Flow-injection spectrophotometric determination of dipyrone in pharmaceutical formulations using ammonium molybdate as chromogenic reagent

A simple and rapid flow-injection spectrophotometric method is reported for the determination of dipyrone in pharmaceutical formulations. The method is based on the reaction of dipyrone with ammonium molybdate in acidic medium to produce blue molybdenum, which was detected spectrophotometrically at 620 nm. The analyte was determined in a single-line flow system. The calibration curve obtained was linear in the range of 5x10(-4) to 8x10(-3) mol L-1 for dipyrone concentration and the precision ( s r =1.7%) was satisfactory. The method proved to be selective and adequately sensitive. Application of the method to the analysis of pharmaceutical samples resulted in excellent accuracy; the percent mean recoveries were in the range 95.3%-101% and relative errors less than 5.0% for five pharmaceutical formulations were found.

A REMOTE SENSING APPROACH TO CHARACTERIZE THE HYDROGEOLOGY OF MOUNTAINOUS AREAS: APPLICATION TO THE QUITO AQUIFER SYSTEM (QAS), ECUADOR

Climate change, intensive use, and population growth are threatening the availability of water resources. New sources of water, better knowledge of existing ones, and improved water management strategies are of paramount importance. Ground water is often considered as primary water source due to its advantages in terms of quantity, spatial distribution, and natural quality. Remote sensing techniques afford scientists a unique opportunity to characterize landscapes in order to assess groundwater resources, particularly in tectonically influenced areas. Aquifers in volcanic basins are considered the most productive aquifers in Latin America. Although topography is considered the primary driving force for groundwater flows in mountainous terrains, tectonic activity increases the complexity of these groundwater systems by altering the integrity of sedimentary rock units and the overlying drainage networks. Structural controls affect the primary hydraulic properties of the rock formations by developing barriers to flow in some cases and zones of preferential infiltration and subterranean in others. The study area focuses on the Quito Aquifer System (QAS) in Ecuador. The characterization of the hydrogeology started with a lineament analysis based on a combined remote sensing and digital terrain analysis approach. The application of classical tools for regional hydrogeological evaluation and shallow geophysical methods were useful to evaluate the impact of faulting and fracturing on the aquifer system. Given the spatial extension of the area and the complexity of the system, two levels of analysis were applied in this study. At the regional level, a lineament map was created for the QAS. Relationships between fractures, faults and lineaments and the configuration of the groundwater flow on the QAS were determined. At the local level, on the Plateaus region of the QAS, a detailed lineament map was obtained by using high-spatial-resolution satellite imagery and aspect map derived from a digital elevation model (DEM). This map was complemented by the analysis of morphotectonic indicators and shallow geophysics that characterize fracture patterns. The development of the groundwater flow system was studied, drawing upon data pertaining to the aquifer system physical characteristics and topography. Hydrochemistry was used to ascertain the groundwater evolution and verify the correspondence of the flow patterns proposed in the flow system analysis. Isotopic analysis was employed to verify the origin of groundwater. The results of this study show that tectonism plays a very important role for the hydrology of the QAS. The results also demonstrate that faults influence a great deal of the topographic characteristics of the QAS and subsequently the configuration of the groundwater flow. Moreover, for the Plateaus region, the results demonstrate that the aquifer flow systems are affected by secondary porosity. This is a new conceptualization of the functioning of the aquifers on the QAS that will significantly contribute to the development of better strategies for the management of this important water resource.

Development of instrumentation for amperometric and coulometric detection using ultramicroelectrodes

In this work it is presented the development of a simple, portable and inexpensive instrumentation for amperometric and coulometric detection in different analytical instrumentation systems utilizing ultramicroelectrodes. The software, developed in LabVIEW 7.1TM, is capable to carry out three main detection techniques (amperometric, pulsed amperometric and coulometric detection) and a voltammetric technique (cyclic voltammetry). The instrumentation was successfully evaluated using the following systems: cyclic voltammograms of metallic electrodes in alkaline solutions, flow electrochemical detection of glucose and glycine and direct determination of herbicide glyphosate (electrochemical detection coupled to HPLC).

Temperature effects on the oscillatory electro-oxidation of methanol on platinum

We report in this paper the effect of temperature on the oscillatory electro-oxidation of methanol on polycrystalline platinum in aqueous sulfuric acid media. Potential oscillations were studied under galvanostatic control and at four temperatures ranging from 5 to 35 degrees C. For a given temperature, the departure from thermodynamic equilibrium does not affect the oscillation period and results in a slight increase of the oscillation amplitude. Apparent activation energies were also evaluated in voltammetric and chronoamperometric experiments and were compared to those obtained under oscillatory conditions. In any case, the apparent activation energies values fell into the region between 50 and 70 kJ mol(-1). Specifically under oscillatory conditions an apparent activation energy of 60 +/- 3 kJ mol(-1) and a temperature coefficient q(10) of about 2.3 were observed. The present findings extend our recently published report (J. Phys. Chem. A, 2008, 112, 4617) on the temperature effect on the oscillatory electro-oxidation of formic acid. We found that, despite the fact that both studies were carried out under similar conditions, unlike the case of formic acid, only conventional, Arrhenius, dynamics was observed for methanol.

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.

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.

Exploiting Pulsed Flows for Heating Improvement: Application to Determination of Total Reducing Sugars in Molasses and Sugar-Cane Juices

Laminar and pulsed flows typical of multi-commuted and multi-pumping flow systems, were evaluated in relation to analytical procedures carried out at high temperatures. As application, the spectrophotometric determination of total reducing sugars (TRS, hydrolyzed sucrose plus reducing sugars) in sugar-cane juice and molasses was selected. The method involves in-line hydrolysis of sucrose and alkaline degradation of the reducing sugars at about 98 degrees C. Better results were obtained with pulsed flows, due to the efficient radial mass transport inherent to the multi-pumping flow system. The proposed system presents favorable characteristics of ruggedness, analytical precision (r.s.d. < 0.013 for typical samples), stability (no measurable baseline drift during 4-h working periods), linearity of the analytical curve (r > 0.992, n = 5, 0.05-0.50% w/v TRS) and sampling rate (65 h(-1)). Results are in agreement with ion chromatography.

Numerical modelling of contaminant transport in coastal aquifers

This paper employs a two-dimensional variable density flow and transport model to investigate the transport of a dense contaminant plume in an unconfined coastal aquifer. Experimental results are also presented to show the contaminant plume in a freshwater-seawater flow system. Both the numerical and experimental results suggest that the neglect of the seawater interface does not noticeably affect the horizontal migration rate of the plume before it reaches the interface. However, the contaminant will travel further seaward and part of the solute mass will exit under the sea if the higher seawater density is not included. If the seawater density is included, the contaminant will travel upwards towards the beach along the freshwater-saltwater interface as shown experimentally. Neglect of seawater density, therefore, will result in an underestimate of solute mass rate exiting around the coastline. (C) 2002 IMACS. Published by Elsevier Science B.V. All rights reserved.

Determinación de sistemas de flujo regionales y locales en las depresiones tectónicas del Baix Empordà y La Selva (NE de España) en base a datos hidroquímicos e isotópicos

The Baix Empordà-Selva-Gavarres aquifer system is related to the fault set that created the tectonic basins of Empordà and Selva areas (NE Spain) during the Neogene. In this work, we describe groundwater hydrogeological, hydrochemical and isotopical (3H, δD, δ18O, and the 87Sr/86Sr ratio) characteristics of this system in order to illustrate the relevance of fault zones in groundwater flow-paths and the recharge. In that way, we identify two flow systems, with distinct hydrochemistry and isotopes. A local flow system originates at the Gavarres Range, and it flows towards the basins of the Baix Empordà and Selva, with an approximate residence time of 20 years. Additionally, a regional flow system has only been identified in the Selva basin. This one is related to the main fault zones, as preferential flow paths. Its recharge is located in mountain ranges with higher altitudes, namely the Transversal and Guilleries Ranges, with residence times larger than 50 years. Isotopical data has also shown mixing processes between both flow systems and rainfall recharge while multivariate statistical analysis of principal components has shown the main processes that control hydrochemistry of each flow systems

Competitive sorption and desorption of phosphate and citrate in clayey and sandy loam soils

The increase of organic acids in soils can reduce phosphorus sorption. The objective of the study was to evaluate the competitive sorption of P and citrate in clayey and sandy loam soils, using a stirred-flow system. Three experiments were performed with soil samples (0-20 cm layer) of clayey (RYL-cl) and sandy loam (RYL-sl) Red Yellow Latosols (Oxisols). In the first study, the treatments were arranged in a 2 × 5 factorial design, with two soil types and five combinations of phosphorus and citrate application (only P; P + citrate; and citrate applied 7, 22, 52 min before P); in the second, the treatments were arranged in a 2 × 2 factorial design, corresponding to two soils and two forms of P and citrate application (only citrate and citrate + P); and in the third study, the treatments in a 2 × 2 × 6 factorial design consisted of two soils, two extractors (citrate and water) and six incubation times. In the RYL-cl and RYL-sl, P sorption was highest (44 and 25 % of P application, respectively), in the absence of citrate application. Under citrate application, P sorption was reduced in all treatments. The combined application of citrate and P reduced P sorption to 25.8 % of the initially applied P in RYL-cl and to 16.7 % in RYL-sl, in comparison to P without citrate. Citrate sorption in RYL-cl and RYL-sl was highest in the absence of P application, corresponding to 32.0 and 30.2 % of the citrate applied, respectively. With P application, citrate sorption was reduced to 26.4 and 19.7 % of the initially applied citrate in RYL-cl and RYL-sl, respectively. Phosphorus desorption was greater when citrate was used. Phosphorus desorption with citrate and water was higher in the beginning (until 24 h of incubation of P) in RYL-cl and RYL-sl, indicating a rapid initial phase, followed by a slow release phase. This suggests that according to the contact time of P with the soil colloids, the previously adsorbed P can be released to the soil solution in the presence of competing ligands such as citrate. In conclusion, a soil management with continuous input of organic acids is desirable, in view of their potential to compete for P sorption sites, especially in rather weathered soils.

Multicomutação e amostragem binária em análise química em fluxo: determinação espectrofotométrica de ortofosfato em águas naturais

A flow system based on multicommutation and binary sampling process was developed to implement the sample zone trapping technique in order to increase the spectrophotometric analytical range and to improve sensitivity. The flow network was designed with active devices in order to provide facilities to determine sequentialy analyte with a wide concentration range, employing a single pumping channel to propel sample and reagents solutions. The procedure was employed to determine ortophosphate ions in water samples of river and waste. Profitable features such as an analytical throughput of 60 samples determination per hour, relative standard deviation (r.s.d.) of 2% (n = 6) for a typical sample with concentration of 2.78 mg/L were achieved. By applying the paired t-test no significant difference at 95% confidence level was observed between the results obtained with the proposed system and those of the usual flow injection system.

Determinação espectrofotométrica de ácido ascórbico em fármacos empregando amostragem binária em fluxo

A flow system procedure for spectrophotometric determination of ascorbic acid in drugs based on [Fe3+(SCN-)n]+3-n complex decomposition by reduction is described. The flow network was constituted by a set of three-way solenoid valves, controlled by a microcomputer running a software wrote in QuickBasic 4.5 language. The feasibility of the procedure was ascertained by determining ascorbic acid in drug samples with mass ranging from 0.0018 up to 0.0180 g. The results showed an agreement of about 7% when compared with recommended method. Other profitable features such as a standard deviation of 1.5% (n = 7) and a throughput of 120 determinations per hour was also achieved.

Construção e avaliação de um eletrodo tubular sensível ao íon hidrogênio como detector em sistemas de análise em fluxo

The construction of a tubular hydrogen ion-selective potentiometric electrode without inner reference solution, based on the tridodecylamine (TDDA) ionophore, and its evaluation in a flow system are described. TDDA was dissolved in 2-nitrophenyl octyl ether, dispersed in a PVC membrane and applied directly to a conducting support which consisted of an epoxy resin and graphite mixture. The electrode was designed with a tubular geometry to effort facilities to be coupled as part of a flow injection network. The main working characteristics such as response time, linear pH range, selectivity and life time were evaluated and compared with those obtained which a conventionally shaped electrode based on the same sensor. The electrode showed a slope of 51-52 mV dec-1 within a linear pH range from 4.0 up to 12.0.

Determinações multi-elementares de metais, Sulfato e Cloreto em amostras de águas por espectrometria de massas com fonte de plasma (ICP-MS)

The multi-element determination of Al, Cr, Mn, Ni, Cu, Zn, Cd, Ba, Pb, SO4= and Cl- in riverine water samples was accomplished by inductively coupled plasma mass spectrometry (ICP-MS). The sample passed through a column containing the anionic resin AG1-X8 and the metals were determined directly. The retained anionic species were eluted and SO4= and Cl- were determined at m/z 48 and 35 correspondent to the ions SO+ and Cl+ formed at the plasma. Accuracy for metals was assessed by analysing the certified reference TM-26 (National Water Research Institute of Canada). Results for SO4= and Cl- were in agreement with those obtained by turbidimetry and spectrophotometry. LOD's of 0.1 µg l-1 for Cd, Ba and Pb; 0.2 µg l-1 for Al, Mn and Cu; 0.5 µg l-1 for Cr; 0.9 for Zn; 2.0 µg l-1for Ni , 60 µg l-1 for S and 200 µg l-1 Cl were attained.

Uma célula simples para adaptação de eletrodos seletivos comerciais em sistemas de análises em fluxo

A simple flow cell for potentiometric detection is described. It was assembled by making use of two perspex pieces fixed together by means of four screws, and allow the connection of plane membrane conventional electrodes to flow system. Details about its construction are presented. The device performance was evaluated by making use of a cyanide ion-selective electrode. The relative standard deviation was about 0.5% with a detection limit of 8.0 x 10-6 mol CN- dm-3. Under experimental conditions, the linear range was 10-5 to10-2 mol dm-3.