Mechanistic changes observed in heavy water for nitrate reduction reaction on palladium-modified Pt(hkl) electrodes

Reduction of nitrate on palladium-modified platinum single-crystal electrodes has been investigated both voltammetrically and spectroscopically in acidic media (pH = 1). Results obtained in H2O and D2O solvents are compared for the three crystallographic orientations. FTIR and differential electrochemical mass spectrometry (DEMS) results clearly indicate that the isotopic substitution of the solvent has a large effect in the mechanism of the reaction, changing the nature of the detected products. For Pt(111)/Pd and Pt(100)/Pd, N2O is detected as the main product of nitrate reduction when D2O is used as solvent, while no N2O is detected when the reaction is performed in H2O. For Pt(110)/Pd, N2O is detected in both solvents, although the use of D2O clearly favours the preferential formation of this product. The magnitude of voltammetric currents is also affected by the nature of the solvent. This has been analysed considering, in addition to the different product distribution, the existence of different transport numbers and optical constants of the solvent.

Drag reduction phenomenon in viscous oil-water dispersed pipe flow: Experimental investigation and phenomenological modeling

An experimental study on drag-reduction phenomenon in dispersed oil-water flow has been performed in a 26-mm-i.d. Twelve meter long horizontal glass pipe. The flow was characterized using a novel wire-mesh sensor based on capacitance measurements and high-speed video recording. New two-phase pressure gradient, volume fraction, and phase distribution data have been used in the analysis. Drag reduction and slip ratio were detected at oil volume fractions between 10 and 45% and high mixture Reynolds numbers, and with water as the dominant phase. Phase-fraction distribution diagrams and cross-sectional imaging of the flow suggested the presence of a higher amount of water near to the pipe wall. Based on that, a phenomenology for explaining drag reduction in dispersed flow in a flow situation where slip ratio is significant is proposed. A simple phenomenological model is developed and the agreement between model predictions and data, including data from the literature, is encouraging. (c) 2011 American Institute of Chemical Engineers AIChE J, 2012

Changes in the intermediate water mass formation rates in the global ocean for the Last Glacial Maximum, mid-Holocene and pre-industrial climates

The paleoclimate version of the National Center for Atmospheric Research Community Climate System Model version 3 (NCAR-CCSM3) is used to analyze changes in the water formation rates in the Atlantic, Pacific, and Indian Oceans for the Last Glacial Maximum (LGM), mid-Holocene (MH) and pre-industrial (PI) control climate. During the MH, CCSM3 exhibits a north-south asymmetric response of intermediate water subduction changes in the Atlantic Ocean, with a reduction of 2 Sv in the North Atlantic and an increase of 2 Sv in the South Atlantic relative to PI. During the LGM, there is increased formation of intermediate water and a more stagnant deep ocean in the North Pacific. The production of North Atlantic Deep Water (NADW) is significantly weakened. The NADW is replaced in large extent by enhanced Antarctic Intermediate Water (AAIW), Glacial North Atlantic Intermediate Water (GNAIW), and also by an intensified of Antarctic Bottom Water (AABW), with the latter being a response to the enhanced salinity and ice formation around Antarctica. Most of the LGM intermediate/mode water is formed at 27.4 < sigma(theta) < 29.0 kg/m(3), while for the MH and PI most of the subduction transport occurs at 26.5 < sigma(theta) < 27.4 kg/m(3). The simulated LGM Southern Hemisphere winds are more intense by 0.2-0.4 dyne/cm(2). Consequently, increased Ekman transport drives the production of intermediate water (low salinity) at a larger rate and at higher densities when compared to the other climatic periods.

H-1 low- and high-field NMR study of the effects of plasma treatment on the oil and water fractions in crude heavy oil

The chemical and physical properties of a Brazilian heavy oil submitted to plasma treatment were investigated by H-1 low-and high-field nuclear magnetic resonance (NMR) combined to the characterization of rheological properties, thermogravimetry and measurement of basic sediments and water (BSW) content. The crude oil was treated in a dielectric barrier discharge plasma reactor, using natural gas, CO2 or H-2 as working gas. The results indicated a large drop in the water content of the plasma-treated samples as compared to the crude oil, giving rise to a reduction in the viscosity. No significant chemical change was produced in the oil portion itself, as observed by H-1 NMR. The water contents determined by H-1 low-field NMR analyses agreed well with those obtained by BSW, indicating the low-field NMR methods as a useful tool for following the effects of plasma treatments on heavy oils, allowing the separation of the effects caused on the water and oil fractions. (C) 2011 Elsevier Ltd. All rights reserved.

Reducing Water and Chloride Penetration Through Silicate Treatments for Concrete as a Mean to Control Corrosion Kinetics

There are currently many types of protective materials for reinforced concrete structures and the influence of these materials in the chloride diffusion coefficient and water penetration still needs more research. The aim of this work is to analyze the contributions regarding the typical three surface concrete protection systems (coatings, linings and pore blockers) and discusses the results of three pore blockers (sodium silicate) tested in this work. To this end, certain tests were used: one involving permeability mechanism (low pressure-immersion absorption), one involving capillary water absorption, and the last, a migration test used to estimate the effective chloride diffusion coefficient in saturated condition. Results indicated reduction in chloride diffusion coefficients and capillary water absorption, therefore, restrictions to water penetration from external environmental. As a consequence, a reduction of the corrosion kinetics and a control of the chloride ingress are expected.

RELATIONS BETWEEN SOIL SURFACE ROUGHNESS, TORTUOSITY, TILLAGE TREATMENTS, RAINFALL INTENSITY AND SOIL AND WATER LOSSES FROM A RED YELLOW LATOSOL

The soil surface roughness increases water retention and infiltration, reduces the runoff volume and speed and influences soil losses by water erosion. Similarly to other parameters, soil roughness is affected by the tillage system and rainfall volume. Based on these assumptions, the main purpose of this study was to evaluate the effect of tillage treatments on soil surface roughness (RR) and tortuosity (T) and to investigate the relationship with soil and water losses in a series of simulated rainfall events. The field study was carried out at the experimental station of EMBRAPA Southeastern Cattle Research Center in Sao Carlos (Fazenda Canchim), in Sao Paulo State, Brazil. Experimental plots of 33 m(2) were treated with two tillage practices in three replications, consisting of: untilled (no-tillage) soil (NTS) and conventionally tilled (plowing plus double disking) soil (CTS). Three successive simulated rain tests were applied in 24 h intervals. The three tests consisted of a first rain of 30 mm/h, a second of 30 mm/h and a third rain of 70 mm/h. Immediately after tilling and each rain simulation test, the surface roughness was measured, using a laser profile meter. The tillage treatments induced significant changes in soil surface roughness and tortuosity, demonstrating the importance of the tillage system for the physical surface conditions, favoring water retention and infiltration in the soil. The increase in surface roughness by the tillage treatments was considerably greater than its reduction by rain action. The surface roughness and tortuosity had more influence on the soil volume lost by surface runoff than in the conventional treatment. Possibly, other variables influenced soil and water losses from the no-tillage treatments, e. g., soil type, declivity, slope length, among others not analyzed in this study.

Ethanol and Water Adsorption on Close-Packed 3d, 4d, and 5d Transition-Metal Surfaces: A Density Functional Theory Investigation with van der Waals Correction

Nowadays, there is a great interest in the economic success of direct ethanol fuel cells; however, our atomistic understanding of the designing of stable and low-cost catalysts for the steam reforming of ethanol is still far from satisfactory, in particular due to the large number of undesirable intermediates. In this study, we will report a first-principles investigation of the adsorption properties of ethanol and water at low coverage on close-packed transition-metal (TM) surfaces, namely, Fe(110), Co(0001), Ni(111), Cu(111), Ru(0001), Rh(111), Pd(111), Ag(111), Os(0001), Ir(111), Pt(111), and Au(111), employing density functional theory (DFT) calculations. We employed the generalized gradient approximation with the formulation proposed by Perdew, Burke, and Erzenholf (PBE) to the exchange correlation functional and the empirical correction proposed by S. Grimme (DFT+D3) for the van der Waals correction. We found that both adsorbates binds preferentially near or on the on top sites of the TM surfaces through the 0 atoms. The PBE adsorption energies of ethanol and water decreases almost linearly with the increased occupation of the 4d and 5d d-band, while there is a deviation for the 3d systems. The van der Waals correction affects the linear behavior and increases the adsorption energy for both adsorbates, which is expected as the van der Waals energy due to the correlation effects is strongly underestimated by DFT-PBE for weak interacting systems. The geometric parameters for water/TM are not affected by the van der Waals correction, i.e., both DFT and DFT+D3 yield an almost parallel orientation for water on the TM surfaces; however, DFT+D3 changes drastically the ethanol orientation. For example, DFT yields an almost perpendicular orientation of the C-C bond to the TM surface, while the C-C bond is almost parallel to the surface using DFT +D3 for all systems, except for ethanol/Fe(110). Thus, the van der Waals correction decreases the distance of the C atoms to the TM surfaces, which might contribute to break the C-C bond. The work function decreases upon the adsorption of ethanol and water, and both follow the same trends, however, with different magnitude (larger for ethanol/TM) due to the weak binding of water to the surface. The electron density increases mainly in the region between the topmost layer and the adsorbates, which explains the reduction of the substrate work function.

Occurrence of molds on laminated paperboard for aseptic packaging, selection of the most hydrogen peroxide- and heat-resistant isolates and determination of their thermal death kinetics in sterile distilled water

This study aimed at enumerating molds (heat-labile and heat-resistant) on the surface of paperboard material to be filled with tomato pulps through an aseptic system and at determining the most heat-and hydrogen peroxide-resistant strains. A total of 118 samples of laminated paperboard before filling were collected, being 68 before and 50 after the hydrogen peroxide bath. Seven molds, including heat-resistant strains (Penicillium variotii and Talaromyces flavus) with counts ranging between 0.71 and 1.02 CFU/cm(2) were isolated. P. variotii was more resistant to hydrogen peroxide than T. flavus and was inactivated after heating at 85 degrees C/15 min. When exposed to 35 % hydrogen peroxide at 25 degrees C, T. flavus (F5E2) and N. fischeri (control) were less resistant than P. variotti (F1A1). P. citrinum (F7E2) was shown to be as resistant as P. variotti. The D values (the time to cause one logarithmic cycle reduction in a microbial population at a determined temperature) for spores of P. variotii (F1A1) and N. fischeri (control) with 4 months of age at 85 and 90 degrees C were 3.9 and 4.5 min, respectively. Although the contamination of packages was low, the presence of heat-and chemical-resistant molds may be of concern for package sterility and product stability during shelf-life. To our knowledge, this is the first report that focuses on the isolation of molds, including heat-resistant ones, contaminating paperboard packaging material and on estimating their resistance to the chemical and physical processes used for packaging sterilization.

Assessment of a UASB reactor for the removal of sulfate from acid mine water

A bench-scale Upflow Anaerobic Sludge Blanket (UASB) reactor was used to study the treatment of acid mine drainage through the biological reduction of sulfate. The reactor was fed with acid mine drainage collected at the Osamu Utsumi uranium mine (Caldas, MG, Brazil) and supplemented with ethanol as an external carbon source. Anaerobic granular sludge originating from a reactor treating poultry slaughterhouse wastewater was used as the inoculum. The reactor's performance was studied according to variations in the chemical oxygen demand (COD)/SO42- ratio, influent dilution and liquid-phase recirculation. The digestion of a dilution of the acid mine drainage resulted in a 46.3% removal of the sulfate and an increase in the effluent pH (COD/SO42- = 0.67). An increase in the COD/SO42- ratio to 1.0 resulted in an 85.6% sulfate reduction. The reduction of sulfate through complete oxidation of the ethanol was the predominant path in the reactor, although the removal of COD was not greater than 68% in any of the operational stages. The replenishment of the liquid phase with tap water positively affected the reactor, whereas the recirculation of treated effluent caused disequilibrium and decreased efficiency. (C) 2012 Elsevier Ltd. All rights reserved.

Sialic acid reduction in the saliva of streptozotocin induced diabetic rats

Objective: Diabetes causes changes in the salivary glands and in the composition of saliva, as well as symptoms such as dry mouth and hyposalivation. Therefore, this study aimed at investigating changes in salivary secretion and composition, in response to parasympathetic stimuli, in diabetic rats induced with streptozotocin. Design: Diabetes was induced by a single intraperitoneal injection of streptozotocin. Thirty days after diabetes induction, the animals were anaesthetized and salivation was stimulated by an intraperitoneal injection of Pilocarpine (0.6 mg/kg body weight) dissolved in distilled water. Saliva was collected for 40 min and immediately stored at -80 degrees C until analysis. The salivary flow rate, amount of total protein, amylase and peroxidase activities, and free and total sialic acid contents were measured. Results: Salivary flow rate was reduced in the diabetic group (p < 0.05). Moreover, increases in total protein amount and in amylase and peroxidase activities were observed in diabetic animals. No difference was observed for free sialic acid content between groups. On the other hand, a significantly decrease in the total sialic acid content was observed in the diabetic group (p < 0.05). Conclusions: Our findings suggest that a decrease in sialic acid in the saliva of diabetic animals can be related to xerostomia reported by diabetic patients. However, further clinical trials are needed to verify if the decrease in sialic acid also occurs in human saliva. (C) 2012 Elsevier Ltd. All rights reserved.

Study of La2-xCaxCuO4 perovskites for the low temperature water gas shift reaction

The effects of small fractions of calcium (x = 0, 0.05, 0.1, 0.15, and 0.20) on the structure and the catalytic properties of La2-xCaxCuO4 peroviskites have been investigated. The samples have been synthesized using the co-precipitation method. Perovskite-type oxides were characterized by XRD, TPR, XPS, XANES, SEM, and TEM. Catalytic tests for the water gas shift reaction (WGSR) were carried out in a tubular reactor at 290 degrees C. All samples showed a well-defined perovskite structure with surface areas between 6 and 18 m(2) g(-1). The partial substitution of La by Ca enhanced the stability of the perovskites and increased their reduction temperature. All catalysts were actives for WGSR, and the best catalytic performance was obtained for the La1.85Ca0.15CuO4 catalyst, but the samples with 5 and 10% of Ca had the best TOF values for reaction. These results can be associated to promoter effect of calcium, the high surface area, and the reducible species Cu-0 and Cu1+. (C) 2011 Elsevier B.V. All rights reserved.

Chemical resistance of the gram-negative bacteria to different sanitizers in a water purification system

Abstract Background Purified water for pharmaceutical purposes must be free of microbial contamination and pyrogens. Even with the additional sanitary and disinfecting treatments applied to the system (sequential operational stages), Pseudomonas aeruginosa, Pseudomonas fluorescens, Pseudomonas alcaligenes, Pseudomonas picketti, Flavobacterium aureum, Acinetobacter lowffi and Pseudomonas diminuta were isolated and identified from a thirteen-stage purification system. To evaluate the efficacy of the chemical agents used in the disinfecting process along with those used to adjust chemical characteristics of the system, over the identified bacteria, the kinetic parameter of killing time (D-value) necessary to inactivate 90% of the initial bioburden (decimal reduction time) was experimentally determined. Methods Pseudomonas aeruginosa, Pseudomonas fluorescens, Pseudomonas alcaligenes, Pseudomonas picketti, Flavobacterium aureum, Acinetobacter lowffi and Pseudomonas diminuta were called in house (wild) bacteria. Pseudomonas diminuta ATCC 11568, Pseudomonas alcaligenes INCQS , Pseudomonas aeruginosa ATCC 15442, Pseudomonas fluorescens ATCC 3178, Pseudomonas picketti ATCC 5031, Bacillus subtilis ATCC 937 and Escherichia coli ATCC 25922 were used as 'standard' bacteria to evaluate resistance at 25°C against either 0.5% citric acid, 0.5% hydrochloric acid, 70% ethanol, 0.5% sodium bisulfite, 0.4% sodium hydroxide, 0.5% sodium hypochlorite, or a mixture of 2.2% hydrogen peroxide (H2O2) and 0.45% peracetic acid. Results The efficacy of the sanitizers varied with concentration and contact time to reduce decimal logarithmic (log10) population (n cycles). To kill 90% of the initial population (or one log10 cycle), the necessary time (D-value) was for P. aeruginosa into: (i) 0.5% citric acid, D = 3.8 min; (ii) 0.5% hydrochloric acid, D = 6.9 min; (iii) 70% ethanol, D = 9.7 min; (iv) 0.5% sodium bisulfite, D = 5.3 min; (v) 0.4% sodium hydroxide, D = 14.2 min; (vi) 0.5% sodium hypochlorite, D = 7.9 min; (vii) mixture of hydrogen peroxide (2.2%) plus peracetic acid (0.45%), D = 5.5 min. Conclusion The contact time of 180 min of the system with the mixture of H2O2+ peracetic acid, a total theoretical reduction of 6 log10 cycles was attained in the water purified storage tank and distribution loop. The contact time between the water purification system (WPS) and the sanitary agents should be reviewed to reach sufficient bioburden reduction (over 6 log10).

Relations between soil surface roughness, tortuosity, tillage treatments, rainfall intensity and soil and water losses from a red yellow latosol

The soil surface roughness increases water retention and infiltration, reduces the runoff volume and speed and influences soil losses by water erosion. Similarly to other parameters, soil roughness is affected by the tillage system and rainfall volume. Based on these assumptions, the main purpose of this study was to evaluate the effect of tillage treatments on soil surface roughness (RR) and tortuosity (T) and to investigate the relationship with soil and water losses in a series of simulated rainfall events. The field study was carried out at the experimental station of EMBRAPA Southeastern Cattle Research Center in São Carlos (Fazenda Canchim), in São Paulo State, Brazil. Experimental plots of 33 m² were treated with two tillage practices in three replications, consisting of: untilled (no-tillage) soil (NTS) and conventionally tilled (plowing plus double disking) soil (CTS). Three successive simulated rain tests were applied in 24 h intervals. The three tests consisted of a first rain of 30 mm/h, a second of 30 mm/h and a third rain of 70 mm/h. Immediately after tilling and each rain simulation test, the surface roughness was measured, using a laser profile meter. The tillage treatments induced significant changes in soil surface roughness and tortuosity, demonstrating the importance of the tillage system for the physical surface conditions, favoring water retention and infiltration in the soil. The increase in surface roughness by the tillage treatments was considerably greater than its reduction by rain action. The surface roughness and tortuosity had more influence on the soil volume lost by surface runoff than in the conventional treatment. Possibly, other variables influenced soil and water losses from the no-tillage treatments, e.g., soil type, declivity, slope length, among others not analyzed in this study.

Renal GLUT1 reduction depends on angiotensin-converting enzyme inhibition in diabetic hypertensive rats

Aims: Angiotensin-converting enzyme (ACE) inhibitors are used in diabetic kidney disease to reduce systemic/intra-glomerular pressure. The objective of this study was to investigate whether reducing blood pressure (BP) could modulate renal glucose transporter expression, and urinary markers of diabetic nephropathy in diabetic hypertensive rats treated with ramipril or amlodipine. Main methods: Diabetes was induced in spontaneously-hypertensive rats (~210 g) by streptozotocin (50 mg/kg). Thirty days later, animals received ramipril 15 μg/kg/day (R, n =10), or amlodipine 10 mg/kg/day (A, n= 8,) or water (C, n = 10) by gavage. After 30-day treatment, body weight, glycaemia, urinary albumin and TGF-β1 (enzyme-linked immunosorbent assay) and BP (tail-cuff pressure method) were evaluated. Kidneys were removed for evaluation of renal cortex glucose transporters (Western blotting) and renal tissue ACE activity (fluorometric assay). Key findings: After treatments, body weight (p = 0.77) and glycaemia (p = 0.22) were similar among the groups. Systolic BP was similarly reduced (p < 0.001) in A and R vs. C (172.4 ± 3.2; 186.7 ± 3.7 and 202.2 ± 4.3 mm Hg; respectively). ACE activity (C: 0.903 ± 0.086; A: 0.654 ± 0.025, and R: 0.389 ± 0.057 mU/mg), albuminuria (C: 264.8 ± 15.4; A: 140.8 ± 13.5 and R: 102.8 ± 6.7 mg/24 h), and renal cortex GLUT1 content (C: 46.81 ± 4.54; A: 40.30 ± 5.39 and R: 26.89 ± 0.79 AU) decreased only in R (p < 0.001, p < 0.05 and p < 0.001; respectively). Significance:We concluded that the blockade of the renin–angiotensin systemwith ramipril reduced earlymarkers of diabetic nephropathy, a phenomenon that cannot be specifically related to decreased BP levels.