heart inflammation, phenolics naturally present in EVOO as well as phenolics chemically added in SO, exhibited quenching abilities in heart TNF-alpha levels of cholesterol-fed rats. TNF-alpha may have played a causative role in oxidative stress induction while the opposite may have also happened, hence setting up a vicious cycle. Overall, diet supplementation with EVOO or SOe attenuated hypercholesterolemia-induced increase in MDA and TNF-alpha in Wistar rat hearts. This is attributed to phenolic compounds either naturally existing in olive oil or as fortificants in seed oil.

Keywords: extra virgin olive oil, hypercholesterolemic rats, MDA, polar phenolics, TNF-alpha

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Authors: Yves Mann Elate Lea Mbassi, Marie Solange Evehe Bebandoue, Wilfred Fon Mbacham

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Improving the catalytic performance of enzymes has been a long-standing theme of analytical biochemistry research. Induction of peroxidase activity by metals is a common reaction in higher plants. We thought that this increase in peroxidase activity may be due, on the one hand, to the stimulation of the gene expression of these enzymes but also to a modification of their chemical reactivity following the binding of some metal ions on their active site. We tested the effect of some metal salts (MgCl₂, MnCl₂, ZnCl₂, CaCl₂ and CuSO₄) on the activity and thermostability of peroxidase A6, a thermostable peroxidase that we discovered and purified in a previous study. The chromogenic substrate used was 3,3′,5,5′-tetramethylbenzidine. Of all the metals tested for their effect on A6, only magnesium and copper had a significant effect on the activity of the enzyme at room temperature. The Mann-Whitney test shows a slight inhibitory effect of activity by the magnesium salt (P = 0.043), while the activity of the enzyme is 5 times higher in the presence of the copper salt (P = 0.002). Moreover, the thermostability of peroxidase A6 is increased when calcium and copper salts are present. The activity in the presence of CaCl₂ is 8 times higher than the residual activity of the enzyme alone after incubation at 80°C for 10 min and 35 times higher in the presence of CuSO4 under the same conditions. In addition, manganese and zinc salts slightly reduce the thermostability of the enzyme. The activity and structural stability of peroxidase A6 can clearly be activated by Cu₂+, which therefore enhance the oxidation of 3,3′,5,5′-tetramethylbenzidine, which was used in this study as a chromogenic substrate. Ca₂+ likely has a more stabilizing function for the catalytic site.

Keywords: peroxidase activity, copper ions, calcium ions, thermostability

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Authors: Shekher Kummari, V. Sunil Kumar, K. Vengatajalabathy Gobi

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A simple, cost-effective, reusable and reagent-free electrochemical biosensor is developed with functionalized multiwall carbon nanotube paste electrode (f-CNTPE) for the sensitive and selective determination of the important chemotherapeutic drug methotrexate (MTX), which is widely used for the treatment of various cancer and autoimmune diseases. The electrochemical response of the fabricated electrode towards the detection of MTX is examined by cyclic voltammetry (CV), differential pulse voltammetry (DPV) and square wave voltammetry (SWV). CV studies have shown that f-CNTPE electrode system exhibited an excellent electrocatalytic activity towards the oxidation of MTX in phosphate buffer (0.2 M) compared with a conventional carbon paste electrode (CPE). The oxidation peak current is enhanced by nearly two times in magnitude. Applying the DPV method under optimized conditions, a linear calibration plot is achieved over a wide range of concentration from 4.0×10⁻⁷ M to 5.5×10⁻⁶ M with the detection limit 1.6×10⁻⁷ M. further, by applying the SWV method a parabolic calibration plot was achieved starting from a very low concentration of 1.0×10⁻⁸ M, and the sensor could detect as low as 2.9×10⁻⁹ M MTX in 10 s and 10 nM were detected in steady state current-time analysis. The f-CNTPE shows very good selectivity towards the specific recognition of MTX in the presence of important biological interference. The electrochemical biosensor detects MTX in-vitro directly from pharmaceutical sample, undiluted urine and human blood serum samples at a concentration range 5.0×10⁻⁷ M with good recovery limits.

Keywords: amperometry, electrochemical detection, human blood serum, methotrexate, MWCNT, SWV

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Authors: K. Tunde Olagunju, C. Scott Allen, Freek Van Der Meer

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Identification of hydrocarbon oil in remote sensing images is often the first step in monitoring oil during spill events. Most remote sensing methods adopt techniques for hydrocarbon identification to achieve detection in order to model an appropriate cleanup program. Identification on optical sensors does not only allow for detection but also for characterization and quantification. Until recently, in optical remote sensing, quantification and characterization are only potentially possible using high-resolution laboratory and airborne imaging spectrometers (hyperspectral data). Unlike multispectral, hyperspectral data are not freely available, as this data category is mainly obtained via airborne survey at present. In this research, two (2) operational high-resolution multispectral satellites (WorldView-3 and Sentinel-2) are theoretically assessed for their suitability for hydrocarbon characterization, using the hydrocarbon spectral slope model (HYSS). This method utilized the two most persistent hydrocarbon diagnostic/absorption features at 1.73 µm and 2.30 µm for hydrocarbon mapping on multispectral data. In this research, spectra measurement of seven (7) different hydrocarbon oils (crude and refined oil) taken on ten (10) different substrates with the use of laboratory ASD Fieldspec were convolved to Sentinel-2 and WorldView-3 resolution, using their full width half maximum (FWHM) parameter. The resulting hydrocarbon slope values obtained from the studied samples enable clear qualitative discrimination of most hydrocarbons, despite the presence of different background substrates, particularly on WorldView-3. Due to close conformity of central wavelengths and narrow bandwidths to key hydrocarbon bands used in HYSS, the statistical significance for qualitative analysis on WorldView-3 sensors for all studied hydrocarbon oil returned with 95% confidence level (P-value ˂ 0.01), except for Diesel. Using multifactor analysis of variance (MANOVA), the discriminating power of HYSS is statistically significant for most hydrocarbon-substrate combinations on Sentinel-2 and WorldView-3 FWHM, revealing the potential of these two operational multispectral sensors as rapid response tools for hydrocarbon mapping. One notable exception is highly transmissive hydrocarbons on Sentinel-2 data due to the non-conformity of spectral bands with key hydrocarbon absorptions and the relatively coarse bandwidth (> 100 nm).

Keywords: hydrocarbon, oil spill, remote sensing, hyperspectral, multispectral, hydrocarbon-substrate combination, Sentinel-2, WorldView-3

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Authors: Temitope L. Baiyegunhi, Christopher Baiyegunhi, Kuiwu Liu, Oswald Gwavava

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Diagenesis is the most important factor that affects or impact the reservoir property. Despite the fact that published data gives a vast amount of information on the geology, sedimentology and lithostratigraphy of the Ecca Group in the Karoo Basin of South Africa, little is known of the diagenesis of the potentially feasible shales and sandstones of the Ecca Group. The study aims to provide a general account of the diagenesis of sandstones and mudstone of the Ecca Group. Twenty-five diagenetic textures and structures are identified and grouped into three regimes or stages that include eogenesis, mesogenesis and telogenesis. Clay minerals are the most common cementing materials in the Ecca sandstones and mudstones. Smectite, kaolinite and illite are the major clay minerals that act as pore lining rims and pore-filling cement. Most of the clay minerals and detrital grains were seriously attacked and replaced by calcite. Calcite precipitates locally in pore spaces and partly or completely replaced feldspar and quartz grains, mostly at their margins. Precipitation of cements and formation of pyrite and authigenic minerals as well as little lithification occurred during the eogenesis. This regime was followed by mesogenesis which brought about an increase in tightness of grain packing, loss of pore spaces and thinning of beds due to weight of overlying sediments and selective dissolution of framework grains. Compaction, mineral overgrowths, mineral replacement, clay-mineral authigenesis, deformation and pressure solution structures occurred during mesogenesis. During rocks were uplifted, weathered and unroofed by erosion, this resulted in additional grain fracturing, decementation and oxidation of iron-rich volcanic fragments and ferromagnesian minerals. The rocks of Ecca Group were subjected to moderate-intense mechanical and chemical compaction during its progressive burial. Intergranular pores, matrix micro pores, secondary intragranular, dissolution and fractured pores are the observed pores. The presence of fractured and dissolution pores tend to enhance reservoir quality. However, the isolated nature of the pores makes them unfavourable producers of hydrocarbons, which at best would require stimulation. The understanding of the space and time distribution of diagenetic processes in these rocks will allow the development of predictive models of their quality, which may contribute to the reduction of risks involved in their exploration.

Keywords: diagenesis, reservoir quality, Ecca Group, Karoo Supergroup

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Authors: Nacira Mecheri, N. Boussid

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A new chemical mechanism designed to study the process of forming the first aromatic ring (benzene) and polycyclic aromatic hydrocarbons (PAH) from a flame of acetylene (C2H2) has been developed. The mechanism developed, contains 50 chemical species involved in 268 reversible elementary reactions. The comparison between the results from modelling and experimental measurements allowed us to test the validity of the postulated mechanism in specific experimental conditions. Kinetic analysis of the flame by calculating the maximum rates for each elementary reaction, allowed us to identify key reactions pathways of consumption and formation of main precursors of soot.

Keywords: benzene, PAH, acetylene, modeling, flame, soot

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Authors: Rong Sun, Laihong Shen

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La-based perovskite oxygen carriers, especially the doped-La(M)FeO₃, showed excellent performances during chemical looping processes. However, the mechanisms of the undoped and doped La(M)FeO₃ are not clear at present, making the mechanisms clear may help the development of chemical looping technologies. In this paper, the method based on the density function theory (DFT) was used to analysis the influence of Ca, Sr, and Ba doping of La on the electronic structure, while the CO oxidation mechanisms on the surface of LaFeO₃ and Ca-doped LaFeO₃ oxygen carriers were also analyzed. The results showed that the band gap was decreased by the doping of low valence. While the doping of low valence element Ca, Sr, and Ba at La site simultaneously resulted to the moving of the valence band toward high energy and made the valence band cross the Fermi energy level. This was resulted from the holes generated by divalent ion substitution. The holes can change the total magnetization from antiferromagnet to weakly ferromagnetism. The calculation results about the formation of oxygen vacancy showed that substitutions of Ca, Sr, and Ba caused a large drop in oxygen vacancy formation energy, indicating that the bulk oxygen transport was improved. Based on the optimized bulk of the undoped and Ca-doped LaFeO₃(010) surface, the CO adsorption was analyzed. The results indicated that the adsorption energy increased by divalent ion substitution, meaning that the adsorption stability decreased. The results can provide a certain theoretical basis for the development of perovskite oxides in chemical looping technologies.

Keywords: chemical looping technologies, lanthanum ferrate (LaFeO₃), divalent ion substitution, CO oxidation

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Authors: Gabriel K. Nzulu, Lina Rostorm, Hans Högberg, Jun Liu, per Eklund, Lars Hultman, Martin Magnuson

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Altered and gangue quartz in hydrothermal veins from the Kubi Gold deposit in Dunkwa on Offin in the central region of Ghana are investigated for possible Au associated pathfinder minerals and to provide understanding and increase the knowledge of the mineral hosting and alteration processes in quartz. X-ray diffraction, air annealing furnace, differential scanning calorimetry, energy dispersive X-ray spectroscopy, and transmission electron microscopy have been applied on different quartz types outcropping from surface and bed rocks at the Kubi Gold Mining to reveal the material properties at different temperatures. From the diffraction results of the fresh and annealed quartz samples, we find that the samples contain pathfinder and the impurity minerals FeS₂, biotite, TiO₂, and magnetite. These minerals, under oxidation process between 574-1400 °C temperatures experienced hematite alterations and a transformation from α-quartz to β-quartz and further to cristobalite as observed from the calorimetry scans for hydrothermally exposed materials. The energy dispersive spectroscopy revealed elemental species of Fe, S, Mg, K, Al, Ti, Na, Si, O, and Ca contained in the samples and these are attributed to the impurity phase minerals observed in the diffraction. The findings also suggest that during the hydrothermal flow regime, impurity minerals and metals can be trapped by voids and faults. Under favorable temperature conditions the trapped minerals can be altered to change color at different depositional stages by oxidation and reduction processes leading to hematite alteration which is a useful pathfinder in mineral exploration.

Keywords: quartz, hydrothermal, minerals, hematite, x-ray diffraction, crystal-structure, defects

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Authors: Fahad Aljasass, Hamza Abu-Tarboush, Salah Aleid, Siddig Hamad

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The effects of different high hydrostatic pressure treatments on the shelf life of camel’s milk were studied. Treatments at 300 to 350 MPa for 5 minutes at 40°C reduced microbial contamination to levels that prolonged the shelf life of refrigerated (3° C) milk up to 28 days. The treatment resulted in a decrease in the proteolytic activity of the milk. The content of proteolytic enzymes in the untreated milk sample was 4.23 µM/ml. This content decreased significantly to 3.61 µM/ml when the sample was treated at 250 MPa. Treatment at 300 MPa decreased the content to 3.90 which was not significantly different from the content of the untreated sample. The content of the sample treated at 350 MPa dropped to 2.98 µM/ml which was significantly lower than the contents of all other treated and untreated samples. High pressure treatment caused a slight but statistically significant increase in the pH of camel’s milk. The pH of the untreated sample was 6.63, which increased significantly to 6.70, in the samples treated at 250 and 350 MPa, but insignificantly in the sample treated at 300 MPa. High pressure treatment resulted in some degree of milk fat oxidation. The thiobarbituric acid (TBA) value of the untreated sample was 0.86 mg malonaldehyde/kg milk. This value remained unchanged in the sample treated at 250 MPa, but then it increased significantly to 1.25 and 1.33 mg/kg in the samples treated at 300 and 350 MPa, respectively. High pressure treatment caused a small increase in the greenness (a* value) of camel’s milk. The value of a* was reduced from -1.17 for the untreated sample to -1.26, -1.21 and -1.30 for the samples treated at 250, 300 and 350 MPa, respectively. Δa* at the 250 MPa treatment was -0.09, which then decreased to -0.04 at the 300 MPa treatment to increase again to -0.13 at the 350 MPa treatment. The yellowness (b* value) of camel’s milk increased significantly as a result of high pressure treatment. The b* value of the untreated sample was 1.40, this value increased to 2.73, 2.31 and 2.18 after treatments at 250, 300 and 350 MPa, respectively. The Δb* value was +1.33 at the treatment 250 MPa, decreased to +0.91 at 300 MPa and further to +0.78 at 350 MPa. The pressure treatment caused slight effect on color, slight decrease in protease activity and a slight increase in the oxidation products of lipids.

Keywords: high hydrostatic pressure, camel’s milk, mesophilic aerobic bacteria, clotting, protease

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Authors: Theo H. G. Moundzounga

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Arsenic and 2-chlorophenol are priority pollutants that pose serious health threats to humans and ecology. An electrochemical sensor, based on graphitic carbon nitride (g-C₃N₄) and carbon dots (CDs), was fabricated and used for the determination of arsenic and 2-chlorophenol. The g-C₃N₄/CDs nanocomposite was prepared via microwave irradiation heating method and was dropped-dried on the surface of the glassy carbon electrode (GCE). Transmission electron microscopy (TEM), X-ray diffraction (XRD), photoluminescence (PL), Fourier transform infrared spectroscopy (FTIR), UV-Vis diffuse reflectance spectroscopy (UV-Vis DRS) were used for the characterization of structure and morphology of the nanocomposite. Electrochemical characterization was done by electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV). The electrochemical behaviors of arsenic and 2-chlorophenol on different electrodes (GCE, CDs/GCE, and g-C₃N₄/CDs/GCE) was investigated by differential pulse voltammetry (DPV). The results demonstrated that the g-C₃N₄/CDs/GCE significantly enhanced the oxidation peak current of both analytes. The analytes detection sensitivity was greatly improved, suggesting that this new modified electrode has great potential in the determination of trace level of arsenic and 2-chlorophenol. Experimental conditions which affect the electrochemical response of arsenic and 2-chlorophenol were studied, the oxidation peak currents displayed a good linear relationship to concentration for 2-chlorophenol (R²=0.948, n=5) and arsenic (R²=0.9524, n=5), with a linear range from 0.5 to 2.5μM for 2-CP and arsenic and a detection limit of 2.15μM and 0.39μM respectively. The modified electrode was used to determine arsenic and 2-chlorophenol in spiked tap and effluent water samples by the standard addition method, and the results were satisfying. According to the measurement, the new modified electrode is a good alternative as chemical sensor for determination of other phenols.

Keywords: electrochemistry, electrode, limit of detection, sensor

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Authors: Adebisi Moruf Ademola

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Hematite (Fe2O3),commonly known as ‘rust’ which usually surfaced on metal when exposed to some climatic materials. This emerges as a promising candidate for photoelectrochemical (PEC) water splitting due to its favorable physiochemical properties of the narrow band gap (2.1–2.2 eV), chemical stability, nontoxicity, abundance, and low cost. However, inherent limitations such as short hole diffusion length (2–4 nm), high charge recombination rate, and slow oxygen evolution reaction kinetics inhibit the PEC performances of a-Fe2O3 photoanodes. As such, given the narrow bandgap enabling excellent optical absorption, increased charge carrier density and accelerated surface oxidation reaction kinetics become the key points for improved photoelectrochemical performances for a-Fe2O3 photoanodes and metal ion doping as an effective way to promote charge transfer by increasing donor density and improving the electronic conductivity of a-Fe2O3. Hematite attracts enormous efforts with a number of metal ions (Ti, Zr, Sn, Pt ,etc.) as dopants. A facile deposition-annealing process showed greatly enhanced PEC performance due to the increased donor density and reduced electron-hole recombination at the time scale beyond a few picoseconds. Zr doping was also found to enhance the PEC performance of a-Fe2O3 nanorod arrays by reducing the rate of electron-hole recombination. Slow water oxidation reaction kinetics, another main factor limiting the PEC water splitting efficiency of aFe2O3 as photoanodes, was previously found to be effectively improved by surface treatment.

Keywords: deposition-annealing, hematite, metal ion doping, nanorod

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Authors: Andrea Dragu, Solen Kinayyigit, Valerie Colliere, Karin Karin Philippot, Camelia Bala, Vasile I. Parvulescu

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The production of transportation fuels from biomass has gained a growing attention due to diminishing fossil fuel reserves, rising petroleum prices and increasing concern about global warming. In recent years, renewable hydrocarbons that are completely fungible with fossil fuels have been suggested to be efficiently produced by catalytic deoxygenation of fatty acids and their derivatives viadecarboxylation / decarbonylation. Several triglycerides (tall oil fatty acids) and saturated/unsaturated fatty acids and their corresponding esters were used as feedstocks. Their impact together with the influence of the reaction conditions and the catalyst composition on the nature of the reaction pathways of the deoxygenation of vegetable oils and their derivatives were recently reviewed. Following this state of the art the aim of the present study was the investigation of Pd NPs deposited onto mesoporous carbon supports as active and stable catalysts for the deoxygenation of oleic acid. The catalysts were prepared by the deposition of Pd NPs synthesised following an organometallic route on mesoporous carbons with different characteristics. Experiments were carried out under both batch and flow conditions. They demonstrated that under batch conditions (200 atm; 573K), the extent of the reaction depended, firstly, on the Pd loading and then on the metal dispersion and the oxidation state of palladium, both influenced by the way the support has been treated before the NPs deposition and by the preparation/stabilization methodology of Pd NPs. No aromatic compounds were detected in the reaction products but octadecanol and octadecane were observed in large extents. Under flow conditions (4 atm; 573 K), the conversion of stearic acid was superior to that observed in batch conditions. The product mixture contained over 20% heptadecane. No octadecanol, octadecane, and aromatic compounds were detected. The maxima in performances are obtained after only 0.5 h. After that, the yields in heptadecane suffer from a severe decrease until 3h reaction time. However, at that time, stopping feeding the reactor with oleic acid and flushing the catalyst only with mesitylene recovered the activity and the selectivity of the catalysts. With the complete removal of H2, the analysis revealed the presence of heptadecene in high excess compared to heptadecane (almost 7 to 1), thus suggesting decarbonylation as the main route. ICP-OES measurements indicated no leaching of palladium and simple washing of catalysts with mesitylene allowed recycling without any change in conversion or product distribution. Noteworthy, mesitylene as solvent exhibited no effect in this reaction. In conclusion, this study demonstrates the feasibility of such catalysts for the green production of fuels from biomass.

Keywords: fuels from biomass, green catalyst, Pd nano-particles , recycble catalyst

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Authors: Lekgowa Collen Makola, Cecil Naphtaly Moro Ouma, Sharon Moeno, Langelihle Dlamini

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In recent years, advancement in the field of nanotechnology has evolved new strategies to address energy and environmental issues. Amongst the developing technologies, visible-light-driven photocatalysis is regarded as a sustainable approach for energy production and environmental detoxifications, where transition metal oxides (TMOs) and metal-free carbon-based semiconductors such as graphitic carbon nitride (CN) evidenced notable potential in this matter. Herein, g-C₃N₄@WO₃@Ti₃C₂Tx three-component multijunction photocatalyst was fabricated via facile ultrasonic-assisted self-assembly, followed by calcination to facilitate extensive integrations of the materials. A series of different Ti₃C₂ wt% loading in the g-C₃N4@WO₃@Ti₃C₂Tx were prepared and represented as 1-CWT, 3-CWT, 5-CWT, and 7-CWT corresponding to 1, 3, 5, and 7wt%, respectively. Systematic characterization using spectroscopic and microscopic techniques were employed to validate the successful preparation of the photocatalysts. Enhanced optoelectronic and photoelectrochemical properties were observed for the WO₃@Ti₃C2@g-C₃N4 heterostructure with respect to the individual materials. Photoluminescence spectra and Nyquist plots show restrained recombination rates and improved photocarrier conductivities, respectively, and this was credited to the synergistic coupling effect and the presence of highly conductive Ti₃C2 MXene. The strong interfacial contact surfaces upon the formation of the composite were confirmed using XPS. Multiple charge transfer mechanisms were proposed for the WO3@Ti3C₂@g-C3N4, which couples Z-scheme and Schottky-junction mediated with Ti3C2 MXene. Bode phase plots show improved charge carrier life-times upon the formation of the multijunctional photocatalyst. Moreover, transient photocurrent density of 7-CWT is 40 and seven (7) times higher compared to that of g-C₃N4 and WO3, correspondingly. Unlike in the traditional Z-Scheme, the formed ternary heterostructure possesses interfaces through the metallic 2D Ti₃C₂ MXene, which provided charge transfer channels for efficient photocarrier transfers with carrier concentrations (ND) of 17.49×1021 cm-3 and 4.86% photo-to-chemical conversion efficiency. The as-prepared ternary g-C₃N₄@WO₃@Ti₃C₂Tx exhibited excellent photoelectrochemical properties with reserved redox band potential potencies to facilitate efficient photo-oxidation and -reduction reactions. The fabricated multijunction photocatalyst exhibits potentials to be used in an extensive range of photocatalytic process vis., production of valuable hydrocarbons from CO₂, production of H₂, and degradation of a plethora of pollutants from wastewater.

Keywords: photocatalysis, Z-scheme, multijunction heterostructure, Ti₃C₂ MXene, g-C₃N₄

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Authors: Nguyen Van Toan, Suguru Sangu, Tetsuro Saito, Naoki Inomata, Takahito Ono

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This paper presents the design and fabrication of an optical window for an optical modulator toward image sensing applications. An optical window consists of micrometer-order SiO2 capillaries (porous solid) that can modulate transmission light intensity by moving the liquid in and out of porous solid. A high optical transmittance of the optical window can be achieved due to refractive index matching when the liquid is penetrated into the porous solid. Otherwise, its light transmittance is lower because of light reflection and scattering by air holes and capillary walls. Silicon capillaries fabricated by deep reactive ion etching (DRIE) process are completely oxidized to form the SiO2 capillaries. Therefore, high aspect ratio SiO2 capillaries can be achieved based on silicon capillaries formed by DRIE technique. Large compressive stress of the oxide causes bending of the capillary structure, which is reduced by optimizing the design of device structure. The large stress of the optical window can be released via thin supporting beams. A 7.2 mm x 9.6 mm optical window area toward a fully integrated with the image sensor format is successfully fabricated and its optical transmittance is evaluated with and without inserting liquids (ethanol and matching oil). The achieved modulation range is approximately 20% to 35% with and without liquid penetration in visible region (wavelength range from 450 nm to 650 nm).

Keywords: thermal oxidation process, SiO2 capillaries, optical window, light transmittance, image sensor, liquid penetration

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Authors: Patrick Mueller, Alan Martin, Justin Stockwell, Robert Goldblatt

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Elevated concentrations of inorganic nitrogen (N) compounds (nitrate, nitrite, and ammonia) are a ubiquitous feature to mine-influenced drainages due to the leaching of blasting residues and use of cyanide in the milling of gold ores. For many mines, the management of N is a focus for environmental protection, therefore understanding the factors controlling the speciation and behavior of N is central to effective decision making. In this paper, the passive attenuation of ammonia and nitrite is described for three northern water bodies (two lakes and a tailings pond) influenced by mining activities. In two of the water bodies, inorganic N compounds originate from explosives residues in mine water and waste rock. The third water body is a decommissioned tailings impoundment, with N compounds largely originating from the breakdown of cyanide compounds used in the processing of gold ores. Empirical observations from water quality monitoring indicate nitrification (the oxidation of ammonia to nitrate) occurs in all three waterbodies, where enrichment of nitrate occurs commensurately with ammonia depletion. The N species conversions in these systems occurred more rapidly than chemical oxidation kinetics permit, indicating that microbial mediated conversion was occurring, despite the cool water temperatures. While nitrification of ammonia and nitrite to nitrate was the primary process, in all three waterbodies nitrite was consistently present at approximately 0.5 to 2.0 % of total N, even following ammonia depletion. The persistence of trace amounts of nitrite under these conditions suggests the co-occurrence denitrification processes in the water column and/or underlying substrates. The implications for N management in mine waters are discussed.

Keywords: explosives, mining, nitrification, water

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Authors: Abd El-Aziz Said

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In this study, natural silica was used as an active, selective, reusable and eco-friendly catalyst for the liquid phase synthesis of iso-amyl, benzyl and cinnamyl esters. The original and calcined natural silica were characterized by TG-DTA, XRF, XRD, FTIR, SEM, and N2-sorption analysis. The surface acidity of the catalysts was determined using isopropanol dehydration and the strength of available acid sites was measured using chemisorption of pyridine (PY) and dimethyl pyridine (DMPY). The results of acidity specified that the acidic sites are of Brönsted type, while PY-TPD demonstrated that almost of the acidic sites over the surface of natural silica are of weak and intermediate strength. The catalytic activity of natural silica towards esterification of acetic acid with alcohols was extensively studied. The results revealed that natural silica had high catalytic activity with 100% selectivity to all targeted esters. In addition, the yields obtained in batch methods were 83, 81, and 80%, respectively, whereas these yields after simple distillation were improved 97, 99.5, and 90%, respectively.

Keywords: liquid-phase esterification, natural silica, acidity esters, characterization

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Authors: Abhishek Sraw, Amit Sobti, Yamini Pandey, R. K. Wanchoo, Amrit Pal Toor

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Monocrotophos (MCP) is a widely used pesticide in India, which belong to an extremely toxic organophosphorus family, is persistent in nature and its toxicity is widely reported in all environmental segments in the country. Advanced Oxidation Process (AOP) is a promising solution to the problem of water pollution. TiO₂ is being widely used as a photocatalyst because of its many advantages, but it has a large band gap, due to which it is modified using metal and nonmetal dopant to make it active under sunlight and visible light. The use of nanosized powdered catalysts makes the recovery process extremely complicated. Hence the aim is to use low cost, easily available, eco-friendly clay material in form of bead as the support for the immobilization of catalyst, to solve the problem of post-separation of suspended catalyst from treated water. A recirculation type photocatalytic reactor (RTPR), using ultraviolet light emitting source (blue black lamp) was designed which work effectively for both suspended catalysts and catalyst coated clay beads. The bare, TiO₂ and W-TiO₂ coated clay beads were characterized by scanning electron microscopy (SEM), electron dispersive spectroscopy (EDS) and N₂ adsorption–desorption measurements techniques (BET) for their structural, textural and electronic properties. The study involved variation of different parameters like light conditions, recirculation rate, light intensity and initial MCP concentration under UV and sunlight for the degradation of MCP. The degradation and mineralization studies of the insecticide solution were performed using UV-Visible spectrophotometer, and COD vario-photometer and GC-MS analysis respectively. The main focus of the work lies in checking the recyclability of the immobilized TiO₂ over clay beads in the developed RTPR up to 30 continuous cycles without reactivation of catalyst. The results demonstrated the economic feasibility of the utilization of developed RTPR for the efficient purification of pesticide polluted water. The prepared TiO₂ clay beads delivered 75.78% degradation of MCP under UV light with negligible catalyst loss. Application of W-TiO₂ coated clay beads filled RTPR for the degradation of MCP under sunlight, however, shows 32% higher degradation of MCP than the same system based on undoped TiO₂. The COD measurements of TiO₂ coated beads led to 73.75% COD reduction while W-TiO₂ resulted in 87.89% COD reduction. The GC-MS analysis confirms the efficient breakdown of complex MCP molecules into simpler hydrocarbons. This supports the promising application of clay beads as a support for the photocatalyst and proves its eco-friendly nature, excellent recyclability, catalyst holding capacity, and economic viability.

Keywords: immobilized clay beads, monocrotophos, recirculation type photocatalytic reactor, TiO₂

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Authors: Sujit Kumar Guchhait, Subir Paul

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One of the major research areas is to find an alternative source of energy to fulfill the energy crisis and environmental problems. The Fuel cell is such kind of energy producing unit. Use of fuel cell to produce renewable energy for commercial purpose is limited by the high cost of Pt based electrode material. Development of high energetic, as well as inexpensive fuel cell electrode materials, is needs of hour to produce clean energy using derive bio-fuel. In this present investigation, inexpensive Cu-Ni-CeO2 electrode material has been synthesized by using pulse current. The surface morphology of the electrode materials is controlled by several deposition parameters to increase the rate of electrochemical oxidation of alcoholic fuel, ethanol. The electrochemical characterization of the developed material was done by Cyclic Voltammetry (CV) and Chronoamperometry (CA) and Electrochemical Impedance Spectroscopy test. It is interesting to find that both these materials have shown high electrocatalytic properties in terms of high exchange current density (I0), low polarization resistance (Rp) and low impedance. It is seen that the addition of CeO2 to Ni-Cu has outperformed Pt as far as high electrocatalytic properties are concerned. The exchange current density on the Cu-Ni-CeO2 electrode surface for ethanol oxidation is about eight times higher than the same on the Pt surface with much lower polarization resistance than the later. The surface morphology of the electrode materials has been revealed by Field Effect Scanning Electron Microscope (FESEM). It is seen that grains are narrow and subspherical with 3D surface containing pores in between two elongated grains. XRD study exhibits the presence of Ni and CeO2 on the Cu surface.

Keywords: electro-catalyst, alcoholic fuel, cyclic voltammetry, potentiodynamic polarization, EIS, XRD, SEM

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Authors: Abdolamir Allameh, Shahnaz Esmaeili, Mina Allameh, Safoura Khajeniazi

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Stem cells with therapeutic applications can be isolated from human placenta/umblical cord blood (UCB) as well as the cord tissue (UC). Stem cells in culture are vulnerable to oxidative stress, particularly when subjected to differentiation process. The aim of this study was to examine the chnages in the rate of oxidation that occurs to cellular macromolecules during hepatic differentiation of mononuclear cells (MSCs). In addition, the impact of the hepatic differentiation process of MSC on cellular and biological activity of the cells will be undertaken. For this purpose, first mononuclear cells (MNCs) were isolated from human UCB which was obtained from a healthy full-term infant. The cells were cultured at a density of 3×10⁵ cells/cm² in DMEM- low-glucose culture media supplemented with 20% FBS, 2 mM L-glutamine, 100 μg/ml streptomycin and 100 U/ml penicillin. Cell cultures were then incubated at 37°C in a humidified 5% CO₂ incubator. After removing non-adherent cells by replacing culture medium, fibroblast-like adherent cells were resuspended in 0.25% trypsin-EDTA and plated in 25 cm² flasks (1×10⁴/ml). Characterization of the MSCs was routinely done by observing their morphology and growth curve. MSCs were subjected to a 2-step hepatocyte differentiation protocol in presence of hepatocyte growth factor (HGF), dexamethazone (DEX) and oncostatin M (OSM). The hepatocyte-like cells derived from MSCs were checked every week for 3 weeks for changes in lipid peroxidation, protein carbonyl formation and DNA oxidation i.e., 8-hydroxy-2'-deoxyguanosine (8-OH-dG) assay. During the 3-week differentiation process of MSCs to hepatocyte-like cells we found that expression liver-specific markers such as albumin, was associated with increased levels of lipid peroxidation and protein carbonyl formation. Whereas, undifferentiated MSCs has relatively low levels of lipid peroxidation products. There was a significant increase ( p < 0.05) in lipid peroxidation products in hepatocytes on days 7, 14, and 21 of differentiation. Likewise, the level of protein carbonyls in the cells was elevated during the differentiation. The level of protein carbonyls measured in hepatocyte-like cells obtained 3 weeks after differentiation induction was estimated to be ~6 fold higher compared to cells recovered on day 7 of differentiation. On the contrary, there was a small but significant decrease in DNA damage marker (8-OH-dG) in hepatocytes recovered 3 weeks after differentiation onset. The level of 8-OHdG which was in consistent with formation of reactive oxygen species (ROS). In conclusion, this data suggest that despite the elevation in oxidation of lipid and protein molecules during hepatocyte development, the cells were normal in terms of DNA integrity, morphology, and biologically activity.

Keywords: adult stem cells, DNA integrity, free radicals, hepatic differentiation

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Authors: Geeta Kumari, Prabu Vairakannu

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Underground coal gasification (UCG) technology is an efficient and an economic in-situ clean coal technology, which converts unmineable coals into calorific valuable gases. This technology avoids ash disposal, coal mining, and storage problems. CO₂ gas can be a potential gasifying medium for UCG. CO₂ is a greenhouse gas and, the liberation of this gas to the atmosphere from thermal power plant industries leads to global warming. Hence, the capture and reutilization of CO₂ gas are crucial for clean energy production. However, the reactivity of high ash Indian coals with CO₂ needs to be assessed. In the present study, two varieties of Indian coals (low ash and high ash) are used for thermogravimetric analyses (TGA). Two low ash north east Indian coals (LAC) and a typical high ash Indian coal (HAC) are procured from the coal mines of India. Low ash coal with 9% ash (LAC-1) and 4% ash (LAC-2) and high ash coal (HAC) with 42% ash are used for the study. TGA studies are carried out to evaluate the activation energy for pyrolysis and gasification of coal under N₂ and CO₂ atmosphere. Coats and Redfern method is used to estimate the activation energy of coal under different temperature regimes. Volumetric model is assumed for the estimation of the activation energy. The activation energy estimated under different temperature range. The inherent properties of coals play a major role in their reactivity. The results show that the activation energy decreases with the decrease in the inherent percentage of coal ash due to the ash layer hindrance. A reverse trend was observed with volatile matter. High volatile matter of coal leads to the estimation of low activation energy. It was observed that the activation energy under CO₂ atmosphere at 400-600°C is less as compared to N₂ inert atmosphere. At this temperature range, it is estimated that 15-23% reduction in the activation energy under CO₂ atmosphere. This shows the reactivity of CO₂ gas with higher hydrocarbons of the coal volatile matters. The reactivity of CO₂ with the volatile matter of coal might occur through dry reforming reaction in which CO₂ reacts with higher hydrocarbon, aromatics of the tar content. The observed trend of Ea in the temperature range of 150-200˚C and 400-600˚C is HAC > LAC-1 >LAC-2 in both N₂ and CO₂ atmosphere. At the temperature range of 850-1000˚C, higher activation energy is estimated when compared to those values in the temperature range of 400-600°C. Above 800°C, char gasification through Boudouard reaction progressed under CO₂ atmosphere. It was observed that 8-20 kJ/mol of activation energy is increased during char gasification above 800°C compared to volatile matter pyrolysis between the temperature ranges of 400-600°C. The overall activation energy of the coals in the temperature range of 30-1000˚C is higher in N₂ atmosphere than CO₂ atmosphere. It can be concluded that higher hydrocarbons such as tar effectively undergoes cracking and reforming reactions in presence of CO₂. Thus, CO₂ gas is beneficial for the production of high calorific value syngas using high ash Indian coals.

Keywords: clean coal technology, CO₂ gasification, activation energy, underground coal gasification

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Authors: Lixin Zhao, Genmao Zhou

Abstract:

Traditional acid in-situ leaching (ISL) is not suitable for the sandstone uranium deposit with low permeability and high content of carbonate minerals, because of the blocking of calcium sulfate precipitates. Another factor influences the uranium acid in-situ leaching is that the pyrite in ore rocks will react with oxidation reagent and produce lots of sulfate ions which may speed up the precipitation process of calcium sulphate and consume lots of oxidation reagent. Due to the advantages such as less chemical reagent consumption and groundwater pollution, CO₂+O₂ in-situ leaching method has become one of the important research areas in uranium mining. China is the second country where CO₂+O₂ ISL has been adopted in industrial uranium production of the world. It is shown that the CO₂+O₂ ISL in China has been successfully developed. The reaction principle, technical process, well field design and drilling engineering, uranium-bearing solution processing, etc. have been fully studied. At current stage, several uranium mines use CO₂+O₂ ISL method to extract uranium from the ore-bearing aquifers. The industrial application and development potential of CO₂+O₂ ISL method in China are summarized. By using CO₂+O₂ neutral leaching technology, the problem of calcium carbonate and calcium sulfate precipitation have been solved during uranium mining. By reasonably regulating the amount of CO₂ and O₂, related ions and hydro-chemical conditions can be controlled within the limited extent for avoiding the occurrence of calcium sulfate and calcium carbonate precipitation. Based on this premise, the demand of CO₂+O₂ uranium leaching has been met to the maximum extent, which not only realizes the effective leaching of uranium, but also avoids the occurrence and precipitation of calcium carbonate and calcium sulfate, realizing the industrial development of the sandstone type uranium deposit.

Keywords: CO₂+O₂ ISL, industrial production, well field layout, uranium processing

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Authors: Parvin Berenjkar, Qiuyan Yuan, Richard Sparling, Stan Lozecznik

Abstract:

Landfills highly contribute to anthropological global warming through CH₄ emissions. Landfills are usually capped by a conventional soil cover to control the migration of gases. Methane is consumed by CH₄-oxidizing microorganisms known as methanotrophs that naturally exist in the landfill soil cover. The growth of methanotrophs can be optimized in a bio-cover that typically consists of a gas distribution layer (GDL) to homogenize landfill gas fluxes and an overlying oxidation layer composed of suitable materials that support methanotrophic populations. Materials such as mature yard waste composts can provide an inexpensive and favourable porous support for the growth and activity of methanotrophs. In areas with seasonal cold climates, it is valuable to know if methanotrophs in a bio-cover can survive in winter until the next spring, and how deep they are active in the bio-cover to mitigate CH₄. In this study, a pilot bio-cover was constructed in a closed landfill cell in Winnipeg that has a very cold climate in Canada. The bio-cover has a surface area of 2.5 m x 3.5 m and 1.5 m of depth, filled with 50 cm of gravel as a GDL and 70 cm of biosolids compost amended with yard and leaf waste compost. The observed in situ potential of methanotrophs for CH₄ oxidation was investigated at a specific period of time from December 2016 to April 2017 as well as November 2017 to April 2018, when the transition to surface frost and thawing happens in the bio-cover. Compost samples taken from different depths of the bio-cover were incubated in the laboratory under standardized conditions; an optimal air: methane atmosphere, at 22ºC, but at in situ moisture content. Results showed that the methanotrophs were alive oxidizing methane without a lag, indicating that there was the potential for methanotrophic activity at some depths of the bio-cover.

Keywords: bio-cover, global warming, landfill, methanotrophic activity

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Authors: Imdad Ullah Khan, Yongseok Yoon, Kyeung Uk Choi, Kwang Rae Jo, Namyul Kim, Eunbee Lee, Wan Hee Kim, Oh-Kyeong Kweon

Abstract:

The primary spinal cord injury (SCI) causes mechanical damage to the neurons and blood vessels. It leads to secondary SCI, which activates multiple pathological pathways, which expand neuronal damage at the injury site. It is characterized by vascular disruption, ischemia, excitotoxicity, oxidation, inflammation, and apoptotic cell death. It causes nerve demyelination and disruption of axons, which perpetuate a loss of impulse conduction through the injured spinal cord. It also leads to the production of myelin inhibitory molecules, which with a concomitant formation of an astroglial scar, impede axonal regeneration. The pivotal role regarding the neuronal necrosis is played by oxidation and inflammation. During an early stage of spinal cord injury, there occurs an abundant expression of reactive oxygen species (ROS) due to defective mitochondrial metabolism and abundant migration of phagocytes (macrophages, neutrophils). ROS cause lipid peroxidation of the cell membrane, and cell death. Abundant migration of neutrophils, macrophages, and lymphocytes collectively produce pro-inflammatory cytokines such as tumor necrosis factor-alpha (TNF-α), interleukin-6 (IL-6), interleukin-1beta (IL-1β), matrix metalloproteinase, superoxide dismutase, and myeloperoxidases which synergize neuronal apoptosis. Therefore, it is crucial to control inflammation and oxidation injury to minimize the nerve cell death during secondary spinal cord injury. Therefore, in response to oxidation and inflammation, heme oxygenase-1 (HO-1) is induced by the resident cells to ameliorate the milieu. In the meanwhile, neurotrophic factors are induced to promote neuroregeneration. However, it seems that anti-stress enzyme (HO-1) and neurotrophic factor (BDNF) do not significantly combat the pathological events during secondary spinal cord injury. Therefore, optimum healing can be induced if anti-inflammatory and neurotrophic factors are administered in a higher amount through an exogenous source. During the first experiment, the inflammation and neuroregeneration were selectively targeted. HO-1 expressing MSCs (HO-1 MSCs) and BDNF expressing MSCs (BDNF MSC) were co-transplanted in one group (combination group) of dogs with subacute spinal cord injury to selectively control the expression of inflammatory cytokines by HO-1 and induce neuroregeneration by BDNF. We compared the combination group with the HO-1 MSCs group, BDNF MSCs group, and GFP MSCs group. We found that the combination group showed significant improvement in functional recovery. It showed increased expression of neural markers and growth-associated proteins (GAP-43) than in other groups, which depicts enhanced neuroregeneration/neural sparing due to reduced expression of pro-inflammatory cytokines such as TNF-alpha, IL-6 and COX-2; and increased expression of anti-inflammatory markers such as IL-10 and HO-1. Histopathological study revealed reduced intra-parenchymal fibrosis in the injured spinal cord segment in the combination group than in other groups. Thus it was concluded that selectively targeting the inflammation and neuronal growth with the combined use of HO-1 MSCs and BDNF MSCs more favorably promote healing of the SCI. HO-1 MSCs play a role in controlling the inflammation, which favors the BDNF induced neuroregeneration at the injured spinal cord segment of dogs.

Keywords: HO-1 MSCs, BDNF MSCs, neuroregeneration, inflammation, anti-inflammation, spinal cord injury, dogs

Procedia PDF Downloads 101