Large Scale Production of Polyhydroxyalkanoates (PHAs) from Wastewater: A Study of Techno-Economics, Energy Use and Greenhouse Gas Emissions

The biodegradable family of polymers polyhydroxyalkanoates is an interesting substitute for convectional fossil-based plastics. However, the manufacturing and environmental impacts associated with their production via intracellular bacterial fermentation are strongly dependent on the raw material used and on energy consumption during the extraction process, limiting their potential for commercialization. Industrial wastewater is studied in this paper as a promising alternative feedstock for waste valorization. Based on results from laboratory and pilot-scale experiments, a conceptual process design, techno-economic analysis and life cycle assessment are developed for the large-scale production of the most common type of polyhydroxyalkanoate, polyhydroxbutyrate. Intracellular polyhydroxybutyrate is obtained via fermentation of microbial community present in industrial wastewater and the downstream processing is based on chemical digestion with surfactant and hypochlorite. The economic potential and environmental performance results help identifying bottlenecks and best opportunities to scale-up the process prior to industrial implementation. The outcome of this research indicates that the fermentation of wastewater towards PHB presents advantages compared to traditional PHAs production from sugars because the null environmental burdens and financial costs of the raw material in the bioplastic production process. Nevertheless, process optimization is still required to compete with the petrochemicals counterparts.

Chloroform-Formic Acid Solvent Systems for Nanofibrous Polycaprolactone Webs

In this study, polycaprolactone (PCL) was dissolved in chloroform:ethanol solvent system at a concentration of 18 w/v %. 1, 2, 4, and 6 droplets of formic acid were added to the prepared 10ml PCL-chloroform:ethanol solutions separately. Fibrous webs were produced by electrospinning technique based on the horizontal working principle. Morphology of the webs was investigated by using scanning electron microscopy (SEM) whereas fiber diameters were measured by Image J Software System. The effect of formic acid addition to the mostly used chloroform solvent on fiber morphology was examined. Results indicate that there is a distinct fall in fiber diameter with the addition of formic acid drops. The average fiber diameter was measured as 2.22μm in PCL /chloroform:ethanol solution system. On the other hand, 328nm and 256 nm average fiber diameters were measured for the samples of 4 drops and 6 drops formic acid added. This study offers alternative solvent systems to produce nanoscaled, nontoxic PCL fibrous webs by electrospinning technique.

Structure and Morphology of Electrodeposited Nickel Nanowires at an Electrode Distance of 20mm

The objective of this work is to study the effect of two key factors - external magnetic field and applied current density during template-based electrodeposition of nickel nanowires using an electrode distance of 20 mm. Morphology, length, crystallite size and crystallographic characterization of the grown nickel nanowires at an electrode distance of 20mm are presented. For this electrode distance of 20 mm, these two key electrodeposition factors when coupled was found to reduce crystallite size with a higher growth length and preferred orientation of Ni crystals. These observed changes can be inferred to be due to coupled interaction forces induced by the intensity of applied electric field (current density) and external magnetic field known as magnetohydrodynamic (MHD) effect during the electrodeposition process.

Standard and Processing of Photodegradable Polyethylene

The introduction of degradable plastic materials into agricultural sectors has represented a promising alternative to promote green agriculture and environmental friendly of modern farming practices. Major challenges of developing degradable agricultural films are to identify the most feasible types of degradation mechanisms, composition of degradable polymers and related processing techniques. The incorrect choice of degradable mechanisms to be applied during the degradation process will cause premature losses of mechanical performance and strength. In order to achieve controlled process of agricultural film degradation, the compositions of degradable agricultural film also important in order to stimulate degradation reaction at required interval of time and to achieve sustainability of the modern agricultural practices. A set of photodegradable polyethylene based agricultural film was developed and produced, following the selective optimization of processing parameters of the agricultural film manufacturing system. Example of agricultural films application for oil palm seedlings cultivation is presented.

Bridging Stress Modeling of Composite Materials Reinforced by Fibers Using Discrete Element Method

The problem of toughening in brittle materials reinforced by fibers is complex, involving all of the mechanical properties of fibers, matrix and the fiber/matrix interface, as well as the geometry of the fiber. Development of new numerical methods appropriate to toughening simulation and analysis is necessary. In this work, we have performed simulations and analysis of toughening in brittle matrix reinforced by randomly distributed fibers by means of the discrete elements method. At first, we put forward a mechanical model of toughening contributed by random fibers. Then with a numerical program, we investigated the stress, damage and bridging force in the composite material when a crack appeared in the brittle matrix. From the results obtained, we conclude that: (i) fibers of high strength and low elasticity modulus are beneficial to toughening; (ii) fibers of relatively high elastic modulus compared to the matrix may result in substantial matrix damage due to spalling effect; (iii) employment of high-strength synthetic fibers is a good option for toughening. We expect that the combination of the discrete element method (DEM) with the finite element method (FEM) can increase the versatility and efficiency of the software developed. The present work can guide the design of ceramic composites of high performance through the optimization of the parameters.

Carbamazepine Co-crystal Screening with Dicarboxylic Acids Co-Crystal Formers

Co-crystal is believed to improve the solubility and dissolution rates and thus, enhanced the bioavailability of poor water soluble drugs particularly during the oral route of administration. With the existing of poorly soluble drugs in pharmaceutical industry, the screening of co-crystal formation using carbamazepine (CBZ) as a model drug compound with dicarboxylic acids co-crystal formers (CCF) namely fumaric (FA) and succinic (SA) acids in ethanol has been studied. The co-crystal formations were studied by varying the mol ratio values of CCF to CBZ to access the effect of CCF concentration on the formation of the co-crystal. Solvent evaporation, slurry and cooling crystallization which representing the solution based method co-crystal screening were used. Based on the differential scanning calorimetry (DSC) analysis, the melting point of CBZ-SA in different ratio was in the range between 188oC-189oC. For CBZ-FA form A and CBZ-FA form B the melting point in different ratio were in the range of 174oC-175oC and 185oC-186oC respectively. The product crystal from the screening was also characterized using X-ray powder diffraction (XRPD). The XRPD pattern profile analysis has shown that the CBZ co-crystals with FA and SA were successfully formed for all ratios studied. The findings revealed that CBZ-FA co-crystal were formed in two different polymorphs. It was found that CBZ-FA form A and form B were formed from evaporation and slurry crystallization methods respectively. On the other hand, in cooling crystallization method, CBZ-FA form A was formed at lower mol ratio of CCF to CBZ and vice versa. This study disclosed that different methods and mol ratios during the co-crystal screening can affect the outcome of co-crystal produced such as polymorphic forms of co-crystal and thereof. Thus, it was suggested that careful attentions is needed during the screening since the co-crystal formation is currently one of the promising approach to be considered in research and development for pharmaceutical industry to improve the poorly soluble drugs.

Investigation of Dissolution in Diammonium Hydrogen Phosphate Solutions of Gypsum

Gypsum (CaSO4.2H2O) is a mineral that is found in large quantities in the Turkey and in the World. In this study, the dissolution of this mineral in the diammonium hydrogen phosphate solutions has been studied. The dissolution and dissolution kinetics of gypsum in diammonium hydrogen phosphate solutions will be useful for evaluating of solid wastes containing gypsum. Parameters such as diammonium hydrogen phosphate concentration, temperature and stirring speed affecting on the dissolution rate of the gypsum in diammonium hydrogen phosphate solutions were investigated. In experimental studies have researched effectiveness of the selected parameters. The dissolution of gypsum were examined in two parts at low and high temperatures. The experimental results were successfully correlated by linear regression using Statistica program. Dissolution curves were evaluated shrinking core models for solidfluid systems. The activation energy was found to be 34.58 kJ/mol and 44.45 kJ/mol for the low and the high temperatures. The dissolution of gypsum was controlled by chemical reaction both low temperatures and high temperatures.

Effects of Kenaf and Rice Husk on Water Absorption and Flexural Properties of Kenaf/CaCO3/HDPE and Rice Husk/CaCO3/HDPE Hybrid Composites

Rice husk and kenaf filled with calcium carbonate (CaCO3) and high density polyethylene (HDPE) composite were prepared separately using twin-screw extruder at 50rpm. Different filler loading up to 30 parts of rice husk particulate and kenaf fiber were mixed with the fixed 30% amount of CaCO3 mineral filler to produce rice husk/CaCO3/HDPE and kenaf/CaCO3/HDPE hybrid composites. In this study, the effects of natural fiber for both rice husk and kenaf in CaCO3/HDPE composite on physical, mechanical and morphology properties were investigated. Field Emission Scanning Microscope (FeSEM) was used to investigate the impact fracture surfaces of the hybrid composite. The property analyses showed that water absorption increased with the presence of kenaf and rice husk fillers. Natural fibers in composite significantly influence water absorption properties due to natural characters of fibers which contain cellulose, hemicellulose and lignin structures. The result showed that 10% of additional natural fibers into hybrid composite had caused decreased flexural strength, however additional of high natural fiber (>10%) filler loading has proved to increase its flexural strength.

Spatial-Temporal Clustering Characteristics of Dengue in the Northern Region of Sri Lanka, 2010-2013

Dengue outbreaks are affected by biological, ecological, socio-economic and demographic factors that vary over time and space. These factors have been examined separately and still require systematic clarification. The present study aimed to investigate the spatial-temporal clustering relationships between these factors and dengue outbreaks in the northern region of Sri Lanka. Remote sensing (RS) data gathered from a plurality of satellites were used to develop an index comprising rainfall, humidity and temperature data. RS data gathered by ALOS/AVNIR-2 were used to detect urbanization, and a digital land cover map was used to extract land cover information. Other data on relevant factors and dengue outbreaks were collected through institutions and extant databases. The analyzed RS data and databases were integrated into geographic information systems, enabling temporal analysis, spatial statistical analysis and space-time clustering analysis. Our present results showed that increases in the number of the combination of ecological factor and socio-economic and demographic factors with above the average or the presence contribute to significantly high rates of space-time dengue clusters.

Effect of Model Dimension in Numerical Simulation on Assessment of Water Inflow to Tunnel in Discontinues Rock

Groundwater inflow to the tunnels is one of the most important problems in tunneling operation. The objective of this study is the investigation of model dimension effects on tunnel inflow assessment in discontinuous rock masses using numerical modeling. In the numerical simulation, the model dimension has an important role in prediction of water inflow rate. When the model dimension is very small, due to low distance to the tunnel border, the model boundary conditions affect the estimated amount of groundwater flow into the tunnel and results show a very high inflow to tunnel. Hence, in this study, the two-dimensional universal distinct element code (UDEC) used and the impact of different model parameters, such as tunnel radius, joint spacing, horizontal and vertical model domain extent has been evaluated. Results show that the model domain extent is a function of the most significant parameters, which are tunnel radius and joint spacing.

Ab initio Study of Co2ZrGe and Co2NbB Full Heusler Compounds

Using the first-principles full-potential linearized augmented plane wave plus local orbital (FP-LAPW+lo) method based on density functional theory (DFT), we have investigated the electronic structure and magnetism of full Heusler alloys Co2ZrGe and Co2NbB. These compounds are predicted to be half-metallic ferromagnets (HMFs) with a total magnetic moment of 2.000 B per formula unit, well consistent with the Slater-Pauling rule. Calculations show that both the alloys have an indirect band gaps, in the minority-spin channel of density of states (DOS), with values of 0.58 eV and 0.47 eV for Co2ZrGe and Co2NbB, respectively. Analysis of the DOS and magnetic moments indicates that their magnetism is mainly related to the d-d hybridization between the Co and Zr (or Nb) atoms. The half-metallicity is found to be relatively robust against volume changes. In addition, an atom inside molecule AIM formalism and an electron localization function ELF were also adopted to study the bonding properties of these compounds, building a bridge between their electronic and bonding behavior. As they have a good crystallographic compatibility with the lattice of semiconductors used industrially and negative calculated cohesive energies with considerable absolute values these two alloys could be promising magnetic materials in the spintronic field.

Using High Performance Computing for Online Flood Monitoring and Prediction

The main goal of this article is to describe the online flood monitoring and prediction system Floreon+ primarily developed for the Moravian-Silesian region in the Czech Republic and the basic process it uses for running automatic rainfall-runoff and hydrodynamic simulations along with their calibration and uncertainty modeling. It takes a long time to execute such process sequentially, which is not acceptable in the online scenario, so the use of a high performance computing environment is proposed for all parts of the process to shorten their duration. Finally, a case study on the Ostravice River catchment is presented that shows actual durations and their gain from the parallel implementation.

Atmospheric Fluid Bed Gasification of Different Biomass Fuels

This paper shortly describes various types of biomass and a growing number of facilities utilizing the biomass in the Czech Republic. The considerable part of this paper deals with energy parameters of the most frequently used types of biomass and results of their gasification testing. Sixteen most used "Czech" woody plants and grasses were selected; raw, element and biochemical analyses were performed and basic calorimetric values, ash composition, and ash characteristic temperatures were identified. Later, each biofuel was tested in a fluidized bed gasifier. The essential part of this paper provides results of the gasification of selected biomass types. Operating conditions are described in detail with a focus on individual fuels properties. Gas composition and impurities content are also identified. In terms of operating conditions and gas quality, the essential difference occurred mainly between woody plants and grasses. The woody plants were evaluated as more suitable fuels for fluidized bed gasifiers. Testing results significantly help with a decision-making process regarding suitability of energy plants for growing and with a selection of optimal biomass-treatment technology.

New Hybrid Method to Model Extreme Rainfalls

Modeling and forecasting dynamics of rainfall occurrences constitute one of the major topics, which have been largely treated by statisticians, hydrologists, climatologists and many other groups of scientists. In the same issue, we propose, in the present paper, a new hybrid method, which combines Extreme Values and fractal theories. We illustrate the use of our methodology for transformed Emberger Index series, constructed basing on data recorded in Oujda (Morocco). The index is treated at first by Peaks Over Threshold (POT) approach, to identify excess observations over an optimal threshold u. In the second step, we consider the resulting excess as a fractal object included in one dimensional space of time. We identify fractal dimension by the box counting. We discuss the prospect descriptions of rainfall data sets under Generalized Pareto Distribution, assured by Extreme Values Theory (EVT). We show that, despite of the appropriateness of return periods given by POT approach, the introduction of fractal dimension provides accurate interpretation results, which can ameliorate apprehension of rainfall occurrences.

Metal(loids) Speciation Using HPLC-ICP-MS Technique in Klodnica River, Upper Silesia, Poland

The work allowed gaining knowledge about redox and speciation changes of As, Cr and Sb ionic forms in Klodnica River water. This kind of studies never has been conducted in this region of Poland. In study optimized and validated previously HPLC-ICP-MS methods for determination of As, Sb and Cr was used. Separation step was done using high-performance liquid chromatograph equipped with ion-exchange column followed by ICP-MS spectrometer detector. Preliminary studies included determination of the total concentration of As, Sb and Cr, pH, Eh, temperature and conductivity of the water samples. The study was conducted monthly from March to August 2014, at six points on the Klodnica River. The results indicate that exceeded at acceptable concentration of total Cr and Sb was observed in Klodnica River and we should qualify Klodnica River waters below the second purity class. In Klodnica River waters dominates oxidized antimony and arsenic forms, as well as the two forms of chromium Cr(VI) and Cr(III). Studies have also shown the methyl derivative of arsenic's presence.

Soil Quality State and Trends in New Zealand’s Largest City after 15 Years

Soil quality monitoring is a science-based soil management tool that assesses soil ecosystem health. A soil monitoring program in Auckland, New Zealand’s largest city extends from 1995 to the present. The objective of this study was to firstly determine changes in soil parameters (basic soil properties and heavy metals) that were assessed from rural land in 1995-2000 and repeated in 2008-2012. The second objective was to determine differences in soil parameters across various land uses including native bush, rural (horticulture, pasture and plantation forestry) and urban land uses using soil data collected in more recent years (2009- 2013). Across rural land, mean concentrations of Olsen P had significantly increased in the second sampling period and was identified as the indicator of most concern, followed by soil macroporosity, particularly for horticultural and pastoral land. Mean concentrations of Cd were also greatest for pastoral and horticultural land and a positive correlation existed between these two parameters, which highlights the importance of analysing basic soil parameters in conjunction with heavy metals. In contrast, mean concentrations of As, Cr, Pb, Ni and Zn were greatest for urban sites. Native bush sites had the lowest concentrations of heavy metals and were used to calculate a ‘pollution index’ (PI). The mean PI was classified as high (PI > 3) for Cd and Ni and moderate for Pb, Zn, Cr, Cu, As and Hg, indicating high levels of heavy metal pollution across both rural and urban soils. From a land use perspective, the mean ‘integrated pollution index’ was highest for urban sites at 2.9 followed by pasture, horticulture and plantation forests at 2.7, 2.6 and 0.9, respectively. It is recommended that soil sampling continues over time because a longer spanning record will allow further identification of where soil problems exist and where resources need to be targeted in the future. Findings from this study will also inform policy and science direction in regional councils.

Adsorption of Acetone Vapors by SBA-16 and MCM-48 Synthesized from Rice Husk Ash

Silica was extracted from agriculture waste rice husk ash (RHA) and was used as the silica source for synthesis of RMCM-48 and RSBA-16. An alkali fusion process was utilized to separate silicate supernatant and the sediment effectively. The CTAB/Si and F127/Si molar ratio was employed to control the structure properties of the obtained RMCM-48 and RSBA-16 materials. The N2 adsorption-desorption results showed the micro-mesoporous RSBA-16 possessed high specific surface areas (662-1001 m2/g). All the obtained RSBA-16 materials were applied as the adsorbents for acetone adsorption. And the breakthrough tests clearly revealed that the RSBA-16(0.004) materials could achieve the highest acetone adsorption capacity of 181 mg/g under 1000 ppmv acetone vapor concentration at 25oC, which was also superior to ZSM-5 (71mg/g) and MCM-41 (157mg/g) under same test conditions. This can help to reduce the solid waste and the high adsorption performance of the obtained materials could consider as potential adsorbents for acetone adsorption.

Propane Dehydrogenation with Better Stability by a Modified Pt-Based Catalyst

The effect of transition metal doping on Pt/Al2O3 catalyst used in propane dehydrogenation reaction at 500°C was studied. The preparation methods investigated were sequential impregnation (Pt followed by the 2nd metal or the 2nd metal followed by Pt) and co-impregnation. The metal contents of these catalysts were fixed as the weight ratio of Pt per the 2nd metal of around 0.075. These catalysts were characterized by N2-physisorption, TPR, COchemisorption and NH3-TPD. It was found that the impregnated 2nd metal had an effect upon reducibility of Pt due to its interaction with transition metal-containing structure. This was in agreement with the CO-chemisorption result that the presence of Pt metal, which is a result from Pt species reduction, was decreased. The total acidity of bimetallic catalysts is decreased but the strong acidity is slightly increased. It was found that the stability of bimetallic catalysts prepared by co-impregnation and sequential impregnation where the 2nd metal was impregnated before Pt were better than that of monometallic catalyst (undoped Pt one) due to the forming of Pt sites located on the transition metal-oxide modified surface. Among all preparation methods, the sequential impregnation method- having Pt impregnated before the 2nd metal gave the worst stability because this catalyst lacked the modified Pt sites and some fraction of Pt sites was covered by the 2nd metal.

Dielectric Properties of MWCNT-Muscovite/Epoxy Hybrid Composites

In the present work, the dielectric properties of Epoxy/MWCNT-muscovite HYBRID and MIXED composites based on a ratio 30:70 were studied. The multi-wall carbon nanotubes (MWCNT) were prepared using two methods: (a) MWCNTmuscovite hybrids were synthesised by chemical vapour deposition (CVD) and (b) physically mixing muscovite with MWCNT. The effects of different preparation of the composites and filler loading were evaluated. It was revealed that the dielectric constants of HYBRID epoxy composites are slightly higher than MIXED epoxy composites. It was also indicated that the dielectric constant increased by increasing the MWCNT filler loading.

Alumina Supported Copper-Manganese Catalysts for Combustion of Exhaust Gases: Effect of Preparation Method

The development of active and stable catalysts without noble metals for low temperature oxidation of exhaust gases remains a significant challenge. The purpose of this study is to determine the influence of the preparation method on the catalytic activity of the supported copper-manganese mixed oxides in terms of VOCs oxidation. The catalysts were prepared by impregnation of γ- Al2O3 with copper and manganese nitrates and acetates and the possibilities for CO, CH3OH and dimethyl ether (DME) oxidation were evaluated using continuous flow equipment with a four-channel isothermal stainless steel reactor. Effect of the support, Cu/Mn mole ratio, heat treatment of the precursor and active component loading were investigated. Highly active alumina supported Cu-Mn catalysts for CO and VOCs oxidation were synthesized. The effect of preparation conditions on the activity behavior of the catalysts was discussed. The synergetic interaction between copper and manganese species increases the activity for complete oxidation over mixed catalysts. Type of support, calcination temperature and active component loading along with catalyst composition are important factors, determining catalytic activity. Cu/Mn molar ratio of 1:5, heat treatment at 450oC and 20 % active component loading are the best compromise for production of active catalyst for simultaneous combustion of CO, CH3OH and DME.