Optimizing the removal of strontium and cesium ions from binary solutions on magnetic nano-zeolite using response surface methodology (RSM) and artificial neural network (ANN).

The feasibility of using magnetic nano-zeolite (MNZ) to remove cesium and strontium from their binary corrosive solutions was investigated by considering the multi-variant/multi-objective nature of the process. RSM (Response Surface Methodology) and ANN (Artificial Neural Network) were used to model and optimize the removal system and assess sensitive parameters that can affect the process reliability. MNZ is characterized by its high surface area and cation exchange capacity and possesses good regeneration behavior for both elements using citric acid. Its stability is comparable to other sorbents in acidic media and the stability increases in alkaline media, where dissolution rate follow first order reaction on heterogeneous sites. MNZ removes both contaminants simultaneously with small tendency toward Cs, where MNZ is suggested for application in pre-treatment of highly contaminated alkaline solutions. The percentage removal, decontamination factors, and separation factors have different dependency on the effluent/process conditions; this dependency is the same for both contaminants. Sorption kinetics is initially controlled by external mass transfer through the boundaries then intra-particle diffusion dominates the reactions. The process sensitivity to pH changes is attributed to changes in structural elements -species distribution at the solid/aqueous interface. Cs+ and Sr+2 are exchanged with Na+ and H+, regardless the effluent pH value, and with Al and Fe cations at specific pH. Isosteric heat of sorption calculations indicated that the total heat needed to complete the reaction was considerably reduced by operating the process at optimized temperature.

Evaluation of SnO2 for sunlight photocatalytic decontamination of water.

The broad bandgap tin (IV) oxide (SnO2) is the least investigated semiconductor material for photocatalytic water decontamination in sunlight exposure. A detailed study covering the synthesis, characterization and the evaluation of photocatalytic activity of SnO2, in the natural sunlight exposure, is presented. The structural characterization by XRD revealed the formation of phase pure tetragonal SnO2 with the average crystallite size of ∼41.5 nm whereas minor Sn2+ states in the material were identified by XPS analysis. As explored by diffuse reflectance (DR) and photoluminescence (PL) spectroscopy, the material exhibited a distinct absorption edge at ∼3.4 eV. The morphological and microstructure analysis of the synthesized SnO2 was carried out by FESEM and HRTEM. The electrochemical impedance spectroscopy (EIS) and chronopotentiometry (CP) predicted the better charge transport and retention ability of the material under illumination whereas the Mott-Schottky extrapolation prophesied the n-type behavior with the flat-band potential of -0.60 V. The photocatalytic activity of SnO2 was assessed in the exposure of complete spectrum natural sunlight for the removal of 2,4,6-trichlorophenol. The HPLC and TOC analysis monitored the progress of degradation and mineralization whereas the released chloride ions were evaluated by ion chromatography. The effect of the transition metal ions (Fe3+, Cu2+, Ni2+, and Zn2+) as electron capture agents and H2O2 as ROS generator was explored during the degradation process. The utility of the material for the simultaneous removal of chlorophenols in the mixture was also investigated. The SnO2 exhibited sustained activity in the repeated use. Based on experimental evidence congregated, the mechanism of the removal process and the efficacy of SnO2 for sunlight photocatalytic decontamination of water was established.

Optimization of food waste compost with the use of biochar.

This paper aims to examine the influence of biochar produced from lawn waste in accelerating the degradation and mineralization rates of food waste compost. Biochar produced at two different temperatures (350 and 450 °C) was applied at the rates 10 and 15% (w/w) of the total waste to an in-vessel compost bioreactor for evaluating its effects on food waste compost. The quality of compost was assessed against stabilization indices such as moisture contents (MC), electrical conductivity (EC), organic matters (OM) degradation, change in total carbon (TC) and mineral nitrogen contents such as ammonium (NH4+) and nitrate (NO3-). The use of biochar significantly improved the composting process and physiochemical properties of the final compost. Results showed that in comparison to control trial, biochar amended compost mixtures rapidly achieved the thermophilic temperature, increased the OM degradation by 14.4-15.3%, concentration of NH4+ by 37.8-45.6% and NO3- by 50-62%. The most prominent effects in term of achieving rapid thermophilic temperature and a higher concentration of NH4+ and NO3- were observed at 15% (w/w) biochar. According to compost quality standard of United States (US), California, Germany, and Austria, the compost stability as a result of biochar addition was achieved in 50-60 days. Nonetheless, the biochar produced at 450 °C had similar effects as to biochar produced at 350 °C for most of the compost parameters. Therefore, it is recommended to produce biochar at 350 °C to reduce the energy requirements for resource recovery of biomass and should be added at a concentration of 15% (w/w) to the compost bioreactor for achieving a stable compost.

Plastic waste to liquid oil through catalytic pyrolysis using natural and synthetic zeolite catalysts.

This study aims to examine the catalytic pyrolysis of various plastic wastes in the presence of natural and synthetic zeolite catalysts. A small pilot scale reactor was commissioned to carry out the catalytic pyrolysis of polystyrene (PS), polypropylene (PP), polyethylene (PE) and their mixtures in different ratios at 450°C and 75min. PS plastic waste resulted in the highest liquid oil yield of 54% using natural zeolite and 50% using synthetic zeolite catalysts. Mixing of PS with other plastic wastes lowered the liquid oil yield whereas all mixtures of PP and PE resulted in higher liquid oil yield than the individual plastic feedstocks using both catalysts. The GC-MS analysis revealed that the pyrolysis liquid oils from all samples mainly consisted of aromatic hydrocarbons with a few aliphatic hydrocarbon compounds. The types and amounts of different compounds present in liquid oils vary with some common compounds such as styrene, ethylbenzene, benzene, azulene, naphthalene, and toluene. The FT-IR data also confirmed that liquid oil contained mostly aromatic compounds with some alkanes, alkenes and small amounts of phenol group. The produced liquid oils have high heating values (HHV) of 40.2-45MJ/kg, which are similar to conventional diesel. The liquid oil has potential to be used as an alternative source of energy or fuel production.

Waste biorefineries: Enabling circular economies in developing countries.

This paper aims to examine the potential of waste biorefineries in developing countries as a solution to current waste disposal problems and as facilities to produce fuels, power, heat, and value-added products. The waste in developing countries represents a significant source of biomass, recycled materials, chemicals, energy, and revenue if wisely managed and used as a potential feedstock in various biorefinery technologies such as fermentation, anaerobic digestion (AD), pyrolysis, incineration, and gasification. However, the selection or integration of biorefinery technologies in any developing country should be based on its waste characterization. Waste biorefineries if developed in developing countries could provide energy generation, land savings, new businesses and consequent job creation, savings of landfills costs, GHG emissions reduction, and savings of natural resources of land, soil, and groundwater. The challenges in route to successful implementation of biorefinery concept in the developing countries are also presented using life cycle assessment (LCA) studies.

Biodiesel production potential from fat fraction of municipal waste in Makkah.

In the Kingdom of Saudi Arabia (KSA), millions of Muslims come to perform Pilgrimage every year. Around one million ton of municipal solid waste (MSW) is generated in Makkah city annually. The collected MSW is disposed of in the landfills without any treatment or energy recovery. As a result, greenhouse gas (GHG) emissions and contamination of the soil and water bodies along with leachate and odors are occurring in waste disposal vicinities. The composition of MSW shows that food waste is the largest waste stream (up to 51%) of the total generated MSW. About 13% of the food waste consists of fat content that is equivalent to about 64 thousand tons per year. This study aims to estimate the production potential of biodiesel first time in Makkah city from fat/oil fractions of MSW and highlight its economic and environmental benefits. It has been estimated that 62.53, 117.15 and 6.38 thousand tons of biodiesel, meat and bone meal (MBM) and glycerol respectively could be produced in 2014. A total electricity potential of 852 Gigawatt hour (GWh) from all three sources based on their energy contents, Higher Heating Value (HHV) of 40.17, 18.33 and 19 MJ/kg, was estimated for 2014 that will increase up to 1777 GWh in 2050. The cumulative net savings from landfill waste diversion (256 to 533 million Saudi Riyal (SAR)), carbon credits (46 to 96 million SAR), fuel savings (146 to 303 million SAR) and electricity generation (273 to 569 million SAR) have a potential to add a total net revenue of 611 to 1274 million SAR every year to the Saudi economy, from 2014 to 2050 respectively. However, further studies including real-time data about annual slaughtering activities and the amount of waste generation and its management are critical to decide optimum waste management practices based on life cycle assessment (LCA) and life cycle costing (LCC) methodologies.

Influence of temperature and reaction time on the conversion of polystyrene waste to pyrolysis liquid oil.

This paper aims to investigate the effect of temperature and reaction time on the yield and quality of liquid oil produced from a pyrolysis process. Polystyrene (PS) type plastic waste was used as a feedstock in a small pilot scale batch pyrolysis reactor. At 400°C with a reaction time of 75min, the gas yield was 8% by mass, the char yield was 16% by mass, while the liquid oil yield was 76% by mass. Raising the temperature to 450°C increased the gas production to 13% by mass, reduced the char production to 6.2% and increased the liquid oil yield to 80.8% by mass. The optimum temperature and reaction time was found to be 450°C and 75min. The liquid oil at optimum conditions had a dynamic viscosity of 1.77mPas, kinematic viscosity of 1.92cSt, a density of 0.92g/cm3, a pour point of -60°C, a freezing point of -64°C, a flash point of 30.2°C and a high heating value (HHV) of 41.6MJ/kg this is similar to conventional diesel. The gas chromatography with mass spectrophotometry (GC-MS) analysis showed that liquid oil contains mainly styrene (48%), toluene (26%) and ethyl-benzene (21%) compounds.

Relationship of polycyclic aromatic hydrocarbons with oxy(quinone) and nitro derivatives during air mass transport.

Airborne concentrations of Polycyclic Aromatic Hydrocarbons (PAH), quinone and nitro derivatives have been measured at three sites on the coast of Saudi Arabia to the north of the city of Jeddah. The PAH show a general reduction in concentrations from northwest to southeast, consistent with a source from a petrochemical works to the northwest of the sampling sites. In comparison, the concentrations of quinones show little variation between the sampling sites consistent with these being predominantly longer lived secondary pollutants formed from PAH oxidation. The nitro-PAH show a gradient in concentrations similar to but smaller than that for the PAH suggesting a balance between atmospheric formation and removal by photolysis. The 2-nitrofluoranthene:1-nitropyrene ratio increases from north to south, consistent with atmospheric chemical formation of the former compound, while the ratio of 2-nitrofluoranthene:2-nitropyrene is consistent with hydroxyl radical as the dominant reactant. An investigation of the changes in PAH congener ratios during air mass transport along the Red Sea coast shows consistency with reaction with a relatively low concentration of hydroxyl radical only for the day with the highest concentrations. It is concluded that while PAH degradation is occurring by chemical reaction, emissions from other locations along the air mass trajectory are most probably also leading to changes in congener ratios.

Assessing ambient ozone injury in olive (Olea europaea L.) plants by using the antioxidant ethylenediurea (EDU) in Saudi Arabia.

The antiozonant chemical, ethylenediurea (N-[2-(2-oxo-1-imidazolidinyl)ethyl]-N'-phenylurea, abbreviated as EDU), was applied as stem injections or soil drenches to 5-year-old containerized plants of olive (Olea europaea L. cultivar Kalamata) in growth chambers in order to assess its ameliorative effects against realistic ozone (O3) stress. Visible injury symptoms were reduced greatly in individuals treated with EDU, with injection applications having greater protection than soil drenches. EDU application caused increases in the measured ecophysiological parameters compared to untreated individuals. In particular, the stem injection protected plants against photosynthetic impairment (unchanged net photosynthetic rates and intercellular CO2 concentration, in comparison to plants grown in filtered air). EDU application increased the protection of PSII from ambient O3 oxidative stress, although it did not retain the proportion of redox state of QA, pigment composition of photosynthetic apparatus and size of light-harvesting complex of PSII. However, the stem injection of plants with EDU induced lower non-photochemical quenching (NPQ) values in comparison to ambient air (-2 %), indicating a better photoprotection of PSII in comparison to soil drench application. EDU application caused increases in the morphological and biometric parameters compared to individuals exposed to ambient air. To the best of our knowledge, this is the first study highlighting the protection of Kalamata olive trees due to EDU in terms of growth, yield, visible injury, and photosynthetic performance. Furthermore, this study proved that EDU could be a low-cost and a low-technology efficient tool for assessing O3 effects on plant performances in the field in Saudi Arabia.

Setting up of in-vacuum PIXE system for direct elemental analysis of thick solid environmental samples.

Experimental set-up, development, characterization, and calibration of an in-vacuum PIXE system at the tandem accelerator facility of the Atomic Energy Commission of Syria (AECS) is described. The PIXE system calibration involved experimental characterization of the X-ray detector parameters and careful determination of the H-values that control dependence of the detector solid angle with the X-ray energies and correct imperfect values of the detector efficiency. Setting up of an electron flood gun to compensate charge built up and utilization of a beam profile monitor to perform indirect measurement of the beam charge, provide a direct PIXE measurement of thick insulating samples in-vacuum. The PIXE system has been subsequently examined to verify its ability to perform direct PIXE measurements on geological materials. A combination of minimum sample preparation procedures and specific experimental conditions applied enables simple and accurate elemental analysis. Elemental concentrations of several elements heavier than sodium in different reference geological samples, at about 5-10% absolute accuracy for most elements, have been determined. Comprehensive discussion of the obtained elemental concentration values, for most elements of visible X-ray peaks in the PIXE spectra, has been considered.

Gas exchange and chlorophyll fluorescence of pea (Pisum sativum L.) plants in response to ambient ozone at a rural site in Egypt.

Egyptian pea cultivars (Pisum sativum L. cultivars Little Marvel, Perfection and Victory) grown in open-top chambers were exposed to either charcoal-filtered (FA) or non-filtered air (NF) for five consecutive years (2009-2013) at a rural site in northern Egypt. Net photosynthetic rates (PN), stomatal conductance (gs), intercellular CO2 (Ci) and chlorophyll fluorescence were measured. Ozone (O3) was found to be the most prevalent pollutant common at the rural site and is suspected to be involved in the alteration of the physiological parameters measured in the present investigation. PN of different cultivars were found to respond similarly; decreases of 23, 29 and 39% were observed in the cultivars Perfection, Little Marvel and Victory, respectively (averaged over the five years) due to ambient O3. The maximum impairment in PN was recorded in the cultivar Victory (46%) in 2013 when the highest O3 levels were recorded (90 nL L(-1)). The average stomatal conductance decreased by 20 and 18% in the cultivars Little Marvel and Perfection, respectively, while the average stomatal conductance increased on average by 27% in the cultivar Victory. A significant correlation was found between PN and Ci, indicating the importance of non-stomatal limitations of photosynthesis, especially in the cultivar Victory. The PN vs. Ci curves were fitted to a non-rectangular hyperbolic model. The actual quantum yield (ΦPSII) and photochemical quenching coefficient (qP) were significantly decreased in the leaves of plants exposed to NF air. Non-photochemical quenching (NPQ) was increased in all cultivars. Exposure to NF air caused reductions in chlorophyll (Chl a) of 19, 16 and 30% in the Little Marvel, Perfection and Victory cultivars, respectively.

Beta-glucanase productivity improvement via cell immobilization of recombinant Escherichia coli cells in different matrices.

The studies have been performed to analyze the production of beta-glucanase by a recombinant strain of Escherichia coli immobilized in different matrices. Porous sintered glass SIRAN, Ceramic supporting matrices and Broken Pumice stone as well as SIRAN Raschig-rings were examined for the immobilization of whole bacterial cells. The beta-glucanase activity of bacteria immobilized in CeramTec PST 5 (4-5 mm) was very low. CeramTec PST 5 (1.5-2.5 mm) was found to be the best carrier compared to all other matrices regarding glucanase production (630 U/ml) and compared to enzyme activity produced by free cells (500 U/ml). Different doses of matrices were applied (2, 5, 7, 10 g/lask) in the form of "matrix weight". Using 2 g/flask of CeramTec PST 5 (1.5-2.5 mm) yielded enzyme activity of 630 U/ml). CeramTec gives highest operational stability of beta-glucanase by repeated batch fermentation to 5 cycles, and activity reached 660 U/ml. Scanning electron microscopy observations showed a high number of vegetative cells that continued growth inside the matrices, indicating that beta-glucanase activity improvement was due to the immobilization of the cells.

Chromatographic separation of neodymium isotopes by using chemical exchange process.

The neodymium isotope effects were investigated in Nd-malate ligand exchange system using the highly porous cation exchange resin SQS-6. The temperature of the chromatographic columns was kept constant at 50°C by temperature controlled water passed through the columns jackets. The separation coefficient of neodymium isotopes, ɛ's, was calculated from the isotopic ratios precisely measured by means of an ICP mass spectrometer equipped with nine collectors as ion detectors. The separation coefficient, ɛ×10(5), were calculated and found to be 1.4, 4.8, 5.4, 10.6, 16.8 and 20.2 for (143)Nd, (144)Nd, (145)Nd, (146)Nd, (148)Nd and (150)Nd, respectively.

Dissociative charge transfer and collision induced dissociation of Ar2+ and Ar3+ clusters in collisions with argon atoms at keV energies.

The dynamics of dissociative charge transfer and collision induced dissociation of Ar(2) (+) and Ar(3) (+) clusters colliding with Ar atoms at 4.8 keV has been investigated using a novel multifragment detection scheme that maps the postcollision vectors of all particles simultaneously. Estimation of internal energies and measurement of pre- and postcollision vectors enables a full description of reaction dynamics. The prominence of electronic excitation in defining the dynamics of these collision systems is demonstrated. The dissociation dynamics of Ar(3) (+) clusters is distinctly different from that of Ar(2) (+). This is attributed to a combination of lower internal energies and predominantly triangular T-shape structure of the Ar(3) (+) ion.

Lifetime and yield of metastable Ar2(+) ions.

Ar2(+) ions produced in a cooled supersonic expansion by electron-impact ionization are accelerated at 2.5 keV and kept during few milliseconds inside a linear electrostatic trap. The lifetime of the metastable Ar2(+) ion is determined from the measurement of the rate of the argon atoms escaping the trap. The lifetime and the relative metastable populations are measured as a function of the pressure and temperature in the supersonic expansion, i.e., of the mean cluster size. Possible mechanisms responsible for the metastable formation are discussed.

Characterization of the metabolites of alosetron in experimental animals and human.

The metabolism of radiolabelled alosetron was studied in rat, dog, rabbit, mouse and human. The metabolism in rat and dog was studied at a low and an elevated dose designed to generate sufficient quantities of metabolite for definitive identification. A strategy for the characterization of metabolites in cases of extensive metabolism was developed and demonstrated for alosetron. Semi-preparative high-performance liquid chromatography (HPLC), liquid chromatography-mass spectrometry (LC-MS), nuclear magnetic resonance (NMR) and liquid chromatography-nuclear magnetic resonance (HPLC-NMR) enabled the isolation and characterization of 28 metabolites of alosetron. The characterization of the metabolites in animal excreta facilitated the identification of human systemic metabolites.

Pharmacokinetics, metabolism and excretion of the glycine antagonist GV150526A in rat and dog.

1. The pharmacokinetics, metabolic fate and excretion of 3-[-2(phenylcarbamoyl) ethenyl-4,6-dichloroindole-2-carboxylic acid (GV150526), a novel glycine antagonist for stroke, in rat and dog following intravenous administration of [C14]-GV150526A were investigated. 2. Studies were also performed in bile duct-cannulated animals to confirm the route of elimination and to obtain more information on metabolite identity. 3. Metabolites in plasma, urine and bile were identified by HPLC-MS/MS and NMR spectroscopy. 4. GV150526A was predominantly excreted in the faeces via the bile, with only trace metabolites of radioactivity in urine (< 5%). Radioactivity in rat bile was predominantly due to metabolites, whereas approximately 50% of the radioactivity in dog bile was due to parent GV150526. 5. The principal metabolites in bile were identified as glucuronide conjugates of the carboxylic acid, whereas in rat urine the main metabolite was a sulphate conjugate of an aromatic oxidation metabolite. Multiple glucuronide peaks were observed and identified as isomeric glucuronides and their anomers arising from acyl migration and muta-rotation.

N-O glucuronidation: a major human metabolic pathway in the elimination of two novel anti-convulsant drug candidates.

1. The urinary metabolites of the anti-convulsant compound 4-amino-1-(2,6-difluorobenzyl)-1H-1,2,3-triazolo[4,5-c]-pyridine hydrochloride (GI265080) obtained following a single oral dose to man have been detected and quantified relative to each other using 19F-NMR spectroscopy. 2. The human urinary metabolites of GI265080 were isolated using semipreparative HPLC and unequivocally characterized using 1H-NMR spectroscopy, two-dimensional heteronuclear NMR spectroscopy and mass spectrometry. The assignments of the N-(5)-oxide and the N-(5)-O-glucuronide metabolites of GI265080 were further confirmed by independent synthesis. The urinary metabolites obtained following single oral doses to dog and rat have also been isolated and characterized. 3. The human urinary metabolites of GI265080 comprise the N-(5)-oxide, the quaternary N+-(5)-glucuronide, the 7-hydroxy glucuronide and a glucuronide conjugate of the N-(5)-oxide. The N-(5)-O-glucuronide conjugate is a novel species in human metabolism and is a significant route of elimination of GI265080 in man. 4. The urinary metabolites of the potential anti-convulsant GW273293 (6-amino-3-(2,3,5-trichlorophenyl)pyrazin-2-ylamine) obtained following a single oral dose to man have also been isolated and characterized. The formation of a novel N-O-glucuronide was also observed and was shown to constitute a significant route of elimination of GW273293 in man.

Formation of a defluorinated metabolite of a quinoxaline antiviral drug catalysed by human cytochrome P450 1A2.

The in-vitro metabolism of GW420867X ((S)-2-ethyl-7-fluoro-3-oxo-3, 4-dihydro-2H-quinoxaline-1-carboxylic acid isopropyl ester), a quinoxaline drug for the potential treatment of HIV, has been studied with singly expressed human cytochromes P450 (CYP 450). No biotransformation of [14C]GW420867X was evident in the presence of any of the CYP 450 isoforms, with the exception of CYP 450 1A2, where a single metabolite was observed in the HPLC radiochromatograms of enzyme incubations with the test compound. The structure of this metabolite was determined by nuclear magnetic resonance spectroscopy and mass spectrometry, and was shown to correspond to the replacement of the aromatic fluorine of GW420867X with a hydroxyl group. Thus, it appeared that CYP 450 1A2 catalysed the specific defluorination of GW420867X, presumably during formation of an arene oxide intermediate during aromatic hydroxylation.

The potential of 19F NMR spectroscopy for rapid screening of cell cultures for models of mammalian drug metabolism.

The use of microbial cultures as a complementary model for mammalian drug metabolism has been well established previously. Here is a preliminary investigation into the potential of 19F NMR spectroscopy as a rapid screening tool to quantify the biotransformations of fluorine-containing model drugs. Biotransformations of three model drugs in 48 taxonomically diverse organisms were measured by acquiring 19F NMR spectra at 376 MHz. The presence of fluorine in the molecules allowed rapid, simultaneous detection of over 20 biotransformation products without sample pretreatment, chromatography, mass spectrometric techniques or the use of radiolabelled substrates. The detection limit at 376 MHz using 5 mm NMR tubes was ca. 0.3 microg ml(-1) using a typical analysis time of 20 min per sample. With the recent advent of flow injection NMR technology, analysis time of 5 min could be achieved with less sample. This approach may be used to develop fast small-scale microbial screens for the biosynthesis of metabolite standards and production of novel drug analogues, whilst also having a role in reducing animal experiments needed to identify animal and human metabolites of fluorinated xenobiotics.