Preconcentration of copper from natural water samples using ligand-less in situ surfactant-based solid phase extraction prior to FAAS determination

In the present work, a simple and rapid ligand-less, in situ, surfactant-based solid phase extraction for the preconcentration of copper in water samples was developed. In this method, a cationic surfactant (n-dodecyltrimethylammonium bromide) was dissolved in an aqueous sample followed by the addition of an appropriate ion-pairing agent (ClO4-). Due to the interaction between the surfactant and ion-pairing agent, solid particles were formed and subsequently used for the adsorption of Cu(OH)2 and CuI. After centrifugation, the sediment was dissolved in 1.0 mL of 1 mol L-1 HNO3 in ethanol and aspirated directly into the flame atomic absorption spectrometer. In order to obtain the optimum conditions, several parameters affecting the performance of the LL-ISS-SPE, including the volumes of DTAB, KClO4, and KI, pH, and potentially interfering ions, were optimized. It was found that KI and phosphate buffer solution (pH = 9) could extract more than 95% of copper ions. The amount of copper ions in the water samples varied from 3.2 to 4.8 ng mL-1, with relative standard deviations of 98.5%-103%. The determination of copper in water samples was linear over a concentration range of 0.5-200.0 ng mL-1. The limit of detection (3Sb/m) was 0.1 ng mL-1 with an enrichment factor of 38.7. The accuracy of the developed method was verified by the determination of copper in two certified reference materials, producing satisfactory results.

Digestão fotoquímica, assistida por microondas, de águas naturais: aplicação em estudos de partição e especiação do cobre

The efficiency of a new procedure for the digestion of natural waters, based on a microwave-activated photochemical reactor was evaluated in this work. Fluorescence spectra showed a 99% reduction in the emission of a 40 mg L-1 humic acid solution after 15 min of UV irradiation. In the presence of H2O2, only 3 min were necessary to accomplish a reduction of almost 100% in the emission and 6 min to reduce the concentration of dissolved organic carbon by 95%. The copper recovery from synthetic samples containing commercial humic acid, from soil suspensions, as well as from natural waters varied between 91.5 and 106.6%. The digestion of dissolved and unfiltered samples was successfully accomplished in 6 and 12 min, respectively. No contaminations or sample losses were observed. Results of copper speciation in natural waters showed that this metal is predominantly bound to natural ligands. Only 3-6% of the total recoverable copper is present in the labile form.

Determination of Hg in water by CVAAS using 2-aminothiazole modified silica

This paper discusses a rapid and sensitive method developed to determine trace levels of mercury in natural water samples by cold vapor atomic absorption spectrometry using a preconcentration system composed by mini-column packed with 100 mg of 2-aminothiazol modified silica gel (SiAT) coupled on-line with the spectrometer's cold vapor generator system. The optimum preconcentration conditions are also described here. The preconcentrated Hg(II) ions were eluted directly from the column to the spectrometer's cold vapor generator system using 100 µL of 2 mol L-1 hydrochloric acid and the retention efficiency achieved exceeded 95%. The enrichment factors determined were 29, 38 and 46 using 3, 4 and 5 mL of preconcentrated aqueous solutions containing 400 ng L-1 of Hg. The detection limit calculated was 5 ng L-1. The preconcentration procedure was applied to determine trace level mercury in spiked river water samples.

Clinical-epidemiological study of leptospirosis in humans and reservoirs in Yucatán, México

A leptospirosis clinical-epidemiological study was made in humans and reservoirs in the state of Yucatán, México. Interviews and serological analyses were made on 400 persons from an open population, 439 probable cases of leptospirosis and 1060 animal reservoirs (cows, pigs, dogs, rats and opossums). IgM Leptospira DipstickTM and Microscopic Agglutination Test (MAT) was used to detect human antibodies to leptospiras and serovar respectively. Leptospirosis incidence in humans was 2.2/100,000 inhab. in 1998, 0.7/100,000 in 1999 and 0.9/100,000 in 2000. Overall seroprevalence was 14.2%, relatively unchanged from seroprevalences observed 20 years ago. Highest seropositivity was found in people over 56 years of age, predominating males over females. Predominant serovars in the open population were tarassovi, hardjo, pomona and panama. Leptospirosis cases were most frequent in rural areas, and the anicteric course predominated over the icteric. The panama, icterohaemorrhagiae and pomona serovars predominated in both anicteric and icteric courses. Dogs, pigs and rodents had the highest seropositivity among the reservoirs. Contact with rodents and natural water sources were significant factors (p £ 0.05). Human cases (74%) occurred during the rainy season. It is concluded that leptospirosis is still a serious illness with important clinical and epidemiological implications in the state of Yucatán, Mexico.

Soil infiltration based on bp neural network and grey relational analysis

Soil infiltration is a key link of the natural water cycle process. Studies on soil permeability are conducive for water resources assessment and estimation, runoff regulation and management, soil erosion modeling, nonpoint and point source pollution of farmland, among other aspects. The unequal influence of rainfall duration, rainfall intensity, antecedent soil moisture, vegetation cover, vegetation type, and slope gradient on soil cumulative infiltration was studied under simulated rainfall and different underlying surfaces. We established a six factor-model of soil cumulative infiltration by the improved back propagation (BP)-based artificial neural network algorithm with a momentum term and self-adjusting learning rate. Compared to the multiple nonlinear regression method, the stability and accuracy of the improved BP algorithm was better. Based on the improved BP model, the sensitive index of these six factors on soil cumulative infiltration was investigated. Secondly, the grey relational analysis method was used to individually study grey correlations among these six factors and soil cumulative infiltration. The results of the two methods were very similar. Rainfall duration was the most influential factor, followed by vegetation cover, vegetation type, rainfall intensity and antecedent soil moisture. The effect of slope gradient on soil cumulative infiltration was not significant.

Determinação de arsênio em águas contaminadas usando fluorescência de raios-X por energia dispersiva

This work proposes a simple, fast and inexpensive method to determine As in natural waters, using X-ray fluorescence. 50 µL of each sample containing 100 mg L-1 of yttrium as internal standard were deposited over a 2.5 µm thickness MylarTM film. The samples were dried at 50 °C for 2 h. X-ray spectra were obtained using an EDXRF apparatus. The accuracy was determined by analyte addition/recovery and by comparison with Hydride Generation Atomic Absorption Spectrometry (HG AAS). A recovery of about 100% was obtained and the results were in good agreement with HG AAS. The method showed a relative standard deviation of 6.8% and a detection limit of 10.5 µg L-1 of As.

Un método de bajo costo para la determinación de cobre a nivel de vestigios en matrices de interés ambiental por espectrofotometría en fase sólida (EFS)

A method for determining copper by solid phase spectrophotometry (SPS) was optimized using the Doehlert design. Copper(II) was sorbed on a styrene-divinylbenzene anion-exchange resin as a Cu(II)-1-(2-pyridylazo)-2-naphthol (PAN) complex, at pH 7.0. Resin phase absorbances at 560 and 800 nm were measured directly. The detection limit was found to be 2.5 µg L-1. The relative standard deviation on ten replicate determinations of 10 µg Cu(II) in 1000 mL samples was 1.1%. The linear range of the determination was 5.0-100 µg L-1. The method was applied successfully to the determination of Cu(II) in natural water and vegetable samples.

Determinação simultânea de As, Cd e Pb em amostras de água purificada para hemodiálise por espectrometria de absorção atômica com forno de grafite, após otimização multivariada baseada no uso de planejamento experimental

This paper reports the development of a methodology for simultaneously determining As, Cd and Pb, employing GF AAS with polarized Zeeman-effect background correction. In order to make the procedure applicable, the influence of pyrolysis and atomization temperatures and the amount of chemical modifiers were studied. Factorial and central composite designs were used to optimize these variables. Precision and accuracy of the method were investigated using Natural Water Reference material, Nist SRM 1640. Results are in agreement with certified values at the 95% confidence limit when the Student t-test is used. This methodology was used for quality control of purified water for hemodialysis.

Fotocatálise heterogênea com TiO2 para oxidação de arsênio e sua remoção de águas por coprecipitação com sulfato férrico

The oxidation of arsenic (As(III) to As(V)) in water samples was performed by heterogeneous photocatalysis using a TiO2 film immobilized inside a photochemical reactor. After oxidation, As(V) was removed from the water samples by coprecipitation with ferric sulfate. The final conditions of oxidation and arsenic removal (TiO2 film prepared with a suspension: 10% (w/v); pH: 7.0; oxidation time: 30 min and Fe3+ concentration: 50 mg L-1) were applied in natural water samples which were supplemented with 1.0 mg L-1 of As(III) to verify the influence of the matrix. After treatment, more than 99% of arsenic was removed from the water.

Planejamento fatorial e superfície de resposta: otimização de um método voltamétrico para a determinação de ag(i) empregando um eletrodo de pasta de nanotubos de carbono

A factorial design applied in a voltammetric stripping method for the measurement of Ag(I) in natural water is described. The procedure is based on the effective pre-concentration of silver ions on electrode surface. The calibration graph was linear in the silver concentration range from 7.92 x 10"7 to 1.07 x 10"5 mol L"1 with a detection limit of 3.81 x 10-7 mol L-1. The determination of Ag(I) in natural water samples was carried out satisfactory with the proposed electrode.

Construction and application of a portable microcontrolled turbidimeter for the in situ determination of sulfate

This study reports on the construction of a turbidimeter employing light emitting diodes as radiation source at a wavelength of 405 nm, a photodiode as detector, a temperature sensor and a microcontroller used for data acquisition and processing. The turbidimeter was applied to determine sulfate concentrations in natural water employing barium chloride as reagent. Potential interferences and recovery studies were performed and an interference of 3.5 % and a recovery between 97.8 and 108 % were estimated. The analytical performance of in situ turbidimeter for the determination of sulfate was evaluated and compared with two commercial spectrophotometers and a good agreement was obtained.

Uso de hardware de código fonte aberto "Arduino" para acionamento de dispositivo solenoide em sistemas de análises em fluxo

This paper describes the use of the open source hardware platform, denominated "Arduino", for controlling solenoid valves for solutions handling in flow analysis systems. System assessment was carried out by spectrophotometric determination of iron (II) in natural water. The sampling rate was estimated as 45 determinations per hour and the coefficient of variation was lower than 3%. Per determination, 208 µg of 1-10-phenanthroline and ascorbic acid were consumed, generating 1.3 mL of waste. "Arduino" proved a reliable microcontroller with low cost and simple interfacing, allowing USB communication for solenoid device switching in flow systems.

Solid phase extraction of zinc with octadecyl silica membrane disks modified by N,N'-disalicylidene-1,2-phenylendiamine and determination by flame atomic absorption spectrometry

A procedure for separation and preconcentration of trace amounts of Zn(II) from aqueous media is proposed. The procedure is based on the adsorption of Zn2+ on octadecyl bonded silica membrane disk modified with N,N'-disalicylidene-1,2-phenylendiamine at pH 7. The retained zinc ions were then stripped from the disk with a minimal amount of 1.5 mol L-1 hydrochloric acid solution as eluent, and determined by flame atomic absorption spectrometry. Maximum capacity of the membrane disk modified with 5 mg of the ligand was found to be 226 µg Zn2+. The relative standard deviation of zinc for ten replicate extraction of 10 µg zinc from 1000 mL samples was 1.2%. The limit of detection of the proposed method was 14 ng of Zn2+ per 1000 mL. The method was successfully applied to the determination of zinc in natural water samples and accuracy was examined by recovery experiments and independent analysis by graphite furnace atomic absorption spectrometry (GFAAS).

Low-flow estimates in regions of extrapolation of the regionalization equations: a new concept

ABSTRACT Knowledge of natural water availability, which is characterized by low flows, is essential for planning and management of water resources. One of the most widely used hydrological techniques to determine streamflow is regionalization, but the extrapolation of regionalization equations beyond the limits of sample data is not recommended. This paper proposes a new method for reducing overestimation errors associated with the extrapolation of regionalization equations for low flows. The method is based on the use of a threshold value for the maximum specific low flow discharge estimated at the gauging sites that are used in the regionalization. When a specific low flow, which has been estimated using the regionalization equation, exceeds the threshold value, the low flow can be obtained by multiplying the drainage area by the threshold value. This restriction imposes a physical limit to the low flow, which reduces the error of overestimating flows in regions of extrapolation. A case study was done in the Urucuia river basin, in Brazil, and the results showed the regionalization equation to perform positively in reducing the risk of extrapolation.

Uses of natural zeolite in the removal of Pb2+ from contaminated water

In this paper, we carry out a study on the process of sorption of lead in polluted waters usingnatural zeolites, with the objective of analyzing their behavior in the purification of water.Experiments are carried out under static and dynamic conditions to determine the influence of other metal ions, such as: Ca (II), Mg (II), K (I) and Na (I), on this process. We demonstrate that the affinity of Pb (II) with regard to zeolite is higher than that of the ions mentioned above. It allows us to use this material in the capture of lead in residual waters. A lineal model of regression was obtained using a computer program called Eureka which relates the capacity of interchange of zeolite with respect to the concentration of the metal ions present in waters. We also studied the selectivity of zeolite in the process of sorption of Pb (II) compared with other heavy metals like Zn (II) and Cd (II).The results achieved in both cases increase the expectancy about the usage of zeolite as a low cost material for purifing waters.