Multiparametric optimization of a new high-sensitive and disposable mercury (II) electrochemical sensor.

An electrochemical sensor for mercury (II) determination was developed by modifying the surface of a commercial screen-printed carbon electrode (SPCE) with a polystyrene sulfonate-NiO-carbon nanopowder composite material. Mercury measurements were performed by differential pulse anodic stripping voltammetry (DPASV). Sensor composition and measurement conditions were optimized using a multivariate experiment design. A screening experiment by using a Plackett-Burman design was first performed in order to determine the main contributing factors to the electrochemical response. The most important factors were employed to establish the interactions between different experimental variables and get the best conditions for mercury determination. For this purpose, a five level central composite design and a response surface methodology were used. The optimized method using the developed NiO-PSS-SPCE sensor presents a very low limit of detection of 0.021 µg L(-1) and a linear response over two concentration ranges with two different slopes, from 0.05 to 2.0 µg L(-1) and between 2.0 and 75 µg L(-1). The sensor was successfully applied to mercury determination in water samples.

Interaction of organic contaminants with natural clay type geosorbents: potential use as geologic barrier in urban landfill.

The aim of this work is to characterize the capability of several clay materials as preservative of organic pollution for use as landfill barrier. Interaction of representative organic pollutants with different polarity and water solubility (atrazine, benzamide, methomyl, paraquat and toluene) with several clay materials coming from several locations of Spain were studied. Batch suspension method was used to study the pesticide adsorption onto the clay sorbents in solution conditions that simulate the composition of a young leachate in its aerobic acetogenic stage (pH=5 and I=0.15) The obtained data of the analytes sorption were modelized by several sorption isotherm models, and the best fitted data were got with a generalized Langmuir adsorption isotherm. The higher maxima adsorptions were observed for paraquat (50-62 mmol kg(-1)) and toluene (19-34 mmol kg(-1)) whereas more hydrophobic compounds present lower adsorption (0.7-2.5 mmol kg(-1)). Paraquat is the compound that presents the higher bonding coefficients. Therefore these clays could be used as components of the multibarriers in controlled urban landfill.

Pollution profiles and physicochemical parameters in old uncontrolled landfills.

The long-term effectiveness of the geological barrier beneath municipal-waste landfills is a critical issue for soil and groundwater protection. This study examines natural clayey soils directly in contact with the waste deposited in three landfills over 12 years old in Spain. Several physicochemical and geological parameters were measured as a function of depth. Electrical conductivity (EC), water-soluble organic carbon (WSOC), Cl(-), NH(4)(+), Na(+) and exchangeable NH(4)(+) and Na(+) were used as parameters to measure the penetration of landfill leachate pollution. Mineralogy, specific surface area and cationic-exchange capacities were analyzed to characterize the materials under the landfills. A principal component analysis, combined with a Varimax rotation, was applied to the data to determine patterns of association between samples and variables not evident upon initial inspection. The main factors explaining the variation in the data are related to waste composition and local geology. Although leachates have been in contact with clays for long time periods (13-24 years), WSOC and EC fronts are attenuated at depths of 0.2-1.5m within the clay layer. Taking into account this depth of the clayey materials, these natural substrata (>45% illite-smectite-type sheet silicates) are suitable for confining leachate pollution and for complying with European legislation. This paper outlines the relevant differences in the clayey materials of the three landfills in which a diffusive flux attenuation capacity (A(c)) is defined as a function (1) of the rate of decrease of the parameters per meter of material, (2) of the age and area of the landfill and (3) of the quantity and quality of the wastes.

Neurologic complications associated with hepatitis C virus infection.

A series of nine patients with neurologic complications of hepatitis C virus infection is reported. Seven patients presented a combination of chronic sensory polyneuropathy, multineuropathy, and encephalopathy related to cryoglobulinemia. The noncryoglobulinemic symptoms consisted of an anterior optic neuropathy and a restless legs syndrome with small-fiber neuropathy. Corticosteroids and cyclophosphamide were useful in controlling vasculitic episodes. Interferon-alpha caused remission in half of the treated patients.

Thiohydrazone copper(II) complexes. The relationship between redox properties and superoxide dismutase mimetic activity.

The redox behaviour of copper(II) complexes with the open chain ligand, benzilbisthiosemicarbazone, and the macrocyclic one [3,4,10,11-tetraphenyl-1,2,5,8,9,12,13-octaazacyclotetradeca-7,14- dithione- 2,4,9,11-tetraene] has been explored by cyclic voltammetry. The half-wave potential values for the copper(II)/copper(I) redox couple and the spectral data obtained on dimethylsulfoxide (DMSO) solution agree with the superoxide dismutase (SOD)-mimetic activity of the complexes. The macrocyclic complexes show more positive reduction potential and more activity than the open chain derivatives. From our results it follows that the structure and conformation of ligand has influence on the redox potential of central atom in coordination compound. The changes in the coordination sphere are connected with the change of biological function of compounds represented by SOD-mimic activity. In addition, the L1H6 derivatives show quasireversible waves associated to Cu(II)/Cu(III) process.

HPLC analysis of thimerosal and its degradation products in ophthalmic solutions with electrochemical detection.

A reverse-phase high-performance liquid chromatographic assay using amperometric detection on a glassy-carbon electrode has been developed for analysis of thimerosal and its main degradation products, thiosalicylic acid and dithiodibenzoic acid, in ophthalmic formulations. A potential value of 0.9 V vs. Ag/AgCl was chosen for simultaneous detection of thimerosal and thiosalicylic acid, obtaining limits of detection of 1.0 and 0.2 ng injected, respectively. A potential value of 1.2V was applied for simultaneous determination of all three compounds studied, obtaining in this case limits of detection of 3,4 and 4 ng injected for thimerosal, thiosalicylic acid and dithiodibenzoic acid, respectively. The results obtained reveal the utility of the HPLC method in quality control of commercial products containing thimerosal with good detectability.