Full-dimensional analytical ab initio potential energy surface of the ground state of HOI

Extensive ab initio calculations using a complete active space second-order perturbation theory wavefunction, including scalar and spin-orbit relativistic effects with a quadruple-zeta quality basis set were used to construct an analytical potential energy surface (PES) of the ground state of the [H, O, I] system. A total of 5344 points were fit to a three-dimensional function of the internuclear distances, with a global root-mean-square error of 1.26 kcal mol(-1). The resulting PES describes accurately the main features of this system: the HOI and HIO isomers, the transition state between them, and all dissociation asymptotes. After a small adjustment, using a scaling factor on the internal coordinates of HOI, the frequencies calculated in this work agree with the experimental data available within 10 cm(-1). (C) 2011 American Institute of Physics. [doi: 10.1063/1.3615545]

A greener and highly sensitive flow-based procedure for carbaryl determination exploiting long pathlength spectrophotometry and photochemical waste degradation

An environmentally friendly analytical procedure with high sensitivity for determination of carbaryl pesticide in natural waters was developed. The flow system was designed with solenoid micro-pumps in order to improve mixing conditions and minimize reagent consumption as well as waste generation. A long pathlength (100 cm) flow cell based on a liquid core waveguide (LCW) was employed to increase the sensitivity in detection of the indophenol formed from the reaction between carbaryl and p-aminophenol (PAP). A clean-up step based on cloud-point extraction was explored to remove the interfering organic matter, avoiding the use of toxic organic solvents. A linear response was observed within the range 5-200 mu g L(-1) and the detection limit, coefficient of variation and sampling rate were estimated as 1.7 mu g L(-1) (99.7% confidence level), 0.7% (n=20) and 55 determinations per hour, respectively. The reagents consumption was 1.9 mu g of PAP and 5.7 mu g of potassium metaperiodate, with volume of 2.6 mL of effluent per determination. The proposed procedure was selective for the determination of carbaryl, without interference from other carbamate pesticides. Recoveries within 84% and 104% were estimated for carbaryl spiked to water samples and the results obtained were also in agreement with those found by a batch spectrophotometric procedure at the 95% confidence level. The waste of the analytical procedure was treated with potassium persulphate and ultraviolet irradiation, yielding a colorless residue and a decrease of 94% of total organic carbon. In addition, the residue after treatment was not toxic for Vibrio fischeri bacteria. (c) 2010 Elsevier B.V. All rights reserved.

Biofuels and Sustainable Energy Development in Brazil

Through the assessment of three decades of the Alcohol Program in Brazil, the paper shows that adequate public policies regarding biomass production can deliver direct benefits like energy security improvement, foreign exchange savings, and local employment generation, reduced urban air pollution and avoided CO(2) emissions. Moreover, the paper shows that Brazilian produced ethanol has faced economies of scale, technical progress and productivity gains and is no longer dependent on subsidies to be competitive. The paper also examines the potential in Brazil for fostering other biofuels, namely biodiesel obtained from vegetable oils, as well as their implications on sustainable energy development. (C) 2011 Elsevier Ltd. All rights reserved.

Energy systems contributions in 2,000 m race simulation: a comparison among rowing ergometers and water

This study investigated the energy system contributions of rowers in three different conditions: rowing on an ergometer without and with the slide and rowing in the water. For this purpose, eight rowers were submitted to 2,000 m race simulations in each of the situations defined above. The fractions of the aerobic (W(AER)), anaerobic alactic (W(PCR)) and anaerobic lactic (W([La-])) systems were calculated based on the oxygen uptake, the fast component of excess post-exercise oxygen uptake and changes in net blood lactate, respectively. In the water, the metabolic work was significantly higher [(851 (82) kJ] than during both ergometer [674 (60) kJ] and ergometer with slide [663 (65) kJ] (P <= 0.05). The time in the water [515 (11) s] was higher (P < 0.001) than in the ergometers with [398 (10) s] and without the slide [402 (15) s], resulting in no difference when relative energy expenditure was considered: in the water [99 (9) kJ min(-1)], ergometer without the slide [99.6 (9) kJ min(-1)] and ergometer with the slide [100.2 (9.6) kJ min(-1)]. The respective contributions of the WAER, WPCR and W[La-] systems were water = 87 (2), 7 (2) and 6 (2)%, ergometer = 84 (2), 7 (2) and 9 (2)%, and ergometer with the slide = 84 (2), 7 (2) and 9 (1)%. (V) over dotO(2), HR and lactate were not different among conditions. These results seem to indicate that the ergometer braking system simulates conditions of a bigger and faster boat and not a single scull. Probably, a 2,500 m test should be used to properly simulate in the water single-scull race.

Acute high-intensity exercise with low energy expenditure reduced LDL-c and total cholesterol in men

A reduction in LDL cholesterol and an increase in HDL cholesterol levels are clinically relevant parameters for the treatment of dyslipidaemia, and exercise is often recommended as an intervention. This study aimed to examine the effects of acute, high-intensity exercise (similar to 90% VO(2max)) and varying carbohydrate levels (control, low and high) on the blood lipid profile. Six male subjects were distributed randomly into exercise groups, based on the carbohydrate diets (control, low and high) to which the subjects were restricted before each exercise session. The lipid profile (triglycerides, VLDL, HDL cholesterol, LDL cholesterol and total cholesterol) was determined at rest, and immediately and 1 h after exercise bouts. There were no changes in the time exhaustion (8.00 +/- A 1.83; 7.82 +/- A 2.66; and 9.09 +/- A 3.51 min) and energy expenditure (496.0 +/- A 224.8; 411.5 +/- A 223.1; and 592.1 +/- A 369.9 kJ) parameters with the three varying carbohydrate intake (control, low and high). Glucose and insulin levels did not show time-dependent changes under the different conditions (P > 0.05). Total cholesterol and LDL cholesterol were reduced after the exhaustion and 1 h recovery periods when compared with rest periods only in the control carbohydrate intake group (P < 0.05), although this relation failed when the diet was manipulated. These results indicate that acute, high-intensity exercise with low energy expenditure induces changes in the cholesterol profile, and that influences of carbohydrate level corresponding to these modifications fail when carbohydrate (low and high) intake is manipulated.

Assessing land availability to produce biomass for energy: The case of Brazilian charcoal for steel making

The paper discusses the availability of biomass in Brazil to supply charcoal to the steel industry on the bases of an initial global assessment of land potentially available for plantations and of Brazilian data that allows refining the assessment and specifying the issue of practical availability. Technical potentials are first assessed through a series of simple rules against direct competition with agriculture, forests and protected areas, and of quantitative criteria, whether geo-climatic (rainfall), demographic (population density) or legal (reserves). Institutional, social and economic factors are then identified and discussed so as to account for the practical availability of Brazilian biomass through six criteria. The ranking of nine Brazilian States according to these criteria brings out the necessary trade-offs in the selection of land for plantations that would efficiently supply charcoal to the steel industry. (C) 2008 Elsevier Ltd. All rights reserved.

Flux Pinning Optimization of MgB(2) Bulk Samples Prepared Using High-Energy Ball Milling and Addition of TaB(2)

MgB(2) is considered to be an important conductor for applications. Optimizing flux pinning in these conductors can improve their critical currents. Doping can influence flux pinning efficiency and grain connectivity, and also affect the resistivity, upper critical field and critical temperature. This study was designed to attempt the doping of MgB(2) on the Mg sites with metal-diborides using high-energy ball milling. MgB(2) samples were prepared by milling pre-reacted MgB(2) and TaB(2) powders using a Spex 8000M mill with WC jars and balls in a nitrogen-filled glove box. The mixing concentration in (Mg(1-x)Ta(x))B(2) was up to x = 0.10. Samples were removed from the WC jars after milling times up to 4000 minutes and formed into pellets using cold isostatic pressing. The pellets were heat treated in a hot isostatic press (HIP) at 1000 degrees C under a pressure of 30 kpsi for 24 hours. The influence that milling time and TaB(2) addition had on the microstructure and the resulting superconducting properties of TaB(2)-added MgB(2) is discussed. Improvement J(c) of at high magnetic fields and of pinning could be obtained in milled samples with added TaB(2) The sample with added 5at.% TaB(2) and milled for 300 minutes showed values of J(c) similar to 7 x 10(5) A/cm(2) and F(p) similar to 14 GN/m(3) at 2T, 4.2 K. The milled and TaB(2)-mixed samples showed higher values of mu(0)H(irr) than the unmilled-unmixed sample.

The influence of microstructure on the maximum load and fracture energy of refractory castables

Refractory castables are composed of fractions of fine to fairly coarse particles. The fine fraction is constituted primarily of raw materials and calcium aluminate cement, which becomes hydrated, forming chemical bonds that stiffen the concrete during the curing process. The present study focused on an evaluation of several characteristics of two refractory castables with similar chemical compositions but containing aggregates of different sizes. The features evaluated were the maximum load, the fracture energy, and the ""relative crack-propagation work"" of the two castables heat-treated at 110, 650, 1100 and 1550 degrees C. The results enabled us to draw the following conclusions: the heat treatment temperature exerts a significant influence on the matrix/aggregate interaction, different microstructures form in the castables with temperature, and a relationship was noted between the maximum load and the fracture energy. (C) 2009 Elsevier Ltd and Techna Group S.r.l. All rights reserved.

Properties of Y-TZP/Al(2)O(3) ceramic nanocomposites obtained by high-energy ball milling

In this work, the synthesis of Y(2)O(3) stabilized tetragonal zirconia polycrystals (Y-TZP)-alumina (Al(2)O(3)) powder mixture was performed by high-energy ball milling and the sintering behavior of this composite was investigated. In order to understand the phase transformations occurring during ball milling, samples were collected after different milling times, from 1 to 60 h. The milled powders were compacted by cold uniaxial pressing and sintered at 1400 and 1600 degrees C. Both powders and sintered samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive spectrometry analysis (EDS) and mechanical properties. Fully dense samples were obtained after sintering at 1600 degrees C, while the samples sintered at 1400 degrees C presented a full density for powder mixtures milled for 30 and 60 h. Fracture toughness and Vickers hardnessvalues of the Y-T-ZP/Al(2)O(3) nanocomposite were improved due to dispersed Al(2)O(3) grains and reduced ZrO(2) grain size. Samples sintered at 1400 degrees C, based on powders milled for 60 h, presented high K(IC) and hardness values near to 8.0 Mpan(1/2) and 15 GPa, respectively (C) 2008 Elsevier B.V. All rights reserved

Constitutive model for long term municipal solid waste mechanical behavior

This paper presents some improvements in the model proposed by Machado et al. [Machado SL, Carvalho MF, Vilar OM. Constitutive model for municipal solid waste. J Geotech Geoenviron Eng ASCE 2002; 128(11):940-51] now considering the influence of biodegradation of organic matter in the mechanical behavior of municipal solid waste. The original framework considers waste as composed of two component groups; fibers and organic paste. The particular laws of behavior are assessed for each component group and then coupled to represent waste behavior. The improvements introduced in this paper take into account the changes in the properties of fibers and mass loss due to organic matter depletion over time. Mass loss is indirectly calculated considering the MSW gas generation potential through a first order decay model. It is shown that as the biodegradation process occurs the proportion of fibers increases, however, they also undergo a degradation process which tends to reduce their ultimate tensile stress and Young modulus. The way these changes influence the behavior of MSW is incorporated in the final framework which captures the main features of the MSW stress-strain behavior under different loading conditions. (C) 2007 Elsevier Ltd. All rights reserved.

Influence of feed time and sulfate load on the organic and sulfate removal in an ASBR

The removal of sulfate and organic matter was assessed in an ASBR, which treated wastewater containing 500 mg COD L(-1) (3 g COD L(-1) d(-1)) in 8 h-cycles at 30 degrees C. The wastewater was enriched with sulfate at [COD/SO(4)(2-]) ratios of 1.34, 0.67 and 0.34 (8.8,4.5 and 2.2 gSO(4)(2-) L(-1) d(-1)). For each COD/[SO(4)(2-)] ratio fill times used were: 10 min (batch), 3 and 6 h (fed-batch), achieving sulfate reduction of 30%, 72% and 72% (COD/[SO(4)(2-)] of 1.34); 25%, 58% and 55% (COD/[SO(4)(2-)] of 0.67) and 23%, 37% and 27% (COD/[SO(4)(2-)] of 0.34), respectively, and organic matter removal of 87%, 68% and 80% (COD/[SO(4)(2-)] of 1.34); 78%, 75% and 69% (COD/[SO(4)(2-)] of 0.67) and 85%, 84% and 83% (COD/[SO(4)(2-)] of 0.34), respectively. The results showed that fed-batch operation improved sulfate reduction, whereas organic matter removals were similar for batch and fed-batch operation. In addition, increase in sulfate loading in the fed-batch operation improved organic matter removal. (C) 2010 Elsevier Ltd. All rights reserved.

Anaerobic degradation of linear alkylbenzene sulfonate (LAS) in fluidized bed reactor by microbial consortia in different support materials

Four anaerobic fluidized bed reactors filled with activated carbon (R1), expanded clay (R2), glass beads (R3) and sand (R4) were tested for anaerobic degradation of LAS. All reactors were inoculated with sludge from a UASB reactor treating swine wastewater and were fed with a synthetic substrate supplemented with approximately 20 mg l(-1) of LAS, on average. To 560 mg l(-1) COD influent, the maximum COD and LAS removal efficiencies were mean values of 97 +/- 2% and 99 +/- 2%, respectively, to all reactors demonstrating the potential applicability of this reactor configuration for treating LAS. The reactors were kept at 30 degrees C and operated with a hydraulic retention time (HRT) of 18 h. The use of glass beads and sand appear attractive because they favor the development of biofilms capable of supporting LAS degradation. Subsequent 16S rRNA gene sequencing and phylogenetic analysis of samples from reactors R3 and R4 revealed that these reactors gave rise to broad microbial diversity, with microorganisms belonging to the phyla Bacteroidetes, Firmicutes, Actinobacteria and Proteobacteria, indicating the role of microbial consortia in degrading the surfactant LAS. (C) 2010 Elsevier Ltd. All rights reserved.

Pentachlorophenol (PCP) dechlorination in horizontal-flow anaerobic immobilized biomass (HAIB) reactors

This study verifies the potential applicability of horizontal-flow anaerobic immobilized biomass (HAIB) reactors to pentachlorophenol (PCP) dechlorination. Two bench-scale HAIB reactors (R1 and R2) were filled with cubic polyurethane foam matrices containing immobilized anaerobic sludge. The reactors were then continuously fed with synthetic wastewater consisting of PCP, glucose, acetic acid, and formic acid as co-substrates for PCP anaerobic degradation. Before being immobilized in polyurethane foam matrices, the biomass was exposed to wastewater containing PCP in reactors fed at a semi-continuous rate of 2.0 mu g PCP g(-1) VS. The applied PCP loading rate was increased from 0.05 to 2.59 mg PCP l(-1) day(-1) for RI, and from 0.06 to 4.15 mg PCP l(-1) day(-1) for R2. The organic loading rates (OLR) were 1.1 and 1.7 kg COD m(-3) day(-1) at hydraulic retention times (HRT) of 24 h for R1 and 18 In for R2. Under such conditions, chemical oxygen demand (COD) removal efficiencies of up to 98% were achieved in the HAIB reactors. Both reactors exhibited the ability to remove 97% of the loaded PCP. Dichlorophenol (DCP) was the primary chlorophenol detected in the effluent. The adsorption of PCP and metabolites formed during PCP degradation in the packed bed was negligible for PCP removal efficiency. (C) 2009 Elsevier Ltd. All rights reserved.

Hydrogen production from soft-drink wastewater in an upflow anaerobic packed-bed reactor

The production of hydrogen from soft-drink wastewater in two upflow anaerobic packed-bed reactors was evaluated. The results show that soft-drink wastewater is a good source for hydrogen generation. Data from both reactors indicate that the reactor without medium containing macro- and micronutrients (R2) provided a higher hydrogen yield (3.5 mol H(2) mol(-1) of sucrose) as compared to the reactor (R1) with a nutrient-containing medium (3.3 mol H(2) mol(-1) of sucrose). Reactor R2 continuously produced hydrogen, whereas reactor R1 exhibited a short period of production and produced lower amounts of hydrogen. Better hydrogen production rates and percentages of biogas were also observed for reactor R2, which produced 0.4 L h(-1) L(-1) and 15.8% of H(2), compared to reactor R1, which produced 0.2 L h(-1) L(-1) and 2.6% of H(2). The difference in performance between the reactors was likely due to changes in the metabolic pathway for hydrogen production and decreases in bed porosity as a result of excessive biomass growth in reactor R1. Molecular biological analyses of samples from reactors R1 and R2 indicated the presence of several microorganisms, including Clostridium (91% similarity), Enterobacter (93% similarity) and Klebsiella (97% similarity). Copyright (C) 2011, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.

Effects of temperature at different organic loading levels on the performance of a fluidized-bed anaerobic sequencing batch bioreactor

An investigation was performed on the effect of temperature and organic load on the stability and efficiency of a 1.8-L fluidized-bed anaerobic sequencing batch reactor (ASBR), containing granulated biomass. Assays were carried out employing superficial up How velocity of 7 m/h, total cycle length of 6 h and synthetic wastewater volume of 1.3 L per cycle. The fluidized-bed ASH was operated at 15, 20, 25 and 30 degrees C with influent organic matter concentrations of 500 and 1000 mgCOD/L The system showed stability under all conditions and presented filtered samples removal efficiency ranging from 79 to 86%. A first-order kinetic model could be fitted to the experimental values of the organic matter concentration profiles. The specific kinetic parameter values of this model ranged from 0.0435 to 0.2360 L/(gTVS h) at the implemented operation conditions. in addition, from the slope of an Arrhenius plot, the activation energy values were calculated to be 16,729 and 12,673 cal/mol for operation with 500 and 1000 mgCOD/L, respectively. These results show that treatment of synthetic wastewater. with concentration of 500 mgCOD/L, was more sensitive to temperature variations than treatment of the same residue with concentration of 1000 mgCOD/L. Comparing the activation energy value for operation at 500 mgCOD/L with the value obtained by Agibert et al. (S.A. Agibert, M.B. Moreira, S.M. Ratusznei, J.A.D. Rodrigues, M. Zaiat, E. Foresti. Influence of temperature on performance of an ASBBR with circulation applied to treatment of low-strength wastewater. journal of Applied Biochemistry and Biotechnology, 136 (2007) 193-206) in an ASBBR treating the same wastewater at the same concentration, the value obtained in the fluidized-bed ASBR showed to be superior, indicating that treatment of synthetic wastewater in a reactor containing granulated biomass was more sensitive to temperature variations than the treatment using immobilized biomass. (c) 2008 Elsevier B.V. All rights reserved.