Experimento para quantificar a eficiência de aspersão de líquidos: aplicação em distribuidores espinha de peixe

This paper describes a device developed on the pilot scale and a simple approach to compare liquid distributor efficiencies. The technique consists basically of analyzing the mass of the liquid collected in 21 vertical pipes measuring 52 mm in internal diameter and 800 mm in length placed in a quadratic arrangement and positioned below the distributor A 50 mm thick acrylic blanket that does not disperse liquids was placed between the distributor and the pipe bank to avoid splashes. Assays were carried out with ladder-type distributors equipped with 4 parallel pipes each for a column measuring 400 nun in diameter as an example of the application. The number (n) of orifices (95, 127, and 159 orifices/m(2)), orifice diameter (d) (2, 3, and 4 mm) and the flowrate (q) (1.2; 1.4; and 1.6 m(3)/h) were varied. The best spread efficiency, which presented the lowest standard deviation, was achieved with 159 orifices, 2 mm and 1.4 m(3)/h. The pressure (p) at the distributor inlet for this condition was only 51000 Pa (0.51 kgf/cm(2)), while the average velocity (v) was 6.3 m/s in each orifice. These results show some limitations of the practical rules used in distributor designs.

Occurrence and behavior of butyltins in intertidal and shallow subtidal surface sediments of an estuarine beach under different sampling conditions

Contamination by butyltin compounds (BTs) has been reported in estuarine environments worldwide, with serious impacts on the biota of these areas. Considering that BTs can be degraded by varying environmental conditions such as incident light and salinity, the short-term variations in such factors may lead to inaccurate estimates of BTs concentrations in nature. Therefore, the present study aimed to evaluate the possibility that measurements of BTs in estuarine sediments are influenced by different sampling conditions, including period of the day (day or night), tidal zone (intertidal or subtidal), and tides (high or low). The study area is located on the Brazilian southeastern coast, Sao Vicente Estuary, at Pescadores Beach, where BT contamination was previously detected. Three replicate samples of surface sediment were collected randomly in each combination of period of the day, tidal zone, and tide condition, from three subareas along the beach, totaling 72 samples. BTs were analyzed by GC-PFPD using a tin filter and a VF-5 column, by means of a validated method. The concentrations of tributyltin (TBT), dibutyltin (DBT), and monobutyltin (MBT) ranged from undetectable to 161 ng Sn g(-1) (d.w.). In most samples (71%), only MBT was quantifiable, whereas TBTs were measured in only 14, suggesting either an old contamination or rapid degradation processes. DBT was found in 27 samples, but could be quantified in only one. MBT concentrations did not differ significantly with time of day, zones, or tide conditions. DBT and TBT could not be compared under all these environmental conditions, because only a few samples were above the quantification limit. Pooled samples of TBT did not reveal any difference between day and night. These results indicated that, in assessing contamination by butyltin compounds, surface-sediment samples can be collected in any environmental conditions. However, the wide variation of BTs concentrations in the study area, i.e., over a very small geographic scale, illustrates the need for representative hierarchical and composite sampling designs that are compatible with the multiscalar temporal and spatial variability common to most marine systems. The use of such sampling designs will be necessary for future attempts to quantitatively evaluate and monitor the occurrence and impact of these compounds in nature

Kinetic and Thermodynamic Studies on the Adsorption of Reactive Red 239 by Carra Sawdust Treated with Formaldehyde

In this study, carra sawdust pre-treated with formaldehyde was used to adsorb reactive red 239 (RR239). The effects of several experimental conditions, including the concentration of dye, sorbent dosage, temperature, ionic strength, stirring speed and solution pH, on the kinetics of the adsorption process have been studied, and the experimental data were fitted to pseudo-second-order model. A study of the intra-particle diffusion model indicates that the mechanism of dye adsorption using carra sawdust is rather complex and is most likely a combination of external mass transfer and intra-particle diffusion. The experimental data obtained at equilibrium were analyzed using the Langmuir and Freundlich isotherm models, and the results indicated that at this concentration range, both models can be applied for obtaining the equilibrium parameters. The maximum dye uptake obtained at 298 K was found to be 15.1 mg g(-1). In contrast to the usual systems, the reactive dye studied in the present work is strongly attached to the sawdust even after several washes with water, allowing it to be discarded as a solid waste.

DETERMINATION OF KINETIC AND THERMODYNAMIC PARAMETERS OF L-CYSTEINE ADSORPTION ONTO GOLD BY THE QCM TECHNIQUE

DETERMINATION OF KINETIC AND THERMODYNAMIC PARAMETERS OF L-CYSTEINE ADSORPTION ONTO GOLD BY THE QCM TECHNIQUE. This article discusses the adsorption kinetics of a L-cysteine monolayer onto a gold surface by means of information obtained through the QCM technique. The results indicate that the adsorption process is rapid and follows the Langmuir isotherm, in which adsorption and desorption are considered. From these measurements the following parameter values were obtained: k(d) = (4.2 +/- 0.4) x 10(-3) s(-1), k(a) = 75 +/- 6 M-1 s(-1), K-eq=(1.8 +/- 0.3) x 10(4) M-1 and Delta G(ads) = -(5.8 +/- 0.2) kcal mol(-1).

Adsorption of phosphate from aqueous solution by hydrous zirconium oxide

Synthetic ZrO2 center dot nH(2)O was used for phosphate removal from aqueous solution. The optimum adsorbent dose obtained for phosphate adsorption on to hydrous zirconium oxide was 0.1 g. The kinetic process was described very well by a pseudo-second-order rate model. The phosphate adsorption tended to increase with the decrease in pH. The adsorption capacity increased from 61 to 66 mg g(-1) when the temperature was increased from 298 to 338 K. A phosphate desorption of approximately 74% was obtained using water at pH 12.

Deslocamento miscível de um efluente de indústria de explosivo em colunas de solo

Este estudo teve como objetivo avaliar alguns impactos decorrentes do deslocamento miscível de efluente de nitração de uma indústria de explosivos aplicado em colunas de um Latossolo Amarelo, horizonte B (LA-B), submetido aos tratamentos: adição de carbonatos (BASE), ácidos (ACID), fosfato (FOSF), carbonatos e fosfato (BASE-FOSF) e ácidos e fosfatos (ACID-FOSF). A recuperação de nitrogênio em relação ao total aplicado varia entre 10,1 (ACID) e 65,5% (BASE). Há correlação significativa entre as curvas de transposição de N obtidas experimentalmente e as simuladas pelo aplicativo STANMOD para a maioria das colunas (p<0,001). A exceção ocorreu para ACID-FOSF (p=0,202). Não há correlação entre carga eletrostática líquida (CEL) e as variáveis de ajuste do modelo: fator de retardamento (FR), coeficiente de dispersão-difusão (D) e taxa de decaimento de primeira ordem m (µ). A adição de fosfato (FOSF) favorece a movimentação do nitrogênio, pois diminui FR (2,35±0,05) e µ (0,498±0,050 h-1) e aumenta D (41,8±5,5 cm2 h-1) em relação ao observado na coluna LA-B (2,51±0,03; 1,697±0,084 h-1e 2,8±1,3 cm2 h-1 respectivamente). A adição de carbonatos e/ou fosfatos (BASE, BASE/FOSF e FOSF) resultou nos maiores valores máximos de demanda química de oxigênio (DQOMÁX). A pequena quantidade de DNA extraída das células bacterianas nos solos sugere que, possivelmente, os processos que governam a adsorção e movimentação de N sejam de natureza não biológica ou que a elevada DQO do líquido percolado prejudica os microrganismos do solo.

Factors controlling water-column respiration in rivers of the central and southwestern Amazon Basin

We examined the factors controlling the variability in water-column respiration rates in Amazonian rivers. Our objectives were to determine the relationship between respiration rates and the in situ concentrations of the size classes of organic carbon (OC), and the biological source (C-3 and C-4 plants and phytoplankton) of organic matter (OM) supporting respiration. Respiration was measured along with OC size fractions and dissolved oxygen isotopes (delta O-18-O-2) in rivers of the central and southwestern Amazon Basin. Rates ranged from 0.034 mu mol O-2 L-1 h(-1) to 1.78 mu mol O-2 L-1 h(-1), and were four-fold higher in rivers with evidence of photosynthetic production (demonstrated by delta O-18-O-2<24.2 parts per thousand) as compared to rivers lacking such evidence (delta O-18-O-2>24.2 parts per thousand; 1.35 +/- 0.22 vs. 0.30 +/- 0.29 mu mol L-1 h(-1)). Rates were likely elevated in the former rivers, which were all sampled during low water, due to the stimulation of heterotrophic respiration via the supply of a labile, algal-derived substrate and/or the occurrence of autotrophic respiration. The organic composition of fine particulate OM (FPOM) of these rivers is consistent with a phytoplankton origin. Multiple linear regression analysis indicates that [FPOC], C:N-FPOC ratios, and [O-2] account for a high amount of the variability in respiration rates (r(2) = 0.80). Accordingly, FPOC derived from algal sources is associated with elevated respiration rates. The delta C-13 of respiration-derived CO2 indicates that the role of phytoplankton, C-3 plants, and C-4 grasses in supporting respiration is temporally and spatially variable. Future scaling work is needed to evaluate the significance of phytoplankton production to basin-wide carbon cycling.

Analysis of carvedilol enantiomers in human plasma using chiral stationary phase column and liquid chromatography with tandem mass spectrometry

Carvedilol is an antihypertensive drug available as a racemic mixture. (-)-(S)-carvedilol is responsible for the nonselective beta-blocker activity but both enantiomers present similar activity on a1-adrenergic receptor. To our knowledge, this is the first study of carvedilol enantiomers in human plasma using a chiral stationary phase column and liquid chromatography with tandem mass spectrometry. The method involves plasma extraction with diisopropyl ether using metoprolol as internal standard and direct separation of the carvedilol enantiomers on a Chirobiotic T (R) (Teicoplanin) column. Protonated ions [M + H]+ and their respective ion products were monitored at transitions of 407 > 100 for the carvedilol enantiomers and 268 > 116 for the internal standard. The quantification limit was 0.2 ng ml-1 for both enantiomers in plasma. The method was applied to study enantioselectivity in the pharmacokinetics of carvedilol administered as a single dose of 25 mg to a hypertensive patient. The results showed a higher plasma concentration of (+)-(R)-carvedilol (AUC08 205.52 vs. 82.61 (ng h) ml-1), with an enantiomer ratio of 2.48. Chirality, 2012. (C) 2012 Wiley Periodicals, Inc.

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.

Thermal design of a tray-type distillation column of an ammonia/water absorption refrigeration cycle

The goal of this paper is to present an analysis of a segmented weir sieve-tray distillation column for a 17.58 kW (5 TR) ammonia/water absorption refrigeration cycle. Balances of mass and energy were performed based on the method of Ponchon-Savarit, from which it was possible to determine the ideal number of trays. The analysis showed that four ideal trays were adequate for that small absorption refrigeration system having the feeding system to the column right above the second tray. It was carried out a sensitivity analysis of the main parameters. Vapor and liquid pressure drop constraint along with ammonia and water mass flow ratios defined the internal geometrical sizes of the column, such as the column diameter and height, as well as other designing parameters. Due to the lack of specific correlations, the present work was based on practical correlations used in the petrochemical and beverage production industries. The analysis also permitted to obtain the recommended values of tray spacing in order to have a compact column. The geometry of the tray turns out to be sensitive to the charge of vapor and, to a lesser extent, to the load of the liquid, being insensible to the diameter of tray holes. It was found a column efficiency of 50%. Finally, the paper presents some recommendations in order to have an optimal geometry for a compact size distillation column. (c) 2011 Elsevier Ltd. All rights reserved.

Adsorption of NO on the Rh-13, Pd-13, Ir-13, and Pt-13 Clusters: A Density Functional Theory Investigation

The adsorption of NO on transition-metal (TM) surfaces has been widely studied by experimental and theoretical techniques; however, our atomistic understanding of the interaction of nitrogen monoxide (NO) with small TM clusters is far from satisfactory, which compromises a deep understanding of real catalyst devices. In this study, we report a density functional theory study of the adsorption properties of NO on the TM13 (TM = Rh, Pd, Ir, Pt) clusters employing the projected augmented wave method. We found that the interaction of NO with TM13 is much more complex than that for NO/TM(111). In particular, for low symmetry TM13 clusters, there is a strong rearrangement of the electronic charge density upon NO adsorption and, as a consequence, the adsorption energy shows a very complex dependence even for adsorption sites with the same local effective coordination. We found a strong enhancement of the binding energy of NO to the TM13 clusters compared with the TM(111) surfaces, as the antibonding NO states are not occupied for NO/TM13, and the general relationship based on the d-band model between adsorption energy and the center of gravity of the occupied d-states does not hold for the studied TM13 clusters, in particular, for clusters with low symmetry. In contrast with the adsorption energy trends, the geometric NO/TM13 parameters and the vibrational N-O frequencies for different coordination sites follow the same trend as for the respective TM(111) surfaces, while the changes in the frequencies between different surfaces and TM13 clusters reflect the strong NO-TM13 interaction.

Sulfur Radicals as Tethers for the Adsorption of Aromatic Molecules on Silicon Surface

In this work we employ the state of the art pseudopotential method, within a generalized gradient approximation to the density functional theory, to investigate the adsorption process of benzenethiol and diphenyl disulfide with the silicon (001) surface. A direct comparison of different adsorption structures with Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS) allow us to identify that benzenethiol and diphenyl disulfide dissociatively adsorb on the silicon surface. In addition, theoretically obtained data suggests that the C6H5SH:Si(001) presents a higher Schottky barrier height contact when compared to other similar aromatic molecules.

Synthesis of high-surface-area gamma-Al2O3 from aluminum scrap and its use for the adsorption of metals: Pb(II), Cd(II) and Zn(II)

Several types of alumina were synthesized from sodium aluminate (NaAlO2) by precipitation with sulfuric acid (H2SO4) and subsequently calcination at 500 degrees C to obtain gamma-Al2O3. The precursor aluminate was derived from aluminum scrap. The various gamma-Al2O3 synthesized were characterized by Fourier-transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), adsorption-desorption of N-2 (S-BET) and scanning electron microscopy (SEM). XRD revealed that distinct phases of Al2O3 were formed during thermal treatment. Moreover, it was observed that conditions of synthesis (pH, aging time and temperature) strongly affect the physicochemical properties of the alumina. A high-surface-area alumina (371 m(2) g(-1)) was synthesized under mild conditions, from inexpensive raw materials. These aluminas were tested for the adsorption of Cd(II), Zn(II) and Pb(II) from aqueous solution at toxic metal concentrations, and isotherms were determined. (C) 2012 Elsevier B.V. All rights reserved.

Application of Polysaccharide Hydrogels in Adsorption and Controlled-Extended Release of Fertilizers Processes

This article studied the applicability of poly(acrylamide) and methylcellulose (PAAm-MC) hydrogels as potential delivery vehicle for the controlled-extended release of ammonium sulfate (NH(4))(2)SO(4) and potassium phosphate (KH(2)PO(4)) fertilizers. PAAm-MC hydrogels with different acrylamide (AAm) and MC concentrations were prepared by a free radical polymerization method. The adsorption and desorption kinetics of fertilizers were determined using conductivity measurements based on previously built analytical curve. The addition of MC in the PAAm chains increased the quantities of (NH(4))(2)SO(4) and KH(2)PO(4) loaded and extended the time and quantities of fertilizers released. Coherently, both loading and releasing processes were strongly influenced by hydrophilic properties of hydrogels (AAm/MC mass proportion). The best sorption (124.0 mg KH(2)PO(4)/g hydrogel and 58.0 mg (NH(4))(2)SO(4)/g hydrogel) and desorption (54.9 mg KH(2)PO(4)/g hydrogel and 49.5 mg (NH(4))(2)SO(4)/g hydrogel) properties were observed for 6.0% AAm-1.0% MC hydrogels (AAm/MC mass proportion equal 6), indicating that these hydrogels are potentially viable to be used in controlled-extended release of fertilizers systems. (C) 2011 Wiley Periodicals, Inc. J Appl Polym Sci 123: 2291-2298, 2012

Adsorption of Sodium Dodecyl Sulfate on Ge Substrate: The Effect of a Low-Polarity Solvent

This paper describes the adsorption of sodium dodecyl sulfate (SDS) molecules in a low polar solvent on Ge substrate by using Fourier transform infrared-attenuated total reflection (FTIR-ATR) spectroscopy and atomic force microscopy (AFM). The maximum SDS amount adsorbed is (5.0 +/- 0.3) x 10(14) molecules cm(-2) in CHCl3, while with the use of CCl4 as subphase the ability of SDS adsorbed is 48% lower. AFM images show that depositions are highly disordered over the interface, and it was possible to establish that the size of the SDS deposition is around 30-40 nm over the Ge surface. A complete description of the infrared spectroscopic bands for the head and tail groups in the SDS molecule is also provided.