Optimization and validation of a LIBS method for the determination of macro and micronutrients in sugar cane leaves

Laser induced breakdown spectrometry (LIBS) was applied for the determination of macro (P, K, Ca, Mg) and micronutrients (B, Cu, Fe, Mn and Zn) in sugar cane leaves, which is one of the most economically important crops in Brazil. Operational conditions were previously optimized by a neuro-genetic approach, by using a laser Nd:YAG at 1064 nm with 110 mJ per pulse focused on a pellet surface prepared with ground plant samples. Emission intensities were measured after 2.0 mu s delay time, with 4.5 mu s integration time gate and 25 accumulated laser pulses. Measurements of LIBS spectra were based on triplicate and each replicate consisted of an average of ten spectra collected in different sites (craters) of the pellet. Quantitative determinations were carried out by using univariate calibration and chemometric methods, such as PLSR and iPLS. The calibration models were obtained by using 26 laboratory samples and the validation was carried out by using 15 test samples. For comparative purpose, these samples were also microwave-assisted digested and further analyzed by ICP OES. In general, most results obtained by LIBS did not differ significantly from ICP OES data by applying a t-test at 95% confidence level. Both LIBS multivariate and univariate calibration methods produced similar results, except for Fe where better results were achieved by the multivariate approach. Repeatability precision varied from 0.7 to 15% and 1.3 to 20% from measurements obtained by multivariate and univariate calibration, respectively. It is demonstrated that LIBS is a powerful tool for analysis of pellets of plant materials for determination of macro and micronutrients by choosing calibration and validation samples with similar matrix composition.

An expert flow system involving in-line prior assay for turbidimetric determination of chloride and sulphate in natural waters

A multi-pumping flow system exploiting prior assay is proposed for sequential turbidimetric determination of sulphate and chloride in natural waters. Both methods are implemented in the same manifold that provides facilities for: in-line sample clean-up with a Bio-Rex 70 mini-column with fluidized beads: addition of low amounts of sulphate or chloride ions to the reaction medium for improving supersaturation; analyte precipitation with Ba(2+) or Ag(+); real-time decision on the need for next assay. The sample is initially run for chloride determination, and the analytical signal is compared with a preset value. If higher, the sample is run again, now for sulphate determination. The strategy may lead to all increased sample throughput. The proposed system is computer-controlled and presents enhanced figures of merit. About 10 samples are run per hour (about 60 measurements) and results are reproducible and Unaffected by the presence of potential interfering ions at concentration levels usually found in natural waters. Accuracy was assessed against ion chromatography. (C) 2008 Elsevier B.V. All rights reserved.

Heat and exercise acclimation increases intracellular levels of Hsp72 and inhibits exercise-induced increase in intracellular and plasma Hsp72 in humans

In order to verify the effects of heat and exercise acclimation (HA) on resting and exercise-induced expression of plasma and leukocyte heat shock protein 72 (Hsp72) in humans, nine healthy young male volunteers (25.0 +/- 0.7 years; 80.5 +/- 2.0 kg; 180 +/- 2 cm, mean +/- SE) exercised for 60 min in a hot, dry environment (40 +/- 0A degrees C and 45 A +/- 0% relative humidity) for 11 days. The protocol consisted of running on a treadmill using a controlled hyperthermia technique in which the work rate was adjusted to elevate the rectal temperature by 1A degrees C in 30 min and maintain it elevated for another 30 min. Before and after the HA, the volunteers performed a heat stress test (HST) at 50% of their individual maximal power output for 90 min in the same environment. Blood was drawn before (REST), immediately after (POST) and 1 h after (1 h POST) HST, and plasma and leukocytes were separated and stored. Subjects showed expected adaptations to HA: reduced exercise rectal and mean skin temperatures and heart rate, and augmented sweat rate and exercise tolerance. In HST1, plasma Hsp72 increased from REST to POST and then returned to resting values 1 h POST (REST: 1.11 A +/- 0.07, POST: 1.48 A +/- 0.10, 1 h POST: 1.22 A +/- 0.11 ng mL(-1); p < 0.05). In HST2, there was no change in plasma Hsp72 (REST: 0.94 A +/- 0.08, POST: 1.20 A +/- 0.15, 1 h POST: 1.17 A +/- 0.16 ng mL(-1); p > 0.05). HA increased resting levels of intracellular Hsp72 (HST1: 1 A +/- 0.02 and HST2: 4.2 A +/- 1.2 density units, p < 0.05). Exercise-induced increased intracellular Hsp72 expression was observed on HST1 (HST1: REST, 1 A +/- 0.02 vs. POST, 2.9 A +/- 0.9 density units, mean +/- SE, p < 0.05) but was inhibited on HST2 (HST2: REST, 4.2 +/- 1.2 vs. POST, 4.4 +/- 1.1 density units, p > 0.05). Regression analysis showed that the lower the pre-exercise expression of intracellular Hsp72, the higher the exercise-induced increase (R = -0.85, p < 0.05). In conclusion, HA increased resting leukocyte Hsp72 levels and inhibited exercise-induced expression. This intracellular adaptation probably induces thermotolerance. In addition, the non-increase in plasma Hsp72 after HA may be related to lower stress at the cellular level in the acclimated individuals.

Effect of hemicellulose and lignin on enzymatic hydrolysis of cellulose from brewer`s spent grain

Enzymatic hydrolysis of brewer`s spent grain in three different forms: original (untreated), pretreated by dilute acid (cellulignin), and pretreated by a sequence of dilute acid and dilute alkali (cellulose pulp), was studied to verify the effect of hemicellulose and lignin on cellulose conversion into glucose. The hydrolysis was carried out using a commercial cellulase concentrate (Celluclast 1.5 L) in an enzyme/substrate ratio of 45 FPU/g, 2% (w/v) substrate concentration, 45 degrees C for 96 h. According to the results, the cellulose hydrolysis was affected by the presence of hemicellulose and/or lignin in the sample. The cellulose conversion ratio (defined as glucose yield + cellobiose yield) from cellulignin was 3.5-times higher than that from untreated sample, whereas from cellulose pulp such value was 4-times higher, correspondent to 91.8% (glucose yield of 85.6%). This best result was probably due to the strong modification in the material structure caused by the hemicellulose and lignin removal from the sample. As a consequence, the cellulose fibers were separated being more susceptible to the enzymatic attack. It was concluded that the lower the hemicellulose and lignin contents in the sample, the higher the efficiency of cellulose hydrolysis. (C) 2007 Elsevier Inc. All rights reserved.

Electrical and Magnetic Characterization of BSCCO and YBCO HTS Tapes for Fault Current Limiter Application

Several high temperature superconductor (HTS) tapes have been developed since the late eighties. Due to the new techniques applied for their production, HTS tapes are becoming feasible and practical for many applications. In this work, we present the test results of five commercial HTS tapes from the BSCCO and YBCO families (short samples of 200 mm). We have measured and analyzed their intrinsic and extrinsic properties and compared their behaviors for fault current limiter (FCL) applications. Electrical measurements were performed to determine the critical current and the n value through the V-I relationship under DC and AC magnetic fields. The resistance per unit length was determined as a function of temperature. The magnetic characteristics were analyzed through susceptibility curves as a function of temperature. As transport current generates a magnetic field surrounding the HTS material, the magnetic measurements indicate the magnetic field supported by the tapes under a peak current 1.5 times higher than the critical current, I(c). By pulsed current tests the recovery time and the energy/volume during a current fault were also analyzed. These results are in agreement with the data found in the literature giving the most appropriate performance conductor for a FCL device (I(peak) = 4 kA) to be used in a 220 V-60 Hz grid.

The roles of xylan and lignin in oxalic acid pretreated corncob during separate enzymatic hydrolysis and ethanol fermentation

High yields of hemicellulosic and cellulosic sugars are critical in obtaining economical conversion of agricultural residues to ethanol. To optimize pretreatment conditions, we evaluated oxalic acid loading rates, treatment temperatures and times in a 2(3) full factorial design. Response-surface analysis revealed an optimal oxalic acid pretreatment condition to release sugar from the cob of Zea mays L ssp. and for Pichia stipitis CBS 6054. To ferment the residual cellulosic sugars to ethanol following enzymatic hydrolysis, highest saccharification and fermentation yields were obtained following pretreatment at 180 degrees C for 50 min with 0.024 g oxalic acid/g substrate. Under these conditions, only 7.5% hemicellulose remained in the pretreated substrate. The rate of cellulose degradation was significantly less than that of hemicellulose and its hydrolysis was not as extensive. Subsequent enzymatic saccharification of the residual cellulose was strongly affected by the pretreatment condition with cellulose hydrolysis ranging between 26.0% and 76.2%. The residual xylan/lignin ratio ranged from 0.31 to 1.85 depending on the pretreatment condition. Fermentable sugar and ethanol were maximal at the lowest ratio of xylan/lignin and at high glucan contents. The model predicts optimal condition of oxalic acid pretreatment at 168 degrees C, 74 min and 0.027 g/g of oxalic acid. From these findings, we surmised that low residual xylan was critical in obtaining maximal glucose yields from saccharification. Published by Elsevier Ltd.

Assessment of the Performance of Acoustic and Mass Balance Methods for Leak Detection in Pipelines for Transporting Liquids

On-line leak detection is a main concern for the safe operation of pipelines. Acoustic and mass balance are the most important and extensively applied technologies in field problems. The objective of this work is to compare these leak detection methods with respect to a given reference situation, i.e., the same pipeline and monitoring signals acquired at the inlet and outlet ends. Experimental tests were conducted in a 749 m long laboratory pipeline transporting water as the working fluid. The instrumentation included pressure transducers and electromagnetic flowmeters. Leaks were simulated by opening solenoid valves placed at known positions and previously calibrated to produce known average leak flow rates. Results have clearly shown the limitations and advantages of each method. It is also quite clear that acoustics and mass balance technologies are, in fact, complementary. In general, an acoustic leak detection system sends out an alarm more rapidly and locates the leak more precisely, provided that the rupture of the pipeline occurs abruptly enough. On the other hand, a mass balance leak detection method is capable of quantifying the leak flow rate very accurately and of detecting progressive leaks.

Manufacture and characterization of ultra and microfiltration ceramic membranes by isostatic pressing

This paper describes the manufacture of tubular UF and MF porous and supported ceramic membranes to oil/water emulsions demulsification. For such a purpose, a rigorous control was realized over the distribution and size of pores. Suspensions at 30 vol.% of solids (zirconia or alumina powder and sucrose) and 70 vol.% of liquids (isopropyl alcohol and PVB) were prepared in a jar mill varying the milling time of the sucrose particles, according to the pores size expected. The membranes were prepared by isostatic pressing method and structurally characterized by SEM, porosimetry by mercury intrusion and measurements of weight by immersion. The morphological characterization of the membranes identified the formation of porous zirconia and alumina membranes and supported membranes. The results of porosimetry analysis by mercury intrusion presented an average pore size of 1.8 mu m for the microfiltration porous membranes and for the ultrafiltration supported membranes, pores with average size of 0.01-0.03 mu m in the top-layer and 1.8 mu m in the support. By means of the manufacture method applied, it was possible to produce ultra and microfiltration membranes with high potential to be applied to the separation of oil/water emulsions. (C) 2011 Elsevier Ltd and Techna Group S.r.l. All rights reserved.

AnSBBR Applied to the Treatment of Metalworking Fluid Wastewater: Effect of Organic and Shock Load

An investigation was performed regarding the application of a mechanically stirred anaerobic sequencing batch biofilm reactor containing immobilized biomass on inert polyurethane foam (AnSBBR) to the treatment of soluble metalworking fluids to remove organic matter and produce methane. The effect of increasing organic matter and reactor fill time, as well as shock load, on reactor stability and efficiency have been analyzed. The 5-L AnSBBR was operated at 30 A degrees C in 8-h cycles, agitation of 400 rpm, and treated 2.0 L effluent per cycle. Organic matter was increased by increasing the influent concentration (500, 1,000, 2,000, and 3,000 mg chemical oxygen demand (COD)/L). Fill times investigated were in the batch mode (fill time 10 min) and fed-batch followed by batch (fill time 4 h). In the batch mode, organic matter removal efficiencies were 87%, 86%, and 80% for influent concentrations of 500, 1,000, and 2,000 mgCOD/L (1.50, 3.12, and 6.08 gCOD/L.d), respectively. At 3,000 mgCOD/L (9.38 gCOD/L.d), operational stability could not be achieved. The reactor managed to maintain stability when a shock load twice as high the feed concentration was applied, evidencing the robustness of the reactor to potential concentration variations in the wastewater being treated. Increasing the fill time to 4 h did not improve removal efficiency, which was 72% for 2,000 mgCOD/L. Thus, gradual feeding did not improve organic matter removal. The concentration of methane formed at 6.08 gCOD/L was 5.20 mmolCH(4), which corresponded to 78% of the biogas composition. The behavior of the reactor during batch and fed-batch feeding could be explained by a kinetic model that considers organic matter consumption, production, and consumption of total volatile acids and methane production.

Application of an anaerobic packed-bed bioreactor for the production of hydrogen and organic acids

This study investigates the feasibility of an anaerobic bioreactor for treating low contents of organic matter to generate organic acids and hydrogen. The device employed for this purpose was a horizontal packed-bed bioreactor fed with glucose-based synthetic wastewater and operated with hydraulic retention times from 0.5 to 2 h. A microbial biofilm was developed without previous inoculation, using expanded clay beads (4.8-6.3 mm) as support material. Alkalinity was found to be the main parameter affecting the production of hydrogen and organic acids, and the system produced optimal output when operating without a buffer agent. The average hydrogen production was 2.48, 2.15 and 1.81 molH(2) mol(-1) of glucose for NaHCO3 influent concentrations of 0, 1000 and 2000 mg L-1, respectively. The operational regime of the bioreactor, the support material and the controlled alkalinity were effective in selecting and immobilizing microbial fermenting biofilms, which successfully produced hydrogen and organic acids throughout the operating period. Exploratory assays indicated the feasibility of organic acid extraction using an anionic polymeric resin. (C) 2007 International Association for Hydrogen Energy. Published by Elsevier Ltd. All rights reserved.

An integrated molecular map of yellow passion fruit based on simultaneous maximum-likelihood estimation of linkage and linkage phases

The development of genetic maps for auto-incompatible species, such as the yellow passion fruit (Passiflora edulis Sims f.flavicarpa Deg.) is restricted due to the unfeasibility of obtaining traditional mapping populations based on inbred lines. For this reason, yellow passion fruit linkage maps were generally constructed using a strategy known as two-way pseudo-testeross, based on monoparental dominant markers segregating in a 1:1 fashion. Due to the lack of information from these markers in one of the parents, two individual (parental) maps were obtained. However, integration of these maps is essential, and biparental markers can be used for such an operation. The objective of our study was to construct an integrated molecular map for a full-sib population of yellow passion fruit combining different loci configuration generated from amplified fragment length polymorphisms (AFLPs) and microsatellite markers and using a novel approach based on simultaneous maximum-likelihood estimation of linkage and linkage phases, specially designed for outcrossing species. Of the total number of loci, approximate to 76%, 21%, 0.7%, and 2.3% did segregate in 1:1, 3:1, 1:2:1, and 1:1:1:1 ratios, respectively. Ten linkage groups (LGs) were established with a logarithm of the odds (LOD) score >= 5.0 assuming a recombination fraction : <= 0.35. On average, 24 markers were assigned per LG, representing a total map length of 1687 cM, with a marker density of 6.9 cM. No markers were placed as accessories on the map as was done with previously constructed individual maps.

Apparent digestibility coefficient of protein and amino acids of acid, biological and enzymatic silage for Nile tilapia (Oreochromis niloticus)

Using the fish silage to partially replace proteic feedstuff in aquafeeds is an alternative to mitigate sanitary and environmental problems caused by the lack of adequate destination for fisheries residues. It would also lower feed costs, consequently improving fish culture profitability. However, using fish silages in aquafeeds depends on determination of its apparent digestibility coefficients (ADC). This work aimed to determining the ADC of crude protein and amino acids of acid silage (AS), biological silage (BS) and enzymatic silage (ES) for juvenile Nile tilapia (94.5 +/- 12.7 g). The ADC(CP) was: 92.0%, 89.1% and 93.7% for AS, BS and SE respectively. The average ADC of amino acids was: 91.8%, 90.8% and 94.6% for AS, BS and ES respectively. Results encourage the use of AS, BS and ES to partially replace protein sources in balanced diets for neotropical fish.

Response of watermelon cultivated under different levels of water and nitrogen

The effect of four irrigation levels (50; 75; 100 and 150% of the evaporation in the class A pan) and four levels of N (0,075; 0, 150; 0,225 and 0,300 kg(-1)), were evaluated on productivity and components of production of the watermelon `Charleston Gray`. The experiment was conducted under field conditions, from October/2003 to January/2004, using a randomized split-plot design, with the factor depths in plot and depths of N in split-plot. It was verified that the factors water and nitrogen presented a highly significant effect in the yield of watermelon, while the interaction among the factors was not significant. The maximum productivity of the watermelon (68.59 Mg ha(-1)) was obtained with 421 mm of water and 267 kg ha(-1) of N. The water was more efficiently used with increments in dosage of N, being the maximum value observed of 279.54 kg ha(-1) mm(-1), obtained with a depth of water of 205 mm and a depths of N of 225 kg ha(-1). The maximum efficiency of the use of the water for the nitro en was 221 kg ha(-1) mm(-1), for 249 kg ha(-1) of N. The sugar content of the watermelon, measured in degrees Brix, was affected by the depths of irrigation, depths of N and by its interactions.

Effect of Brazil nut supplementation on the blood levels of selenium and glutathione peroxidase in hemodialysis patients

Objective: In patients who have undergone hemodialysis, large amounts of reactive oxygen species (ROS) are produced and, at higher concentrations, ROS are thought to be involved in the pathogenesis of cardiovascular disease. It has been proposed that selenium (Se) may exert an anti-atherogenic influence by reducing oxidative stress. The richest known food source of selenium is the Brazil nut (Bertholletia excelsa, family Lecythidaceae), found in the Amazon region. We evaluated the effect of Brazil nut supplementation on blood levels of Se and glutathione peroxidase (GSH-Px) activity in patients on hemodialysis. Methods: A total of 81 patients on hemodialysis (52.0 +/- 15.2 y old, average time on dialysis 82.3 +/- 91.4 mo, body mass index 24.9 +/- 4.4 kg/m(2)) from the RenalCor and RenalVida Clinics in Rio de Janeiro, Brazil, were studied. All patients received one nut (around 5 g, averaging 58.1 mu g Se/g) a day for 3 mo. The Se concentrations in the nuts and in plasma and erythrocytes were determined by atomic absorption spectrophotometry with hydride generation (Hitachi, Z-500). GSH-Px levels were measured using Randox commercial kits. Results: Plasma Se (18.8 +/- 17.4 mu g/L) and erythrocyte (72.4 +/- 37.9 mg/L) levels were below the normal, range before nut supplementation. After supplementation, the plasma level increased to 104.0 +/- 65.0 mu g/L and erythrocytes to 244.1 +/- 119.5 mg/L (P<0.0001). The activity of GSH-Px also increased after supplementation, from 46.6 +/- 14.9 to 55.9 +/- 23.6 U/g of hemoglobin (P<0.0001). Before supplementation, 11% of patients had GSH-Px activity below the normal range (27.5-73.6 U/g of hemoglobin). After supplementation, all patients showed GSH-Px activity within the normal range. Conclusion: The data revealed that the investigated patients presented Se deficiency and that the consumption of only one Brazil nut a day (5 g) during 3 mo was effective to increase the Se concentration and GSH-Px activity in these patients, thus improving their antioxidant status. (C) 2010 Elsevier Inc. All rights reserved.

Separation of Steroids and the Determination of Estradiol Content in Transdermic Patches by Microemulsion Electrokinetic Chromatography

A novel microemulsion electrokinetic capillary chromatography (MEEKC) method has been developed which separates a range of nine steroids. A microemulsion containing ethyl acetate, butan-1-ol, sodium dodecyl sulfate, 15% (v/v) acetonitrile and 12 mmol L(-1) sodium tetraborate aqueous buffer at pH 9.2 was used with direct UV detection at 200 nm. The method was validated for the determination of 17 beta-estradiol content, a hormone steroid, in transdermal patches. Adequate sensitivity (DL = 0.88 mu g mL(-1); QL = 2.65 mu g mL(-1)) without interference from sample excipients was obtained. 17 beta-Estradiol migrates in approximately 5.4 min. Estrone was used as internal standard and acceptable precision (< 1.2% RSD), linearity (r = 0.9996; range from 40.0 to 60.0 mu g mL(-1)), and recovery (100.4 +/- A 0.9% at three concentration levels) were obtained. The principal advantage of the method is that it is rapid and avoids the need of time consuming and expensive sample pre-treatment steps.