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.

Total carbon measurement in whole tropical soil sample

Soils are an important component in the biogeochemical cycle of carbon, storing about four times more carbon than biomass plants and nearly three times more than the atmosphere. Moreover, the carbon content is directly related on the capacity of water retention, fertility. among other properties. Thus, soil carbon quantification in field conditions is an important challenge related to carbon cycle and global climatic changes. Nowadays. Laser Induced Breakdown Spectroscopy (LIBS) can be used for qualitative elemental analyses without previous treatment of samples and the results are obtained quickly. New optical technologies made possible the portable LIBS systems and now, the great expectation is the development of methods that make possible quantitative measurements with LIBS. The goal of this work is to calibrate a portable LIBS system to carry out quantitative measures of carbon in whole tropical soil sample. For this, six samples from the Brazilian Cerrado region (Argisoil) were used. Tropical soils have large amounts of iron in their compositions, so the carbon line at 247.86 nm presents strong interference of this element (iron lines at 247.86 and 247.95). For this reason, in this work the carbon line at 193.03 nm was used. Using methods of statistical analysis as a simple linear regression, multivariate linear regression and cross-validation were possible to obtain correlation coefficients higher than 0.91. These results show the great potential of using portable LIBS systems for quantitative carbon measurements in tropical soils. (C) 2008 Elsevier B.V. All rights reserved.

Soil nitrous oxide emissions in long-term cover crops-based rotations under subtropical climate

It has been shown that cover crops can enhance soil nitrous oxide (N(2)O) emissions, but the magnitude of increase depends on the quantity and quality of the crop residues. Therefore, this study aimed to evaluate the effect of long-term (19 and 21 years) no-till maize crop rotations including grass [black oat (Avena strigosa Schreb)] and legume cover crops [vetch (Vigna sativa L), cowpea (Vigna unguiculata L. Walp), pigeon pea (Cajanus cajan L. Millsp.) and lablab (Dolichos lablab)] on annual soil N(2)O emissions in a subtropical Acrisol in Southern Brazil. Greater soil N(2)O emissions were observed in the first 45 days after the cover crop residue management in all crop rotations, varying from -20.2 +/- 1.9 to 163.9 +/- 24.3 mu g N m(-2) h(-1). Legume-based crop rotations had the largest cumulative emissions in this period, which were directly related to the quantity of N (r(2) = 0.60, p = 0.13)and inversely related to the lignin:N ratio(r(2) = 0.89,p = 0.01) of the cover crop residues. After this period, the mean fluxes were smaller and were closely related to the total soil N stocks (r(2) = 0.96, p = 0.002). The annual soil N(2)O emission represented 0.39-0.75% of the total N added by the legume cover crops. Management-control led soil variables such as mineral N (NO(3)(-) and NH(4)(+)) and dissolved organic C influenced more the N(2)O fluxes than environmental-related variables as water-filled pore space and air and soil temperature. Consequently, the synchronization between N mineralization and N uptake by plants seems to be the main challenge to reduce N(2)O emissions while maintaining the environmental and agronomic services provided by legume cover crops in agricultural systems. (C) 2009 Elsevier B.V. All rights reserved.

Partial microwave-assisted wet digestion of animal tissue using a baby-bottle sterilizer for analyte determination by inductively coupled plasma optical emission spectrometry

A procedure for partial digestion of bovine tissue is proposed using polytetrafluoroethylene (PTFE) microvessels inside a baby-bottle sterilizer under microwave radiation for multi-element determination by inductively coupled plasma optical emission spectrometry (ICP OES). Samples were directly weighed in laboratory-made polytetrafluoroethylene vessels. Nitric acid and hydrogen peroxide were added to the uncovered vessels, which were positioned inside the baby-bottle sterilizer, containing 500 mL of water. The hydrogen peroxide volume was fixed at 100 mu L The system was placed in a domestic microwave oven and partial digestion was carried out for the determination of Ca, Cu, Fe. Mg, Mn and Zn by inductively coupled plasma optical emission spectrometry. The single-vessel approach was used in the entire procedure, to minimize contamination in trace analysis. Better recoveries and lower residual carbon content (RCC) levels were obtained under the conditions established through a 2(4-1) fractional factorial design: 650 W microwave power, 7 min digestion time, 50 mu L nitric acid and 50 mg sample mass. The digestion efficiency was ascertained according to the residual carbon content determined by inductively coupled plasma optical emission spectrometry. The accuracy of the proposed procedure was checked against two certified reference materials. (C) 2009 Elsevier B.V. All rights reserved.

Contribuition of nitrogen from biological nitrogen fixation, nitrogen fertilizer and soil nitrogen on the growth of the common bean and cowpea

Biological nitrogen fixation (BNF) constitutes a valuable source of this nutrient for the common bean Phaseolus vulgaris L and cowpea Vigna unguiculata (L.) Walp., being its avaibility affected by mineral N in the soil solution. The objectives of this work were to evaluate the effects of nitrogen rate, as urea, on symbiotic fixation of N(2) in common bean and cowpea plants, using the isotopic technique, and quantifying the relative contributions of N sources symbiotic N(2) fixation, soil native nitrogen and urea N on the growth of the common bean and cowpea. Non nodulating soybean plants were used as standard. The research was carried out in greenhouse, using pots with 5 kg of soil from a Typic Haplustox (Dystrophic Red Yellow Latosol). The experimental design was completely randomized blocks, with 30 treatments and three replications, arranged in 5x3x2 factorial outline. The treatments consisted of five N rates: 2, 15, 30, 45 and 60 mg N kg(-1) soil; three sampling times: 23, 40 and 76 days after sowing (DAS) and two crops: common bean and cowpea. The BNF decreased with increase N rates, varying from 81.5% to 55.6% for cowpea, and from 71.9% to 55.1% for common bean. The symbiotic N(2) fixation in cowpea can substitute totally the nitrogen fertilization. The nitrogen absorption from soil is not affected by nitrogen fertilizer rate. The N recovery from fertilizer at 76 DAS was of 60.7% by common bean, and 57.1% by cowpea. The symbiotic association in common bean needs the application of a starting dose (40 kg N ha(-1)) for economically acceptable yields.

Macronutrients in Marandu Palisade Grass as Influenced by Lime, Slag, and Nitrogen Fertilization

Soil acidity is one of the main limiting factors for the growth of pasture grasses in Brazilian soils. In addition to lime, slag can be used to correct soil acidity and help plants to absorb nutrients in adequate amounts. The objective of this experiment was to evaluate, under greenhouse conditions, the effects of slag and lime plus nitrogen (N) on marandu palisade grass plants` nutritional status as well as the absorption of macronutrients submitted to two cuts. The treatments consisted of two corrective materials (slag and lime), three corrective material rates (0.81, 1.61, and 3.22 g dm-3 of ECaCO3), three N rates (75, 150, and 300 mg dm-3) plus a control treatment, with four replications. Macronutrient contents in the forage plants were found to be present in adequate levels. The mean value of N accumulated in the shoot was 40.1 mg per plant, phosphorus (P) was 4.6 mg per plant, potassium (K) was 38.6 mg per plant, calcium (Ca) was 7.3 mg per plant, magnesium (Mg) was 6.7 mg per plant, and sulfur (S) was 3.5 mg per plant at the first cut. At the second cut, the nutrient accumulations values were N 50.8 mg per plant, P 6.3 mg per plant, K 20.7 mg per plant, Ca 21.6 mg per plant, Mg 24.0 mg per plant, and S 4.7 mg per plant. Macronutrients accumulation in the shoot of grass increased with the addition of both the correctives as well as the N rates.

Barium uptake by maize plants as affected by sewage sludge in a long-term field study

Along-term experiment was carried out under field conditions in Jaboticabal, SP, Brazil, with the objective of evaluating the concentration of Ba in soil and in maize plants grown in a soil treated with sewage sludge for nine consecutive years. During 2005/2006, maize was used as test plants and the experimental design was in randomized complete blocks with four treatments and five replicates. Treatments consisted of: 0.0, 45.0, 90.0 and 127.5 t ha(-1) sewage sludge (dry basis). Sewage sludge application increased soil Ba concentration. Barium accumulated in the parts of maize plants were generally affected by the successive applications of sewage sludge to the soil. However, the concentration of Ba in maize grain did not exceed the critical levels of Ba for human consumption. Sewage sludge applied to soil for a long time did not affect dry matter and grain production, nevertheless had the similar effect of mineral fertilization. Published by Elsevier B.V.

Characterization and greenhouse evaluation of Brazilian calcined nonapatite phosphate rocks for rice

Little information is available on the agronomic effectiveness of calcined nonapatite phosphate rock (PR) sources containing crandallite minerals in the form of Ca-Fe-Al-P for flooded and upland rice (Oryza sativa L.). We conducted laboratory and greenhouse studies to (i) characterize the mineralogical composition, (ii) investigate the solubility and dissolution behavior, and (iii) evaluate the agronomic effectiveness of two nonapatite PR sources (Juquia and Sapucaia) from Brazil and compared them with (i) a highly reactive Gafsa PR (Tunisia) containing apatite in the form of Ca-P and (ii) a reference water-soluble triple superphosphate (TSP) for flooded and upland rice. After calcination at 500 degrees C for 4 h, the solubility of Juquia PR and Sapucaia PR in neutral ammonium citrate (NAC) significantly increased from almost nil to a maximum of 39.3 and 114 g P kg(-1), respectively. X-ray diffraction showed that crystalline crandallite mineral was transformed to an amophorus form after calcination. The solubility behavior of the two calcined PR sources followed the same trend as Gafsa PR, that is, P release decreased with increasing equilibrium pH in the 0.01 M KCl solution (PH 3.0-8.0). At PH 3, the solubility followed: Gafsa PR > calcined Sapucaia PR > calcined Juquia PR. No P release was detected from any of the PR sources at pH >= 5.0 in the solution, indicating the Ca-P characteristic of the Ca-Fe-Al-P mineral controlled P dissolution of the calcined PR. Without calcination, both Juquia PR and Sapucaia PR were totally ineffective for upland rice grown on a Hiwassee clay loam (fine, kaolinitic, thermic Rhodic Kanhapludult) with pH 5.4 whereas a significant P response was observed with the calcined PR samples. For flooded rice grown on Hiwassee soil, the calcined Juquia PR and Sapucaia PR were 66 and 72%, respectively, as effective as TSP in increasing rice grain yield whereas Gafsa PR was ineffective. For upland rice grown on the unlimed soil, Gafsa PR was as effective as TSP in increasing rice grain yield whereas calcined Juquia PR and Sapucaia PR were 89 and 83% of TSP. The effectiveness of Gafsa PR was reduced to 0% after the soil was limed to pH 7.0 whereas the two calcined PR sources were reduced to 49% of TSP. Soil available P extracted by iron oxide impregnated filter paper (Pi test) or anion-exchange resin after rice harvest correlated well with P uptake by rice grain for flooded and upland rice.

Agronomic evaluation of calcined crandallite from three Brazilian phosphate deposits

Samples from the weathering mantle containing crandallite of three Brazilian phosphate deposits, Tapira, Catalo, and Juqui, were characterized, calcined, and agronomically evaluated. The calcination process increased total phosphorus (P) and neutral ammonium citrate soluble (NAC) P contents of all samples. The NAC solubility of original Tapira, Catalo, and Juqui was about 5% of total P, whereas for calcined samples it was 54, 16, and 53%, respectively. In a greenhouse study, rates of P were applied at 0, 10, 20, 40, 80, and 120mg P kg(-1) from the calcined materials and MCP (monocalcium phosphate) to an Ultisol cropped with upland and flooded rice for 65 days. The results showed that the calcined P samples increased dry-matter yield and P uptake with increasing rates of P applied for both crops. Tapira and Juqui were more effective for flooded than for upland rice. The calculated values of relative agronomic effectiveness of Tapira, Catalo, and Juqui with respect to MCP were 57, 48, and 53% in dry-matter yield for upland rice and 64, 50, and 69% for flooded rice, respectively.

Deep weathering and landscape evolution in a tropical plateau

The thick weathering profiles of humid tropical areas are an important, yet generally neglected, source of information on landscape evolution. Six complete profiles of the weathering mantle were sampled by drilling on the three stepped levels of the Campos do Jordao Plateau, on the NW flank of the Continental Rift of Southeastern Brazil. Mineralogical and micromorphological analyses of drill core samples, complemented by geochemical interpretations and by previous data on the upper saprolite, indicate continuity of a general lateritic trend during the entire process of mantle formation. Lateritization phases of different intensity were defined and considered to reflect adjustment to changes in environmental conditions created by the gradual uplift of the plateau to its present position. Older and more superficial materials related to intense lateritic weathering are characterized by allitization with direct formation of gibbsite from silicates, probably related to tropical climates existing immediately before the formation of the continental rift, during the Paleogene, and also before any significant increase in altitude. Monosialitization phase with general kaolinitization and restricted indirect formation of gibbsite from silicates could be associated to less aggressive climates that followed the Neogene (Miocene?) accentuation of uplift rates along the continental rift. The changes produced by uplift in the tropical climate eventually favored the development of a podzolization trend in soils above 1800m. (C) 2011 Elsevier BM. All rights reserved.

A study on chemical constituents and sugars extraction from spent coffee grounds

Spent coffee grounds (SCG) the residual materials obtained during the processing of raw coffee powder to prepare instant coffee are the main coffee Industry residues In the present work this material was chemically characterized and subsequently submitted to a dilute acid hydrolysis aiming to recover the hemicellulose sugars Reactions were performed according to experimental designs to verify the effects of the variables H(2)SO(4) concentration liquid-to-solid ratio temperature and reaction time on the efficiency of hydrolysis SCG was found to be rich in sugars (45 3% w/w) among of which hemicellulose (constituted by mannose galactose and arabinose) and cellulose (glucose homopolymer) correspond to 367% (w/w) and 8 6% (w/w) respectively Optimal conditions for hemicellulose sugars extraction consisted in using 100 mg acid/g dry matter 10g liquid/g solid at 163 degrees C for 45 min Under these conditions hydrolysis efficiencies of 100% 774% and 895% may be achieved for galactan mannan and arabinan respectively corresponding to a hemicellulose hydrolysis efficiency of 874% (C) 2010 Elsevier Ltd All rights reserved

Hydrogen peroxide bleaching of cellulose pulps obtained from brewer`s spent grain

Brewer`s spent grain (BSG) was evaluated for bleached pulp production. Two cellulose pulps with different chemical compositions were produced by soda pulping: one from the original raw material and the other from material pretreated by dilute acid. Both of them were bleached by a totally chlorine-free sequence performed in three stages, using 5% hydrogen peroxide in the two initial, and a 0.25 N NaOH solution in the last one. Chemical composition, kappa number, viscosity, brightness and yield of bleached and unbleached pulps were evaluated. The high hemicellulose (28.4% w/w) and extractives (5.8% w/w) contents in original BSG affected the pulping and bleaching processes. However, soda pulping of acid pretreated BSG gave a cellulose-rich pulp (90.4% w/w) with low hemicellulose and extractives contents (7.9% w/w and < 3.4% w/w, respectively), which was easily bleached achieving a kappa number of 11.21, viscosity of 3.12 cp, brightness of 71.3%, cellulose content of 95.7% w/w, and residual lignin of 3.4% w/w. Alkaline and oxidative delignification of acid pretreated BSG was found as an attractive approach for producing high-purity, chlorine-free cellulose pulp.

Sequential production of amylolytic and lipolytic enzymes by bacterium strain isolated from petroleum contaminated soil

Amylases and lipases are highly demanded industrial enzymes in various sectors such as food, pharmaceuticals, textiles, and detergents. Amylases are of ubiquitous occurrence and hold the maximum market share of enzyme sales. Lipases are the most versatile biocatalyst and bring about a range of bioconversion reactions such as hydrolysis, inter-esterification, esterification, alcoholysis, acidolysis, and aminolysis. The objective of this work was to study the feasibility for amylolitic and lipolytic production using a bacterium strain isolated from petroleum contaminated soil in the same submerged fermentation. This was a sequential process based on starch and vegetable oils feedstocks. Run were performed in batchwise using 2% starch supplemented with suitable nutrients and different vegetable oils as a lipase inducers. Fermentation conditions were pH 5.0; 30 degrees C, and stirred speed (200 rpm). Maxima activities for amyloglucosidase and lipase were, respectively, 0.18 and 1,150 U/ml. These results showed a promising methodology to obtain both enzymes using industrial waste resources containing vegetable oils.

Mechanical properties of Y-TPZ ceramics obtained by liquid phase sintering using bioglass as additive

Yttria stabilized tetragonal zirconia (Y-TZP) ceramics were sintered by liquid phase sintering at low temperatures using bioglass as sintering additive. ZrO2-bioglass ceramics were prepared by mixing a ZrO2 stabilized with 3 Mol%Y2O3 and different amounts of bioglass based on 3CaO center dot P2O5-MgO-SiO2 system. Mixtures were compacted by uniaxial cold pressing and sintered in air, at 1200 and 1300 degrees C for 120 min. The influence of the bioglass content on the densification, tetragonal phase stability, bending strength, hardness and fracture toughness was investigated. The ceramics sintered at 1300 degrees C and prepared by addition of 3% of bioglass, exhibited the highest strength of 435 MPa, hardness of 1170 HV and fracture toughness of 6.3 MPa m(1/2). These results are related to the low monoclinic phase content, high relative density and the presence of the thermal residual stress generated between the ZrO2-matrix and bioglass grain boundary, contributing to the activation of the toughening mechanisms. (c) 2007 Elsevier B.V. All rights reserved.