Evaluation of grinding methods for pellets preparation aiming at the analysis of plant materials by laser induced breakdown spectrometry

It has been demonstrated that laser induced breakdown spectrometry (LIBS) can be used as an alternative method for the determination of macro (P, K. Ca, Mg) and micronutrients (B, Fe, Cu, Mn, Zn) in pellets of plant materials. However, information is required regarding the sample preparation for plant analysis by LIBS. In this work, methods involving cryogenic grinding and planetary ball milling were evaluated for leaves comminution before pellets preparation. The particle sizes were associated to chemical sample properties such as fiber and cellulose contents, as well as to pellets porosity and density. The pellets were ablated at 30 different sites by applying 25 laser pulses per site (Nd:YAG@1064 nm, 5 ns, 10 Hz, 25J cm(-2)). The plasma emission collected by lenses was directed through an optical fiber towards a high resolution echelle spectrometer equipped with an ICCD. Delay time and integration time gate were fixed at 2.0 and 4.5 mu s, respectively. Experiments carried out with pellets of sugarcane, orange tree and soy leaves showed a significant effect of the plant species for choosing the most appropriate grinding conditions. By using ball milling with agate materials, 20 min grinding for orange tree and soy, and 60 min for sugarcane leaves led to particle size distributions generally lower than 75 mu m. Cryogenic grinding yielded similar particle size distributions after 10 min for orange tree, 20 min for soy and 30 min for sugarcane leaves. There was up to 50% emission signal enhancement on LIBS measurements for most elements by improving particle size distribution and consequently the pellet porosity. (C) 2011 Elsevier B.V. All rights reserved.

Comparison of univariate and multivariate calibration for the determination of micronutrients in pellets of plant materials by laser induced breakdown spectrometry

The application of laser induced breakdown spectrometry (LIBS) aiming the direct analysis of plant materials is a great challenge that still needs efforts for its development and validation. In this way, a series of experimental approaches has been carried out in order to show that LIBS can be used as an alternative method to wet acid digestions based methods for analysis of agricultural and environmental samples. The large amount of information provided by LIBS spectra for these complex samples increases the difficulties for selecting the most appropriated wavelengths for each analyte. Some applications have suggested that improvements in both accuracy and precision can be achieved by the application of multivariate calibration in LIBS data when compared to the univariate regression developed with line emission intensities. In the present work, the performance of univariate and multivariate calibration, based on partial least squares regression (PLSR), was compared for analysis of pellets of plant materials made from an appropriate mixture of cryogenically ground samples with cellulose as the binding agent. The development of a specific PLSR model for each analyte and the selection of spectral regions containing only lines of the analyte of interest were the best conditions for the analysis. In this particular application, these models showed a similar performance. but PLSR seemed to be more robust due to a lower occurrence of outliers in comparison to the univariate method. Data suggests that efforts dealing with sample presentation and fitness of standards for LIBS analysis must be done in order to fulfill the boundary conditions for matrix independent development and validation. (C) 2009 Elsevier B.V. All rights reserved.

Simultaneous optimization by neuro-genetic approach for analysis of plant materials by laser induced breakdown spectroscopy

A simultaneous optimization strategy based on a neuro-genetic approach is proposed for selection of laser induced breakdown spectroscopy operational conditions for the simultaneous determination of macronutrients (Ca, Mg and P), micro-nutrients (B, Cu, Fe, Mn and Zn), Al and Si in plant samples. A laser induced breakdown spectroscopy system equipped with a 10 Hz Q-switched Nd:YAG laser (12 ns, 532 nm, 140 mJ) and an Echelle spectrometer with intensified coupled-charge device was used. Integration time gate, delay time, amplification gain and number of pulses were optimized. Pellets of spinach leaves (NIST 1570a) were employed as laboratory samples. In order to find a model that could correlate laser induced breakdown spectroscopy operational conditions with compromised high peak areas of all elements simultaneously, a Bayesian Regularized Artificial Neural Network approach was employed. Subsequently, a genetic algorithm was applied to find optimal conditions for the neural network model, in an approach called neuro-genetic, A single laser induced breakdown spectroscopy working condition that maximizes peak areas of all elements simultaneously, was obtained with the following optimized parameters: 9.0 mu s integration time gate, 1.1 mu s delay time, 225 (a.u.) amplification gain and 30 accumulated laser pulses. The proposed approach is a useful and a suitable tool for the optimization process of such a complex analytical problem. (C) 2009 Elsevier B.V. All rights reserved.

Evaluation of laser induced breakdown spectroscopy for the determination of micronutrients in plant materials

Laser induced breakdown spectroscopy (LIBS) has been evaluated for the determination of micronutrients (B, Cu, Fe, Mn and Zn) in pellets of plant materials, using NIST, BCR and GBW biological certified reference materials for analytical calibration. Pellets of approximately 2 mm thick and 15 mm diameter were prepared by transferring 0.5 g of powdered material to a 15 mm die set and applying 8.0 tons cm(-2). An experimental setup was designed by using a Nd:YAG laser operating at 1064 nm (200 mJ per pulse, 10 Hz) and an Echelle spectrometer with ICCD detector. Repeatability precision varied from 4 to 30% from measurements obtained in 10 different positions (8 laser shots per test portion) in the same sample pellet. Limits of detection were appropriate for routine analysis of plant materials and were 2.2 mg kg(-1) B, 3.0 mg kg(-1) Cu, 3.6 mg kg(-1) Fe, 1.8 mg kg(-1) Mn and 1.2 mg kg(-1) Zn. Analysis of different plant samples were carried out by LIBS and results were compared with those obtained by ICP OES after wet acid decomposition. (C) 2009 Elsevier B.V. All rights reserved.

Evaluation of laser induced breakdown spectroscopy for the determination of macronutrients in plant materials

Laser induced breakdown spectroscopy (LIBS) has become an analytical tool for the direct analysis of a large variety of materials in order to provide qualitative and/or quantitative information. However, there is a lack of information for LIBS analysis of agricultural and environmental samples. In this work a LIBS system has been evaluated for the determination of macronutrients (P, K, Ca, Mg) in pellets of vegetal reference materials. An experimental setup was designed by using a Nd:YAG laser operating at 1064 nm and an Echelle spectrometer with ICCD detector. The plasma temperature was estimated by Boltzmann plots and instrumental paragmeters such as delay time, lens-to-sample distance and pulse energy were evaluated. Certified reference materials as well as reference materials were used for analytical calibrations of P, K, Ca, and Mg. Most results of the direct analysis of plant samples by LIBS were in reasonable agreement with those obtained by ICP OES after wet acid decomposition. (C) 2008 Elsevier B.V. All rights reserved.

Interesterification of milkfat with soybean oil catalysed by Rhizopus oryzae lipase immobilised on SiO(2)-PVA on packed bed reactor

The potential of the lipase from Rhizopus oryzae immobilised on SiO(2)-PVA to catalyse the interesterification of the milkfat with soybean oil in a packed bed reactor running on continuous mode was evaluated. The reactor operated continuously for 35 days at 45 degrees C, and during 12 days, no significant decrease in the initial lipase activity was verified. Interesterification yields were in the range from 35 to 38% wt, which gave an interesterified product having 59% lower consistency in relation to non-interesterified blend. Results showed the potential of the lipase from Rhizopus oryzae to mediate the interesterification of milkfat with soybean oil in packed bed reactor, attaining a more spreadable product under a cool temperature. The biocatalyst operational stability was assessed and an inactivation profile was found to follow the Arrhenius model, revealing values of 34 days and 0.034 day(-1), for half-life and a deactivation coefficient, respectively.

The effect of agitation speed, enzyme loading and substrate concentration on enzymatic hydrolysis of cellulose from brewer`s spent grain

Brewer`s spent grain components (cellulose, hemicellulose and lignin) were fractionated in a two-step chemical pretreatment process using dilute sulfuric acid and sodium hydroxide solutions. The cellulose pulp produced was hydrolyzed with a cellulolytic complex, Celluclast 1.5 L, at 45 degrees C to convert the cellulose into glucose. Several conditions were examined: agitation speed (100, 150 and 200 rpm), enzyme loading (5, 25 and 45 FPU/g substrate), and substrate concentration (2, 5 and 8% w/v), according to a 2(3) full factorial design aiming to maximize the glucose yield. The obtained results were interpreted by analysis of variance and response surface methodology. The optimal conditions for enzymatic hydrolysis of brewer`s spent grain were identified as 100 rpm, 45 FPU/g and 2% w/v substrate. Under these conditions, a glucose yield of 93.1% and a cellulose conversion (into glucose and cellobiose) of 99.4% was achieved. The easiness of glucose release from BSG makes this substrate a raw material with great potential to be used in bioconversion processes.

Evaluation of hydrodynamic parameters of a fluidized-bed reactor with immobilized yeast

The fluidized bed reactor has successfully been used to perform biotechnological processes addressed to the production of high added value. The present work evaluates hydrodynamic parameters of a bench-scale fluidized bed reactor with cells of the yeast Candida guilliermondii immobilized either in calcium alginate beads or in polyvinyl alcohol (PVA). The effects of the following variables on cell immobilization were evaluated at 30 degrees C and feeding a synthetic medium containing 50 g L-1 xylose: total particle density (cells plus support), terminal velocity, particle drag force, minimum fluidization velocity and bed porosity. According to the results obtained, the reactor was shown to operate like a fixed-bed bioreactor at xi < 0.5 and a fluidized bed bioreactor at xi > 0.5. The maximum flow rate needed to obtain maximum bed fluidization in the reactor was equal to the terminal velocity of the immobilized cell particles. Particles of cells immobilized within these supports showed values of drag coefficient lower than those reported for other high-density supports. The evaluation of these hydrodynamic characteristics lead to an adequate bed fluidization inside the reactor, thus improving oxygen transference and availability in the fermentation medium, making the process more viable for future scale-up. (c) 2008 Society of Chemical Industry.

Composite materials obtained from textile fiber residue

This article presents the use of fibers residue from textile industry to minimize environmental problems associated with material accumulation. Composite materials utilizing textile fiber residues and high density polyethylene were prepared. Effect of treatment with hot water on fibers to prepare composites was studied to provide an improvement in mechanical properties of these materials. This treatment on fibers was evaluated by X-ray diffraction and scanning electron microscopy techniques. Experimental results of mechanical properties indicated higher mechanical strength for treated fiber composites compared to the untreated fiber composites.

Packed-Bed Reactor Running on Babassu Oil and Glycerol to Produce Monoglycerides by Enzymatic Route using Immobilized Burkholderia cepacia Lipase

The aim of this study was the glycerolysis of babassu oil catalyzed by immobilized lipase from Burkholderia cepacia, in a continuous packed-bed reactor. The best reaction conditions were previously established in batchwise via response surface methodology as a function of glycerol-to-oil molar ratio and reaction temperature. The reactor operated continuously for 22 days at 50 A degrees C, and during the first 6 days, no significant decrease on the initial lipase activity was observed. Monoglycerides concentration was in the range from 25 to 33 wt.%. Subsequently, a progressive decrease in the activity was detected, and an inactivation profile described by Arrhenius model estimated values of 50 days and 1.37 x 10(-2) h(-1), for the half-life and deactivation coefficient, respectively.

Experimental analysis of active-passive vibration control using viscoelastic materials and extension and shear piezoelectric actuators

Hybrid active-passive damping treatments combine the reliability, low cost and robustness of viscoelastic damping treatments and the high-performance, modal selective and adaptive piezoelectric active control. Numerous hybrid damping treatments have been reported in the literature. They differ mainly by the relative positions of viscoelastic treatments, sensors and piezoelectric actuators. In this work we present an experimental analysis of three active-passive damping design configurations applied to a cantilever beam. In particular, two design configurations based on the extension mode of piezoelectric actuators combined with viscoelastic constrained layer damping treatments and one design configuration with shear piezoelectric actuators embedded in a sandwich beam with viscoelastic core are analyzed. For comparison purposes, a purely active design configuration with an extension piezoelectric actuator bonded to an elastic beam is also analyzed. The active-passive damping performance of the four design configurations is compared. Results show that active-passive design configurations provide more reliable and wider-range damping performance than the purely active configuration.

Non-linear boundary element formulation with tangent operator to analyse crack propagation in quasi-brittle materials

This work deals with analysis of cracked structures using BEM. Two formulations to analyse the crack growth process in quasi-brittle materials are discussed. They are based on the dual formulation of BEM where two different integral equations are employed along the opposite sides of the crack surface. The first presented formulation uses the concept of constant operator, in which the corrections of the nonlinear process are made only by applying appropriate tractions along the crack surfaces. The second presented BEM formulation to analyse crack growth problems is an implicit technique based on the use of a consistent tangent operator. This formulation is accurate, stable and always requires much less iterations to reach the equilibrium within a given load increment in comparison with the classical approach. Comparison examples of classical problem of crack growth are shown to illustrate the performance of the two formulations. (C) 2009 Elsevier Ltd. All rights reserved.

Analytical formulae for electromechanical effective properties of 3-1 longitudinally porous piezoelectric materials

A unidirectional fiber composite is considered here, the fibers of which are empty cylindrical holes periodically distributed in a transversely isotropic piezoelectric matrix, The empty-fiber cross-section is circular and the periodicity is the same in two directions at an angle pi/2 or pi/3. Closed-form formulae for all electromechanical effective properties of these 3-1 longitudinally periodic porous piezoelectric materials are presented. The derivation of such expressions is based on the asymptotic homogenization method as a limit of the effective properties of two-phase transversely isotropic parallel fiber-reinforced composites when the fibers properties tend to zero. The plane effective coefficients satisfy the corresponding Schulgasser-Benveniste-Dvorak universal type of relations, A new relation among the antiplane effective constants from the solutions of two antiplane strains and potential local problems is found. This relation is valid for arbitrary shapes of the empty-fiber cross-sections. Based on such a relation, and using recent numerical results for isotropic conductive composites, the antiplane effective properties are computed for different geometrical shapes of the empty-fiber cross-section. Comparisons with other analytical and numerical theories are presented. (c) 2008 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Sorption aspects for unconsolidated materials of the Sao Carlos region (SP), Brazil

The transport of liquid and gaseous pollutants through porous geological media depends on the physical and chemical characteristics of the unconsolidated material, rocks and water associated with the characteristics of the pollutants. Of these characteristics, the sorption aspect is of fundamental importance and is a function of the mineral proportions, pH, Eh and void aspects encountered in the porous media. In the Sao Carlos region, located in the eastern-central part of the 9 ate of Sao Paulo, Brazil, there are basically two types of unconsolidated materials: the first is a residual from sandstones cemented with fines and the secondarily composed of claystones, siltstones and conglomerates from the Cretaceous Period that constitute the Itaqueri Formation; the second is a sandy sediment of the Tertiary Period. These geological conditions are found in areas where chemical products are disposed of characterized as either diffuse or point pollutions sources. Because of this situation, a study was developed to evaluate the sorption aspects of some inorganic cations that are frequently found in these sources, in varied concentrations. Taken into consideration were their physical/chemical properties, such as: specific weight, grain size, mineralogy, cationic exchange capacity, pH, hydraulic conductivity. Batch tests were run using solutions of KCl, ZnCl(2) and CuCl center dot H(2)O at three different pH values, and then with a combined solution (KCl + ZnCl(2) + CuCl center dot H(2)O), also at three different pH values.

Full-scale anaerobic sequencing batch biofilm reactor for sulfate-rich wastewater treatment

This paper describes the performance and biofilm characteristics of a full-scale anaerobic sequencing batch biofilm reactor (ASBBR; 20 m(3)) containing biomass immobilized on an inert support (mineral coal) for the treatment of industrial wastewater containing a high sulfate concentration. The ASBBR reactor was operated during 110 cycles (48 h each) at sulfate loading rates ranging from 6.9 to 62.4 kgSO(4)(2-)/cycle corresponding to sulfate concentrations of 0.58-5.2 gSO(4)(2-)/L. Domestic sewage and ethanol were utilized as electron donors for sulfate reduction. After 71 cycles the mean sulfate removal efficiency was 99%, demonstrating a high potential for biological sulfate reduction. The biofilm formed in the reactor occurred in two different patterns, one at the beginning of the colonization and the other of a mature biofilm. These different colonization patterns are due to the low adhesion of the microorganisms on the inert support in the start-up period. The biofilm population is mainly made up of syntrophic consortia among sulfate-reducing bacteria and methanogenic archaea such as Methanosaeta spp.