Single interface flow analysis with accuracy assessment

Single interface flow systems (SIFA) present some noteworthy advantages when compared to other flow systems, such as a simpler configuration, a more straightforward operation and control and an undemanding optimisation routine. Moreover, the plain reaction zone establishment, which relies strictly on the mutual inter-dispersion of the adjoining solutions, could be exploited to set up multiple sequential reaction schemes providing supplementary information regarding the species under determination. In this context, strategies for accuracy assessment could be favourably implemented. To this end, the sample could be processed by two quasi-independent analytical methods and the final result would be calculated after considering the two different methods. Intrinsically more precise and accurate results would be then gathered. In order to demonstrate the feasibility of the approach, a SIFA system with spectrophotometric detection was designed for the determination of lansoprazole in pharmaceutical formulations. Two reaction interfaces with two distinct pi-acceptors, chloranilic acid (CIA) and 2,3-dichloro-5,6-dicyano-p-benzoquinone (DDQ) were implemented. Linear working concentration ranges between 2.71 x 10(-4) to 8.12 x 10(-4) mol L(-1) and 2.17 x 10(-4) to 8.12 x 10(-4) mol L(-1) were obtained for DDQ and CIA methods, respectively. When compared with the results furnished by the reference procedure, the results showed relative deviations lower than 2.7%. Furthermore. the repeatability was good, with r.s.d. lower than 3.8% and 4.7% for DDQ and CIA methods, respectively. Determination rate was about 30 h(-1). (C) 2009 Elsevier B.V. All rights reserved.

Multi-commutation in spectrometry

We review recent developments in manifold components and the introduction of light-emitting-diode technology in spectroscopic detection in order to evaluate the tremendous possibilities offered by multi-commutation for infield and in-situ measurements, based on the use of multi-pumping and low-voltage, portable batteries, which make possible a dramatic reduction in size, weight and power requirements of spectrometric devices. (C) 2009 Elsevier Ltd. All rights reserved.

An improved procedure for flow-based turbidimetric sulphate determination based on a liquid core waveguide and pulsed flows

An improved flow-based procedure is proposed for turbidimetric sulphate determination in waters. The flow system was designed with solenoid micro-pumps in order to improve mixing conditions and minimize reagent consumption as well as waste generation. Stable baselines were observed in view of the pulsed flow characteristic of the systems designed with solenoid micro-pumps, thus making the use of washing solutions unnecessary. The nucleation process was improved by stopping the flow prior to the measurement, thus avoiding the need of sulphate addition. When a 1-cm optical path flow cell was employed, linear response was achieved within 20-200 mg L(-1), described by the equation S = -0.0767 + 0.00438C (mg L(-1)), r = 0.999. The detection limit was estimated as 3 mg L(-1) at the 99.7% confidence level and the coefficient of variation was 2.4% (n = 20). The sampling rate was estimated as 33 determinations per hour. A long pathlength (100-cm) flow cell based on a liquid core waveguide was exploited to increase sensitivity in turbidimetry. Baseline drifts were avoided by a periodical washing step with EDTA in alkaline medium. Linear response was observed within 7-16 mg L(-1), described by the equation S = -0.865 + 0.132C (mg L(-1)), r = 0.999. The detection limit was estimated as 150 mu g L(-1) at the 99.7% confidence level and the coefficient of variation was 3.0% (n = 20). The sampling rate was estimated as 25 determinations per hour. The results obtained for freshwater and rain water samples were in agreement with those achieved by batch turbidimetry at the 95% confidence level. (C) 2008 Elsevier B.V All rights reserved.

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.

Fractionation of Zn, Cd and Pb in a Tropical Soil After Nine-Year Sewage Sludge Applications

A long-term field experiment was carried out in the experiment farm of the Sao Paulo State University, Brazil, to evaluate the phytoavailability of Zn, Cd and Pb in a Typic Eutrorthox soil treated with sewage sludge for nine consecutive years, using the sequential extraction and organic matter fractionation methods. During 2005-2006, maize (Zea mays L.) was used as test plants and the experimental design was in randomized complete blocks with four treatments and five replicates. The treatments consisted of four sewage sludge rates (in a dry basis): 0.0 (control, with mineral fertilization), 45.0, 90.0 and 127.5 t ha(-1), annually for nine years. Before maize sowing, the sewage sludge was manually applied to the soil and incorporated at 10 cm depth. Soil samples (0-20 cm layer) for Zn, Cd and Pb analysis were collected 60 days after sowing. The successive applications of sewage sludge to the soil did not affect heavy metal (Cd and Pb) fractions in the soil, with exception of Zn fractions. The Zn, Cd and Pb distributions in the soil were strongly associated with humin and residual fractions, which are characterized by stable chemical bonds. Zinc, Cd and Pb in the soil showed low phytoavailability after nine-year successive applications of sewage sludge to the soil.

Categories of manual asymmetry and their variation with advancing age

Manual asymmetries were analyzed in 18- to 63-year-old right-handers in different motor tasks. This analysis aimed at describing the asymmetry profile for each task and assessing their stability across ages. For this purpose, performance of the right and left hands were analyzed in the following aspects: simple reaction time, rate of sequential finger movements, maximum grip force, accuracy in anticipatory timing, rate of repetitive tapping, and rate of drawing movements. In addition, stability of manual preference across ages was assessed through the Edinburgh inventory (Oldfield, 1971). The results indicated different profiles of manual asymmetry, with identification of three categories across tasks: symmetric performance (asymmetry indices close to zero), inconsistent asymmetry (asymmetry indices variable in magnitude and direction), and consistent asymmetry (asymmetry indices favoring a single hand). The different profiles observed in the young adults were stable across ages with two exceptions: decreased lateral asymmetry for maximum grip force and increased asymmetry for sequential drawing in older individuals. These results indicate that manual asymmetries are task specific. Such task specificity is interpreted to be the result of different sensorimotor requirements imposed by each motor task in association with motor experiences accumulated over the lifetime. Analysis of manual preference showed that strength of preference for the right hand was greater in older individuals. (C) 2008 Elsevier Masson Srl. All rights reserved.

Clarification of a wheat straw-derived medium with ion-exchange resins for xylitol crystallization

BACKGROUND: Xylitol bioproduction from lignocellulosic residues comprises hydrolysis of the hemicellulose, detoxification of the hydrolysate, bioconversion of the xylose, and recovery of xylitol from the fermented hydrolysate. There are relatively few reports on xylitol recovery from fermented media. In the present study, ion-exchange resins were used to clarify a fermented wheat straw hemicellulosic hydrolysate, which was then vacuum-concentrated and submitted to cooling in the presence of ethanol for xylitol crystallization. RESULTS: Sequential adsorption into two anion-exchange resins (A-860S and A-500PS) promoted considerable reductions in the content of soluble by-products (up to 97.5%) and in medium coloration (99.5%). Vacuum concentration led to a dark-colored viscous solution that inhibited xylitol crystallization. This inhibition could be overcome by mixing the concentrated medium with a commercial xylitol solution. Such a strategy led to xylitol crystals with up to 95.9% purity. The crystallization yield (43.5%) was close to that observed when using commercial xylitol solution (51.4%). CONCLUSION: The experimental data demonstrate the feasibility of using ion-exchange resins followed by cooling in the presence of ethanol as a strategy to promote the fast recovery and purification of xylitol from hemicellulose-derived fermentation media. (c) 2008 Society of Chemical Industry.

Simultaneous saccharification and ethanol fermentation of oxalic acid pretreated corncob assessed with response surface methodology

Response surface methodology was used to evaluate optimal time, temperature and oxalic acid concentration for simultaneous saccharification and fermentation (SSF) of corncob particles by Pichia stipitis CBS 6054. Fifteen different conditions for pretreatment were examined in a 2(3) full factorial design with six axial points. Temperatures ranged from 132 to 180 degrees C, time from 10 to 90 min and oxalic acid loadings from 0.01 to 0.038 g/g solids. Separate maxima were found for enzymatic saccharification and hemicellulose fermentation, respectively, with the condition for maximum saccharification being significantly more severe. Ethanol production was affected by reaction temperature more than by oxalic acid and reaction time over the ranges examined. The effect of reaction temperature was significant at a 95% confidence level in its effect on ethanol production. Oxalic acid and reaction time were statistically significant at the 90% level. The highest ethanol concentration (20 g/l) was obtained after 48 h with an ethanol volumetric production rate of 0.42 g ethanol l(-1) h(-1). The ethanol yield after SSF with P. stipitis was significantly higher than predicted by sequential saccharification and fermentation of substrate pretreated under the same condition. This was attributed to the secretion of beta-glucosidase by P. stipitis. During SSF, free extracellular beta-glucosidase activity was 1.30 pNPG U/g with P. stipitis, while saccharification without the yeast was 0.66 pNPG U/g. Published by Elsevier Ltd.

Artificial neural networks analysis of Sao Paulo subway tunnel settlement data

Artificial neural networks have been used to analyze a number of engineering problems, including settlement caused by different tunneling methods in various types of ground mass. This paper focuses on settlement over shotcrete- supported tunnels on Sao Paulo subway line 2 (West Extension) that were excavated in Tertiary sediments using the sequential excavation method. The adjusted network is a good tool for predicting settlement above new tunnels to be excavated in similar conditions. The influence of network training parameters on the quality of results is also discussed. (C) 2007 Elsevier Ltd. All rights reserved.

Performance and molecular evaluation of an anaerobic system with suspended biomass for treating wastewater with high fat content after enzymatic hydrolysis

The effect of a lipase-rich fungal enzymatic preparation, produced by a Penicillium sp. during solid-state fermentation, was evaluated in an anaerobic digester treating dairy wastewater with 1200 mg of oil and grease/L The oil and grease hydrolysis step was carried out with 0.1% (w/v) of solid enzymatic preparation at 30 degrees C for 24 h, and resulted in a final free acid concentration eight times higher than the initial value. The digester operated in sequential batches of 48 h at 30 degrees C for 245 days, and had high chemical oxygen demand (COD) removal efficiencies (around 90%) when fed with pre-hydrolyzed wastewater. However, when the pre-hydrolysis step was removed, the anaerobic digester performed poorly (with an average COD removal of 32%), as the oil and grease accumulated in the biomass and effluent oil and grease concentration increased throughout the operational period. PCR-DGGE analysis of the Bacteria and Archaea domains revealed remarkable differences in the microbial profiles in trials conducted with and without the pre-hydrolysis step, indicating that differences observed in overall parameters were intrinsically related to the microbial diversity of the anaerobic sludge. (C) 2009 Elsevier Ltd. All rights reserved.