A greener and highly sensitive flow-based procedure for carbaryl determination exploiting long pathlength spectrophotometry and photochemical waste degradation

An environmentally friendly analytical procedure with high sensitivity for determination of carbaryl pesticide in natural waters was developed. The flow system was designed with solenoid micro-pumps in order to improve mixing conditions and minimize reagent consumption as well as waste generation. A long pathlength (100 cm) flow cell based on a liquid core waveguide (LCW) was employed to increase the sensitivity in detection of the indophenol formed from the reaction between carbaryl and p-aminophenol (PAP). A clean-up step based on cloud-point extraction was explored to remove the interfering organic matter, avoiding the use of toxic organic solvents. A linear response was observed within the range 5-200 mu g L(-1) and the detection limit, coefficient of variation and sampling rate were estimated as 1.7 mu g L(-1) (99.7% confidence level), 0.7% (n=20) and 55 determinations per hour, respectively. The reagents consumption was 1.9 mu g of PAP and 5.7 mu g of potassium metaperiodate, with volume of 2.6 mL of effluent per determination. The proposed procedure was selective for the determination of carbaryl, without interference from other carbamate pesticides. Recoveries within 84% and 104% were estimated for carbaryl spiked to water samples and the results obtained were also in agreement with those found by a batch spectrophotometric procedure at the 95% confidence level. The waste of the analytical procedure was treated with potassium persulphate and ultraviolet irradiation, yielding a colorless residue and a decrease of 94% of total organic carbon. In addition, the residue after treatment was not toxic for Vibrio fischeri bacteria. (c) 2010 Elsevier B.V. All rights reserved.

A flow-based procedure with solenoid micro-pumps for the spectrophotometric determination of uric acid in urine

The determination of uric acid in urine shows clinical importance, once it can be related to human organism dysfunctions, such as gout. An analytical procedure employing a multicommuted flow system was developed for the determination of uric acid in urine samples. Cu(II) ions are reduced by uric acid to Cu(I) that can be quantified by spectrophotometry in the presence of 2,2`-biquinoline 4,4`-dicarboxylic acid (BCA). The analytical response was linear between 10 and 100 mu mol L(-1) uric acid with a detection limit of 3.0 mu mol L(-1) (99.7% confidence level). Coefficient of variation of 1.2% and sampling rate of 150 determinations per hour were achieved. Per determination, 32 mu g of CuSO(4) and 200 mu g of BCA were consumed, generating 2.0 mL of waste. Recoveries from 91 to 112% were estimated and the results for 7 urine samples agreed with those obtained by the commercially available enzymatic kit for determination of uric acid. The procedure required 100-fold dilution of urine samples, minimizing sample consumption and interfering effects. In order to avoid the manual dilution step, on-line sample dilution was achieved by a simple system reconfiguration attaining a sampling rate of 95 h(-1). (C) 2009 Elsevier B.V. All rights reserved.

Green Chemistry-Sensitive Analytical Procedure for Photometric Determination of Orthophosphate in River and Tap Water by Use of a Simple LED-Based Photometer

In the current work a Green Analytical Chemistry (GAC) procedure for photometric determination of orthophosphate in river water at mu g L-1 concentration level is described. The flow system module and the LED-based photometer were assembled together to constitute a compact unit in order to allow that a flow cell with optical path-length of 100mm was coupled to them. The photometric procedure based on the molybdenum blue method was implemented employing the multicommuted flow injection analysis approach, which provided facilities to allow reduction of reagent consumption and as well as waste generation. Aiming to prove the usefulness of the system, orthophosphate in river and tap waters was determined. Accuracy was ascertained by spiking samples with orthophosphate solution yielding recoveries ranging from 96% up to 107%. Other profitable features such as a wide linear response range between 10 to 800 mu g L-1 [image omitted]; a detection limit (3 sigma criterion) of 2.4 mu g L-1 [image omitted]; a relative standard deviation (n=7) of 2% using a typical water sample with concentration of 120 mu g L-1 [image omitted]; reagent consumption of 3.0mg ammonium molybdate, 0.3mg hydrazine sulfate, and 0.03mg stannous chloride per determination; a waste generation of 2.4mL per determination; and a sampling throughput of 20 determination per hours were also achieved.

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 improved flow-based procedure for microdetermination of total tannins in beverages with minimized reagent consumption

A flow system designed with solenoid micro-pumps is introduced for spectrophotometric determination of total tannins based on the Folin- Denis reaction. The procedure minimizes the main drawbacks related to the AOAC batch procedure, i.e. interferences from reducing species in the samples, high reagent consumption and waste generation, and low sampling rate. Linear response was observed for tannic acid concentrations in the range 2-100 mg L-1, with a detection limit (99.7% confidence level) of 0.3 mg L-1. The sampling rate and coefficient of variation (n = 10) were estimated as 75 measurements per hour and 1.1%, respectively. Results of determination of total tannin in tea, beer and wine samples were in agreement with those achieved by the batch reference procedure at the 95% confidence level. In comparison to the batch procedure, the reagent consumption and effluent generation were 83 and 60-fold lower, respectively.

A flow-based analytical procedure for salbutamol determination exploiting chemiluminescence in a liquid-core waveguide

Salbutamol is a bronchodilator whose use is restricted due to its anabolic effects. A flow-based procedure for salbutamol determination based on the inhibition of chemiluminescence of the luminol/hypochlorite system was developed. A flow cell constructed with a liquid-core waveguide was employed to constrain the emitted radiation, minimizing losses during transport to detector. Linear response was observed within 2.5 x 10(-6) and 1.0 x 10(-5) mol L-1 with a detection limit estimated as 1 x 10(-7) mol L-1 at the 99.7% confidence level. The coefficient of variation (n = 20), sampling rate, and luminol consumption per determination were estimated as 2.8%, 164 determinations h(-1), and 50 mu g, respectively. Results for pharmaceutical samples were in agreement with those obtained by reference procedures at the 95% confidence level.

A FEM procedure based on positions and unconstrained vectors applied to non-linear dynamic of 3D frames

This study presents an alternative three-dimensional geometric non-linear frame formulation based on generalized unconstrained vector and positions to solve structures and mechanisms subjected to dynamic loading. The formulation is classified as total Lagrangian with exact kinematics description. The resulting element presents warping and non-constant transverse strain modes, which guarantees locking-free behavior for the adopted three-dimensional constitutive relation, Saint-Venant-Kirchhoff, for instance. The application of generalized vectors is an alternative to the use of finite rotations and rigid triad`s formulae. Spherical and revolute joints are considered and selected dynamic and static examples are presented to demonstrate the accuracy and generality of the proposed technique. (C) 2010 Elsevier B.V. All rights reserved.

A Procedure for Semantic Querying in the Adaptive Formalism

This paper contains a new proposal for the definition of the fundamental operation of query under the Adaptive Formalism, one capable of locating functional nuclei from descriptions of their semantics. To demonstrate the method`s applicability, an implementation of the query procedure constrained to a specific class of devices is shown, and its asymptotic computational complexity is discussed.

A procedure to evaluate environmental rehabilitation in limestone quarries

A procedure to evaluate mine rehabilitation practices during the operational phase was developed and validated. It is based on a comparison of actually observed or documented practices with internationally recommended best practices (BP). A set of 150 BP statements was derived from international guides in order to establish the benchmark. The statements are arranged in six rehabilitation programs under three categories: (1) planning (2) operational and (3) management, corresponding to the adoption of the plan-do-check-act management systems model to mine rehabilitation. The procedure consists of (i) performing technical inspections guided by a series of field forms containing BP statements; (ii) classifying evidences in five categories; and (iii) calculating conformity indexes and levels. For testing and calibration purposes, the procedure was applied to nine limestone quarries and conformity indexes were calculated for the rehabilitation programs in each quarry. Most quarries featured poor planning practices, operational practices reached high conformity levels in 50% of the cases and management practices scored moderate conformity. Despite all quarries being ISO 14001 certified, their management systems pay low attention to issues pertaining to land rehabilitation and biodiversity. The best results were achieved by a quarry whose expansion was recently submitted to the environmental impact assessment process, suggesting that public scrutiny may play a positive role in enhancing rehabilitation practices. Conformity indexes and levels can be used to chart the evolution of rehabilitation practices at regular intervals, to establish corporate goals and for communication with stakeholders. (C) 2010 Elsevier Ltd. All rights reserved.

Effects of weld strength mismatch on J and CTOD estimation procedure for SE(B) specimens

This work examines the effect of weld strength mismatch on fracture toughness measurements defined by J and CTOD fracture parameters using single edge notch bend (SE(B)) specimens. A central objective of the present study is to enlarge on previous developments of J and CTOD estimation procedures for welded bend specimens based upon plastic eta factors (eta) and plastic rotational factors (r (p) ). Very detailed non-linear finite element analyses for plane-strain models of standard SE(B) fracture specimens with a notch located at the center of square groove welds and in the heat affected zone provide the evolution of load with increased crack mouth opening displacement required for the estimation procedure. One key result emerging from the analyses is that levels of weld strength mismatch within the range +/- 20% mismatch do not affect significantly J and CTOD estimation expressions applicable to homogeneous materials, particularly for deeply cracked fracture specimens with relatively large weld grooves. The present study provides additional understanding on the effect of weld strength mismatch on J and CTOD toughness measurements while, at the same time, adding a fairly extensive body of results to determine parameters J and CTOD for different materials using bend specimens with varying geometries and mismatch levels.

Bayesian ratemaking procedure of crop insurance contracts with skewed distribution

Over the years, crop insurance programs became the focus of agricultural policy in the USA, Spain, Mexico, and more recently in Brazil. Given the increasing interest in insurance, accurate calculation of the premium rate is of great importance. We address the crop-yield distribution issue and its implications in pricing an insurance contract considering the dynamic structure of the data and incorporating the spatial correlation in the Hierarchical Bayesian framework. Results show that empirical (insurers) rates are higher in low risk areas and lower in high risk areas. Such methodological improvement is primarily important in situations of limited data.

Test procedure for variable rate fertilizer on coffee

The objective was to develop and test a procedure for applying variable rates of fertilizers and evaluate yield response in coffee (Coffea arabica L.) with regard to the application of phosphorus and potassium. The work was conducted during the 2004 season in a 6.4 ha field located in central Sao Paulo state. Two treatments were applied with alternating strips of fixed and variable rates during the whole season: one following the fertilizing procedures recommended locally, and the other based on a grid soil sampling. A prototype pneumatic fertilizer applicator was used, carrying two conveyor belts, one for each row. Harvesting was done with a commercial harvester equipped with a customized volumetric yield monitor, separating the two treatments. Data were analyzed based on geostatistics, correlations and regressions. The procedure showed to be feasible and effective. The area that received fertilizer applications at a variable rate showed a 34% yield increase compared to the area that received a fixed rate. The variable rate fertilizer resulted in a savings of 23% in phosphate fertilizer and a 13% increase in potassium fertilizer, when compared to fixed rate fertilizer. Yield in 2005, the year after the variable rate treatments, still presented residual effect from treatments carried out during the previous cycle.

Effectiveness of the standard evaluation method for hydraulic nozzles employed in stored grain protection trials

In stored grains, smaller depositions and great variation with respect to theoretical insecticide doses are frequently found. The objective of this work was to study the effectiveness of the standard method (ISO 5682/1-1996) employed to evaluate hydraulic nozzles used in stored corn and wheat grain protection experiments. The transversal volumetric distribution and droplet spectrum of a model TJ-60 8002EVS nozzle were determined in order to calibrate a spraying system for an application rate of 5 L/t and to obtain theoretical concentrations of 10 and 0.5 mg/kg of fenitrothion and esfenvalerate, respectively. After treatment, the corn and wheat grains were processed and deposition was analyzed by gas chromatography. The type of grain did not have any influence on insecticide deposition and was dependent upon insecticide only. The insecticide deposits on the grains only reached 42.1 and 38.2% of the intended theoretical values for fenitrothion and esfenvalerate concentrations, respectively. These results demonstrate the ineffectiveness of the standard evaluation method for hydraulic nozzles employed in stored grain protection experiments.

Effect of natural pigments on the oxidative stability of sausages stored under refrigeration

The objective was to use natural pigments to replace sodium erythorbate (NaEry), a synthetic compound used as an antioxidant in sausage formulations, and to evaluate the oxidative stability of the samples. Six assays were prepared in which sodium erythorbate (ERY) at 0.05 g/100 g was substituted by norbixin (NOR), lycopene (LYC), zeaxanthin (ZEA), beta-carotene (CAR) or dextrose (used as a control (CON)). Physical, chemical, color, texture and sensory parameters were measured on the first day and after 45 days of storage at 4 degrees C. All pigments used in the sausage formulations were able to maintain the oxidative stability of the sausages (MDA equivalents <038 mg/kg). Zeaxanthin and norbixin were the most efficient antioxidants of those tested. This antioxidant effect might be associated with the intermediate polarities of these two compounds, which would allow them to concentrate in the membrane lipids or emulsion interface, where lipid oxidation is most prevalent. Other volatile secondary products of oxidation besides MDA should be evaluated in further studies involving natural pigments and sensory oxidative stability. (C) 2009 Elsevier Ltd. All rights reserved.

Methylmercury and inorganic mercury determination in blood by using liquid chromatography with inductively coupled plasma mass spectrometry and a fast sample preparation procedure

Despite the necessity to differentiate chemical species of mercury in clinical specimens, there area limited number of methods for this purpose. Then, this paper describes a simple method for the determination of methylmercury and inorganic mercury in blood by using liquid chromatography with inductively coupled mass spectrometry (LC-ICP-MS) and a fast sample preparation procedure. Prior to analysis, blood (250 mu L) is accurately weighed into 15-mL conical tubes. Then, an extractant solution containing mercaptoethanol, L-cysteine and HCI was added to the samples following sonication for 15 min. Quantitative mercury extraction was achieved with the proposed procedure. Separation of mercury species was accomplished in less than 5 min on a C18 reverse-phase column with a mobile phase containing 0.05% (v/v) mercaptoethanol, 0.4% (m/v) L-cysteine, 0.06 mol L(-1) ammonium acetate and 5% (v/v) methanol. The method detection limits were found to be 0.25 mu g L(-1) and 0.1 mu Lg L(-1) for inorganic mercury and methylmercury, respectively. Method accuracy is traceable to Standard Reference Material (SRM) 966 Toxic Metals in Bovine Blood from the National Institute of Standards and Technology (NIST). The proposed method was also applied to the speciation of mercury in blood samples collected from fish-eating communities and from rats exposed to thimerosal. With the proposed method there is a considerable reduction of the time of sample preparation prior to speciation of Hg by LC-ICP-MS. Finally, after the application of the proposed method, we demonstrated an interesting in vivo ethylmercury conversion to inorganic mercury. (C) 2009 Elsevier B.V. All rights reserved.