Paolo Pastore

Effect of eluent composition and pH and chemiluminescent reagent pH on ion chromatographic selectivity and luminol-based chemiluminescence detection of Co2+, Mn2+ and Fe2+ at trace levels

The alkaline-luminol/H(2)O(2)-based chemiluminescent (CL) detection of Fe(2+), Co(2+), and Mn(2+), separated with a Dionex CS5A ion chromatographic phase was studied by means of a multi-pump flow system allowing the variation of the post-column solution composition. A perchlorate gradient at pH 1.9 (with HCl) was used to separate cations partially complexed with 5.6mM oxalate present in the eluent and necessary for the chosen separation phase. A 0.91mM luminol, 3.3mM H(2)O(2) in 0.25M carbonate buffer at pH 10.5 composition was chosen as CL reagent solution. The chosen pH value warrants signal repeatability and wider linearity range although absolute signal is not maximum. The CL signal was related to the pH of the two post-column mixing solutions. Calibration plots of Co(2+) and Fe(2+) were linear in the chosen concentration range whilst a parabolic model was the best fit for Mn(2+). Detection limits were 0.24, 0.50 and 375nM for Co(2+), Fe(2+) and Mn(2+), respectively. The method was used to determine Co(2+) at trace level in commercial copper chelates used for animal feeding. A comparison with a chromatographic method with spectrophotometric detection was made giving results comparable both in absolute values and accuracy.

Performance of a numerical method based on the hopscotch algorithm and on an oblate spheroidal space coordinate-expanding time grid for simulation of v

Abstract The application of a simulation procedure which combines the Hopscoth alogrithm with a hyperbolic space grid in solving the initial value problems at an inlaid disk electrode for electrochemical processes of any reversibility degree is discussed. The importance of the resolution of the space and time grid in connection with the use of the Hopscotch algorithm and of the Butler-Volmer equation to gain good accuracy, is stressed. The improvements introduced to define analytically the diffusion layer at different mass transfer conditions and to save computing time with the use of an exponentially expanding time grid and a cubic-spline interpolation make the simulation algorithm suitable to regression procedures for parameter estimation.

Ion Chromatographic Determination of Nitrite in the Presence of a Large Amount of Chloride.

Abstract Different procedures for the quantitation of nitrite in the presence of a large excess of chloride are described. The results obtained show that, in general, solutions characterized by N0 2 - /Cl - ratios of about 1/10 000 can very easily be analyzed. The best results were obtained with amperometric detection in conjunction with NaCI as the eluent which allows ratios down to about 1/700 000 to be employed. One of the procedures investigated was successfully applied to the analysis of samples of sea-water from fish breeding pools.

Digital simulation via the hopscotch algorithm of a microelectrode-based channel flow-through amperometric detector

Abstract The current flowing at a band ultramicroelectrode in a rectangular channel under mass transfer-limited conditions is computed numerically. The procedure is based on the “hopscotch” algorithm and on an appropriate space transformation, δ = tanh( x /α). The edge effect is found to influence the response depending on the flow rate. The polarization times necessary to reach the steady-state current are also computed under different operating conditions.

Does seawater acidification affect survival, growth and shell integrity in bivalve juveniles?

Anthropogenic emissions of carbon dioxide are leading to decreases in pH and changes in the carbonate chemistry of seawater. Ocean acidification may negatively affect the ability of marine organisms to produce calcareous structures while also influencing their physiological responses and growth. The aim of this study was to evaluate the effects of reduced pH on the survival, growth and shell integrity of juveniles of two marine bivalves from the Northern Adriatic sea: the Mediterranean mussel Mytilus galloprovincialis and the striped venus clam Chamelea gallina. An outdoor flow-through plant was set up and two pH levels (natural seawater pH as a control, pH 7.4 as the treatment) were tested in long-term experiments. Mortality was low throughout the first experiment for both mussels and clams, but a significant increase, which was sensibly higher in clams, was observed at the end of the experiment (6 months). Significant decreases in the live weight (-26%) and, surprisingly, in the shell length (-5%) were observed in treated clams, but not in mussels. In the controls of both species, no shell damage was ever recorded; in the treated mussels and clams, damage proceeded via different modes and to different extents. The severity of shell injuries was maximal in the mussels after just 3 months of exposure to a reduced pH, whereas it progressively increased in clams until the end of the experiment. In shells of both species, the damaged area increased throughout the experiment, peaking at 35% in mussels and 11% in clams. The shell thickness of the treated and control animals significantly decreased after 3 months in clams and after 6 months in mussels. In the second experiment (3 months), only juvenile mussels were exposed to a reduced pH. After 3 months, the mussels at a natural pH level or pH 7.4 did not differ in their survival, shell length or live weight. Conversely, shell damage was clearly visible in the treated mussels from the 1st month onward. Monitoring the chemistry of seawater carbonates always showed aragonite undersaturation at 7.4 pH, whereas calcite undersaturation occurred in only 37% of the measurements. The present study highlighted the contrasting effects of acidification in two bivalve species living in the same region, although not exactly in the same habitat.

The use of nitrite ion in the chromatographic determination of large amounts of hypochlorite ion and of traces of chlorite and chlorate ions

An ion chromatographic procedure was developed for the one-run determination of ClO–, ClO2– and ClO3– present at very different concentration levels in the same sample. The method is based on the quantitative and fast reduction of HClO in slightly acidic medium by added sodium nitrite, followed by the ion chromatographic determination of ClO2–, ClO3– and the generated NO3–. The possibility of amperometric titration of the ‘free chlorine’ with a standard solution of NaNO2 was also ascertained. The performance characteristics of the analysis were defined.

Occurrence of PAH in the seasonal snowpack of the Eastern Italian Alps.

PAH concentrations have been determined in 47 seasonal snowpack samples collected in the Valbelluna valley and in the Bellunesi Dolomites National Park, in the Italian North-Eastern Alps, during the winter of 2005. The SigmaPAH concentration in high-altitude alpine sites (above 1700 m) was 32+/-20 ng/kg while in valley bottom urban areas it was 165+/-54 ng/kg with maximum values of 290 ng/kg. The GIS mapping technique was employed to produce a PAH spatial distribution. The urbanized Valbelluna valley, and in particular the SW part, had the highest accumulation of all PAH, with values an order of magnitude more than those in rural and alpine areas. This behaviour is consistent with urban air quality data, and is due to geo-morphological and meteorological factors such as the deeper shape of the valley at the position of the town of Feltre and the low altitude of the boundary layer during the winter season.

Radical scavenging and antimicrobial activities of Croton zehntneri, Pterodon emarginatus and Schinopsis brasiliensis essential oils and their major constituents: estragole, trans-anethole, β-caryophyllene and myrcene

The essential oils (EOs) from the Brazilian species Croton zehntneri, Pterodon emarginatus and Schinopsis brasiliensis were examined for their chemical constituents, and antioxidant and antimicrobial activities. The composition of EOs was determined by using gas chromatography coupled with mass spectrometry analysis, while the antioxidant activity was evaluated through the 1,1-diphenyl-2-picrylhydrazyl (DPPH) and oxygen radical absorbance capacity (ORAC) assays. Furthermore, the antimicrobial activity was investigated against Escherichia coli and Pseudomonas aeruginosa (both Gram-negative), Staphylococcus aureus (Gram-positive) and Candida parapsilosis (fungus). The main components of C. zehntneri, P. emarginatus and S. brasiliensis were identified as estragole, trans-anethole, β-caryophyllene and myrcene. Among the EOs, P. emarginatus showed the highest antioxidant activity, with an IC50 of 7.36 mg/mL and a Trolox equivalent antioxidant capacity of 3748 μmol/g determined by DPPH and ORAC assays, respectively. All EOs showed low activities against the bacterial strains tested, whereas the C. zehntneri oil and its main constituent estragole exhibited an appreciable antifungal activity against C. parapsilosis.

Comparison of the simplex, marquardt, and extended and iterated extended kalman filter procedures in the estimation of parameters from voltammetric curves

Abstract The use of the simplex, Marquardt, and extended and iterated extended Kalman filter nonlinear least-squares curve-fitting methods is examined for evaluation of parameters in linear-sweep and cyclic voltammetric curves. The EE mechanism (two-electron transfer) is considered as a reference process and the relevant results are compared on the basis of accuracy, computing time and robustness. The E° values for l -β-3,4-dihydroxyphenylalanine are calculated.

Application of LC‐MS and LC‐MS‐MS to the analysis of photo‐decomposed crystal violet in the investigation of cultural heritage materials aging

In this work, the accurate liquid chromatography-ultraviolet-visible (LC-UV-Vis), LC-mass spectrometry (MS) and LC-MS-MS analysis of the photo-degradation products of crystal violet (CV) is reported. CV is a light fugitive early synthetic dye which had a widespread diffusion into the market starting from the end of the XIX century and was used among others by V. Van Gogh and P. Gauguin in their writings, drawings or paintings. On-line photodiode array detector enabled simultaneous UV-Vis spectra acquisition. Many degradation compounds were identified through their exact mass (2 ppm accuracy) and MS-MS technique. In particular, all CV demethylated products, demethylated Michlers ketone and particularly some compounds that most likely contain oxygen, such as N-oxides, were found. Fragmentation products are all justified by the proposed fragmentation scheme, in term of precursor exact mass and isotopic profile, characteristic losses in fragmentation and rebuilt structure formula. In particular, we hypothesized the presence of N-imido oxides and hydroxylamine derivates, never reported before, together with the demethylated derivatives of the studied dyes. All these compounds, although at trace level in our samples, contribute to the discoloration and fading of works of arts made with CV. In particular, demethylation of CV by UV light leads to formation of compounds absorbing at shorter wavelengths than CV (blue shift) or no-absorbing in visible range (yellow-colourless) with an overall effect that may appear reddish-brown. This phenomenon justifies drawings appearing grey or brown on aged yellowed paper, when CV-based inks or paints were used. The final aim was to better characterize the photo-degradation of early synthetic dyes (in particular of CV) and to gain a better insight into the discoloration and fading of purple ink strokes made of CV.