Solid-phase microextraction and gas chromatography-mass spectrometry for the determination of polycyclic aromatic hydrocarbons in environmental solid matrices

A solid-phase microextraction (SPME) and gas chromatography-mass spectrometry method for determining polycyclic aromatic hydrocarbons (PAHs) in environmental solid matrices is developed. Investigated matrices include seaweed (Undaria pinnatifida and Himanthalia elongata), humic substances (isolated from a wetland out-flow and purchased from Aldrich), and soil. Optimal conditions for a good SPME efficiency of 16 hydrocarbon compounds are obtained using a 100- micro m polydimethylsiloxane fiber directly immersed in aqueous carrier medium. The method is remarkable for presenting short extraction times and considerably high sensitivities. The SPME results obtained by using internal calibration give the total analyte concentration based on the identical partitioning behavior of native and spiked pollutants. The detection limits range from 0.001 to 0.1 mg of PAH per kilogram of dry matrix. SPME external calibration provides information regarding freely dissolved analytes. The detection limits range from 0.001 to 0.05 micro g of PAH per liter of carrier medium. The SPME with external calibration procedure can be applied to measure free concentrations of a target compound spiked into a carrier medium and onto a matrix. Based on a comparison of results obtained for the two samples, the partitioning of the target analyte between the matrix and the carrier medium is calculated.     

Equilibrium in Saturated Ca(OH)2 Solutions: Parameters and Dissociation Constants

A new computer program has been developed for the calculation of pH, pOH, hydroxide ion concentration m _OH, species distribution coefficients _i, ionic activity coefficients _i ionic strength I, buffer capacity , solubility product K _s0, and the two dissociation constants, K _b1 and K _b2, corresponding, respectively, to first and second dissociation steps of Ca(OH)₂ in aqueous solution. Previously developed methodology, for the calculation of pH, _i, _i I, and parameters of pH buffer solutions, starting from the corresponding acidity constants, has been adapted for the case of aqueous Ca(OH)₂ solutions, for which the pertinent stoichiometric relationships are different from those applicable to mixtures of acids and their salts. The results show that, contrary to what is currently assumed, the first dissociation is far from complete. Values are given for the concentrations and activities of species Ca(OH)₂(aq), Ca(OH)⁺(aq), and Ca²⁺ (aq) in saturated calcium hydroxide solutions at 25°C.     

Analysis of ecdysteroids by micellar electrokinetic chromatography with on-line preconcentration

In order to enhance the UV detection sensitivity, an application study of an on-line preconcentration technique for micellar electrokinetic chromatographic (MEKC) was carried out. The simultaneous determination of four test ecdysteroids, 20-hydroxyecdysone, ajugasterone C, polypodine B and ponasterone A has been investigated by using the normal stacking mode in MEKC with UV detection. The effects of anionic surfactant composition and concentration, the applied voltage, the pH buffer, the kind and the amount of organic solvent and the injection time on the analyte resolution were evaluated. The optimised conditions for the separation involved the use of a 50 mM borate as the running buffer containing 50 mM of a mixture of sodium dodecyl sulphate (SDS) and sodium cholate (SC) in the ratio of 1:1 together with a concentration of 10% (v/v) of 2-PrOH at pH 9.0. Hydrodynamic injection of 12 s at 50 mbar and separation voltage of 20 kV at temperature of 20 degrees C were employed. These conditions allowed a repeatability separation within 21 min. Concentration detection limit for the neutral analytes studied improve about an order of magnitude. The method was also applied to the determination of ecdysteroids in a real sample.     

On the design and performance of printed-circuit filters and diplexers for millimeter-wave integrated circuits

This paper describes the design and performance of various millimeter-wave printed-circuit filters and diplexers. These components include microstrip/suspended stripline and finline lowpass filters, capacitive-gap and inductive-iris-coupled bandpass filters, spurline bandstop filters, and finline diplexers. State-of-the-art performances from Ka-band (26.5 to 40 GHz) to D-band (110 to 170 GHz) have been obtained. Agreement between the measured and calculated results was also achieved.     

Meeting the Requirements of the Silver/Silver Chloride Reference Electrode

Potentiometric cells from which the pH values of standard buffer solutions are computed rely on the silver–silver chloride reference electrode which has proved to be convenient, reproducible and reliable. Of the various methods of preparation of silver-silver chloride electrodes only one concerns us here: the thermal–electrolytic type that has been used more extensively than any other form. Once prepared, the electrodes need to be equilibrated before use and between experiments. The equilibration technique must ensure voltage stability and inter-electrode, or bias, potential below 0.1 mV. In potentiometry the stability of a reference electrode is of utmost importance since an offset of 1 mV is equivalent to a deviation of about 0.02 in the pH value.     

DSC Application in the Conservation Field

Differential scanning calorimetry (DSC) has been scarcely used in conservation field and in particular, in the study of painting layers. However DSC is a micro-destructive technique (sample from .05 to 1 mg can be analysed) because no pre-treatment of the sample is required and so it can give rapid and useful information. The aim of the present work is, in fact, to describe useful applications of DSC on the study of materials used in art. The analyses have been conducted under oxygen flow in order to register the thermo-oxidative reactions of the organic binder or protective. In the first part of the paper, materials of different chemical composition have been analysed to build up a data base of DSC profiles. Standard painting layers artificially degraded by treatment with ultraviolet light (365 nm) for 21 days and with NO_x (5 ppm)have be en analysed. Comparing the behaviour of the treated to the reference sample, it is useful to study what kind of changes the treatments have produced on the sample. Another possible application of DSC is the study of the formation of the film; analysing the raw,liquid binders and the different naturally aged films an evolution of the chemical structure canbe registered. As a conclusion, DSC analyses on standard used in artistic field allow to investigate their thermal behaviour and to understand the effect of natural and artificial ageing. This revised version was published online in July 2006 with corrections to the Cover Date.     

Phase Doppler measurements of spray impact onto rigid walls

In this work, an experimental study of spray impact onto a horizontal flat and rigid surface is presented. The phase Doppler technique has been used to characterize both the impacting and the secondary spray in terms of mass and number flux, size distribution and velocities of the droplets above the target. A high-resolution CCD camera has been used to measure the average liquid film thickness formed due to spray impact, whereas a high-speed CMOS camera has been used to characterize the splashing droplets from the wall. This visualization of the splashing phenomenon and the knowledge about the liquid film thickness are used to formulate a new physical model of the crown evolution. Furthermore, information about the incident-to-ejected mass fraction and number fraction are novel contributions of this study. Considerable data are provided comparing the impact of single drops onto a liquid film to impact of drops in a spray, and the significance of the observed differences for modelling efforts is discussed. The measurements of this study are also shown to be rather sensitive to the placement of the phase Doppler measurement volume above the surface and to the operating parameters of the instrument. These effects have been documented and discussed for this particular measurement situation.