Gasification reactivity of charcoal with CO2. Part I: Conversion and structural phenomena

The gasification reaction of fir charcoal with CO₂ was studied by isothermal thermogravimetric analysis under kinetic control. The derived reaction rate (r=dX/dt) as a function of the converted carbon mass (X) was compared with random pore model predictions and found to be much higher at elevated conversion levels than predicted by theory. Similar enhanced reaction rate behaviour was evidenced after removing the natural alkali catalyst from the charcoal by acid washing, suggesting that with untreated charcoal the late reaction rate contribution stems from both, catalytic and additional structure effects. Literature attributes the unpredicted late reaction rate behaviour to the disintegration of the porous char particle into small fragments, which, in line with percolation theory predictions, seems to occur only after a critical conversion level has been reached. However, our gasification data reveal a gradual rise in the charcoal reactivity thereafter, suggesting a breaking up (embrittlement) of the solid phase accompanied by the exposure of fresh surface area from fracturing. The original random pore model derivation given by Bhatia and Perlmutter is extended to account also for these peculiarities and the resulting kinetic relation described our reaction rate data well over the entire conversion range.     

Residual effect of long-term applications of farmyard manure to silage maize

Sluijsmans and Kolenbrander developed a simple model to describe the availability of animal manure, assuming a readily available, an easily decomposable and a slowly decomposable N fraction. We tested this model on data from an experiment in which farmyard manure had been applied for eleven successive years to silage maize [Zea mays L.] grown on a light sandy soil. The residual effects of this FYM were then measured by growing Italian ryegrass [Lolium multiflorum Lamk.] in the 12th year. The measured uptake of N by the grass of the FYM residues was then compared with the computed values. The measured amounts of N taken up agreed fairly well with the calculated amounts for applications of 50 and 100 t FYM per ha per year.If the rates of manure application are adjusted to crop requirement, the model shows that the potential, long-term release of N from the residual N fraction of FYM will not exceed 20 kg N per ha. For cattle slurry with a smaller residual fraction, the release will be at most 10% of the total annual N application.     

Exafs study of the local structure of Ni in Ni-MoS2/C hydrodesulfurization catalysts

To study the local structure of the Ni promoter atom, the Ni and Mo K edge EXAFS spectra of Ni-MoS₂/C hydrodesulfurization catalyst were measured in an in-situ EXAFS cell at 77 K. The Ni atom is situated in a square pyramid of five S atoms at a distance of 2.21 Å from the S atoms. In addition an EXAFS contribution due to a Mo atom at 2.82 Å from the Ni atom could be identified. This local structure indicates that the Ni atoms are situated on top of the S₄ squares at the MoS₂ edges in millerite-type Ni sites. The Ni atoms are situated in the planes of the Mo atoms and not in the intercalation plane midway between successive MoS₂ sandwich layers.     

Chaotic fluid mixing by alternating microparticle topologies to enhance biochemical reactions

We report experimental results on chaotic mass transport induced by alternating topological changes of magnetic particle chains actuated by a rotating magnetic field. Results on the induced fluid flows, through particle tracing experiments and mixing experiments, are obtained for (1) the regime of rigid chain rotation and (2) the regime wherein chains periodically fragment and reform. In the case of rigid rotating chains, the overall tracer particle trajectories are steady, slightly modulated circles around the center of the microparticle chains. In the regime of periodic chain breaking and reformation, the tracer particle trajectories become chaotic. The level of mixing is measured by using a mixing index (M) in a water–dye system, i.e., in a perfectly mixed system M = 0, while in an unmixed system M = 1. When particle chains periodically break and reform, we observe that the mixing index M decreases from 1 to 0.1 within 15 rotational cycles. For rigid rotating chains, M reaches a minimum of only 0.5. We also report the effect of the different actuation regimes on a biological binding reaction in the solution and indeed found that the reaction product (at equal actuation time) is significantly enhanced (3 times) by the dynamic chain regime as compared to the rigid chain regime. We conclude that the alternating topological change of microparticle chains—with repetitive chain breakup and chain reformation—is an effective mechanism to achieve chaotic mixing and thereby promote and homogenize reactions in lab-on-a-chip systems.     

Biaxial orientation of linear polyethylenes using the compressive deformation process

The tensile properties of three grades of linear polyethylene were enhanced by a factor of as much as 15 using a melt/solid phase compressive deformation process that produced equi-biaxial planar orientation in the sheet. Ultra high molecular weight polyethylene with planar isotropy and an in-plane modulus of 10 GPa and a tensile strength of 330 MPa was produced using this method. It was found that the molecular weight had a significant influence on the optimum processing temperature, the ultimate biaxial deformation ratio and hence the ultimate tensile properties. High density polyethylene processed under ideal conditions had a tensile modulus of 2.3 GPa and a tensile strength of 250 MPa. The tensile strength increased linearly with increasing biaxial deformation ratio and the tensile modulus increased non-linearly with increasing biaxial deformation ratio. The deformation rate and the dwell time did not have a significant effect on the tensile properties. Shrinkage tests showed that biaxial deformation was less effective than uniaxial deformation in inducing orientation of the polymer chains, however differential scanning calorimetry results were consistent with the presence of extended chain crystals in very highly oriented ultra high molecular weight polyethylene sheets.     

Validation of GOES and MODIS active fire detection products using ASTER and ETM+ data

In this study we implemented a comprehensive analysis to validate the MODIS and GOES satellite active fire detection products (MOD14 and WFABBA, respectively) and characterize their major sources of omission and commission errors which have important implications for a large community of fire data users. Our analyses were primarily based on the use of 30 m resolution ASTER and ETM+ imagery as our validation data. We found that at the 50% true positive detection probability mark, WFABBA requires four times more active fire area than is necessary for MOD14 to achieve the same probability of detection, despite the 16× factor separating the nominal spatial resolutions of the two products. Approximately 75% and 95% of all fires sampled were omitted by the MOD14 and WFABBA instantaneous products, respectively; whereas an omission error of 38% was obtained for WFABBA when considering the 30-minute interval of the GOES data. Commission errors for MOD14 and WFABBA were found to be similar and highly dependent on the vegetation conditions of the areas imaged, with the larger commission errors (approximately 35%) estimated over regions of active deforestation. Nonetheless, the vast majority (> 80%) of the commission errors were indeed associated with recent burning activity where scars could be visually confirmed in the higher resolution data. Differences in thermal dynamics of vegetated and non-vegetated areas were found to produce a reduction of approximately 50% in the commission errors estimated towards the hours of maximum fire activity (i.e., early-afternoon hours) which coincided with the MODIS/Aqua overpass. Lastly, we demonstrate the potential use of temporal metrics applied to the mid-infrared bands of MODIS and GOES data to reduce the commission errors found with the validation analyses.     

A reactive GRASP and path relinking for a combined production–distribution problem

An NP-hard production–distribution problem for one product over a multi-period horizon is investigated. The aim is to minimize total cost taking production setups, inventory levels and distribution into account. An integer linear model is proposed as a compact problem specification but it cannot be solved to optimality for large instances. Instead of using a classical two-phase approach (production planning and then route construction for each day), metaheuristics that simultaneously tackle production and routing decisions are developed: a GRASP (greedy randomized adaptive search procedure) and two improved versions using either a reactive mechanism or a path-relinking process. These algorithms are evaluated on 90 randomly generated instances with 50, 100 and 200 customers and 20 periods. The results confirm the interest of integrating production and distribution decisions, compared to classical two-phase methods. Moreover, reaction and path-relinking give better results than the GRASP alone.     

A multi-start iterated local search with tabu list and path relinking for the two-echelon location-routing problem

The two-echelon location-routing problem (LRP-2E) is raised by the design of transportation networks with two types of trips: first-level trips serving from one main depot a set of satellite depots, to be located, and second-level trips supplying customers from these satellites. In the proposed multi-start iterated local search (MS-ILS), three greedy randomized heuristics are used cyclically to get initial solutions. Each ILS run alternates between two search spaces: LRP-2E solutions, and travelling salesman (TSP) tours covering the main depot and the customers. The number of iterations allotted to a run is reduced whenever a known solution (stored in a tabu list) is revisited. MS-ILS can be reinforced by a path-relinking procedure (PR), used internally for intensification, as post-optimization, or both. On two sets with 24 and 30 LRP-2E instances, MS-ILS outperforms on average two GRASP algorithms and adding PR brings a further improvement. Our metaheuristic also surpasses a tabu search on 30 instances for a more general problem with several main depots. It is still effective on a particular case, the capacitated location-routing problem (CLRP): In a comparison with four published metaheuristics, only one (LRGTS, Prins et al., 2007) does better.     

Landsat approaches to map agro-pastoral farming in the wetlands of southern Sudan

Machine-learning algorithms (MLA) are coming of age within satellite remote sensing (SRS). This study compares the performance of a number of MLAs with more traditional indices and algorithms to map annual agro-pastoralist farming activity in southern Sudan. Two Landsat images from the early dry season 2014 and 2015 were analysed thoroughly and evaluated by interpretation of farming cover from very high resolution (VHR) images on Google Earth (GE). Traditional SRS indices based upon red and near infrared (NIR) bands used for monitoring rangelands did not perform well for the wet rangeland conditions compared to the use of blue and shortwave infrared (SWIR) bands. The species distribution model programme, MaxEnt, was used to produce a continuous farming activity indices using only Landsat-derived variables. Compared to other SRS classification approaches, maximum entropy (MaxEnt) showed the best overall performance to map farming activity followed by classification tree analysis (CTA). Overall mapping agreement >95.0% was reached for most methodologies, with MaxEnt showing very high mapping agreement (≥98.5%) for both years. When the result of MaxEnt’s good performance is put together in a 2014–15 or a 1999–2002 change detection scenario, it corroborates ground reports on massive human abuses that have taken place in Unity state of southern Sudan.     

Estrogen receptor-beta messenger ribonucleic acid ontogeny in the prostate of normal and neonatally estrogenized rats

Neonatal exposure to estrogens permanently alters rat prostate growth and epithelial differentiation leading to prostatic dysplasia on aging. The effects are lobe-specific, with the greatest response observed in the ventral lobe. Recently, a novel estrogen receptor (ER) complementary DNA was cloned from the rat prostate and termed ER-beta (ER beta) due to its high homology with the classical ER alpha. The protein possesses high affinity for 17beta-estradiol, indicating that ER beta is an alternate molecule for mediating estrogenic effects. Importantly, ER beta messenger RNA (mRNA) was localized to rat prostatic epithelial cells, which contrasts with the stromal localization of ER alpha in the rat prostate. The present study was undertaken to determine the ontogeny of ER beta mRNA expression in the rat prostate lobes and to examine the effects of early estrogen exposure on prostatic ER beta expression. Male rat pups were given 25 microg estradiol or oil on days 1, 3, and 5; were killed on day 1, 3 (oils only), 6, 10, 30, or 90; and prostate lobes were frozen. Longitudinal sections were processed for in situ hybridization using an 35S-labeled antisense mRNA probe corresponding to a 400-bp EcoRI-AccI fragment in the 5' untranslated region of rat ER beta complementary DNA. Image analysis was used to quantitate silver grains. In addition, total RNA was isolated from the ventral prostate (VP) and used for semiquantitative RT-PCR. Results from in situ hybridization revealed that at birth, ER beta was equivalently expressed at low levels in both mesenchymal and epithelial cells in oil-treated rats. From day 1 onwards, expression in all stromal cells slowly and significantly declined, so that in the control adult prostate, stromal ER beta mRNA was slightly above background. In the oil-treated control rats, epithelial ER beta mRNA increased to moderate levels between days 6-10 in the VP and days 10-15 in the dorsal and lateral lobes as cells began differentiation and ducts lumenized. A further significant increase in ER beta message was observed at day 30, which indicates that full epithelial ER beta expression may require the completion of functional differentiation. By day 90, expression levels were maximal and similar between the lobes. RT-PCR substantiated this developmental increase in ER beta between days 1-90. Neonatal exposure to estrogens did not have an immediate effect on prostatic ER beta mRNA levels as determined by in situ hybridization and RT-PCR. However, the marked increase in epithelial cell expression at day 30 observed in the control VP was dampened in the VP of animals exposed neonatally to estrogens. By day 90, the VP of estrogenized rats possessed low ER beta message levels compared with the high expression in oil controls. In contrast, the dorsal and lateral lobes of neonatally estrogenized rats possessed high levels of ER beta mRNA at day 90, equivalent to controls. The present data demonstrate that ER beta mRNA expression in the rat prostate is developmentally regulated, and that neonatal estrogen can affect this expression in the adult VP. Because the effect of neonatal estrogens was not immediate, the data imply that early estrogen exposure may not directly autoregulate ER beta expression, and suggests that the adult effects on ER beta mRNA expression may be indirect. The differences in ER beta mRNA imprinting in the separate lobes may account for or reflect the lobe-specific neonatal estrogen imprints previously observed in the rat prostate.