The identification of surface sulfide and polysulfide species based on the curve fitting of S2p photoelectron\ud spectra and, for the first time, of X-ray excited S KLL Auger spectra has been performed. The different sulfur\ud chemical states present on the surface (sulfide S2, central S and terminal S in polysulfide chains) could be\ud unambiguously assigned in the chemical state plot. Sulfur atoms in the central or terminal position,\ud respectively, are found on a line with slope ca. 3 irrespective of the cation indicating similar initial state\ud effects. On the other hand, for a given polysulfide, e.g. K2Sn, sulfur atoms both in central or terminal\ud positions are found on the same line with slope 1 indicating similar final state effects. This behavior can\ud be rationalized with the fact that the negative charge in polysulfide chains is located mainly on sulfur\ud atoms in the terminal position; indeed, sulfur present as central S shows a binding energy shift of 0.6\ud eV with respect to elemental sulfur (S8), and sulfur in terminal S a shift of 2.4 eV. An application of this\ud approach tested on commercial alkali polysulfides is provided for the curve fitting of SKLL signals and\ud sulfur speciation of three different sulfide minerals enargite (Cu3AsS4), chalcopyrite (CuFeS2) and\ud arsenopyrite (FeAsS). Also for the surface of mineral sulfides, terminal S atoms and central S atoms in the\ud polysulfide chains can successfully be identified

Electrochemical impedance spectroscopy is used to monitor the long-term stability (up to 150 days) of mechanically polished commercial pure titanium, Ti6Al4V, Ti6Al7Nb, and CoCrMo alloys in 0.1M sodium sulfate and fetal bovine serum. A capacitive spectrum in the frequency range from 10(-3) to 10(5) Hz is always found and the impedance spectra can be fitted by a simple parallel RC circuit with a constant phase element. The open circuit potential observed in serum is always more cathodic and the polarization resistance (R(p)) is higher than that recorded in sodium sulfate solutions. The observed variation of the equivalent capacitance in serum bovine suggests that an adsorption layer of organic molecules develops on the electrode surface and it is responsible for both the decrease in open circuit potential and the higher R(p), because it hinders the oxygen evolution reaction and the charge transfer responsible for the passive film dissolution (or growth). Among the alloys studied, Ti6Al4V displayed the highest steady-state values of R(p) both in serum and in sodium sulfate.

In advanced cancer patients, the oxidative stress could take place either at the onset of disease or as a function of disease progression. To test this hypothesis, the following parameters were investigated: the erythrocyte activity of the enzymes superoxide dismutase (SOD) and glutathione peroxidase (GPx), the serum activity of glutathione reductase (GR) and the serum total antioxidant status (TAS). The total antioxidant capacity of plasma LMWA was evaluated by the cyclic voltammetry methodology. We further determined the serum levels of proinflammatory cytokines (IL-6 and TNF␣), IL-2, leptin and C-reactive protein (CRP). All of these parameters have been correlated with the most important clinical indices of patients such as Stage of disease, ECOG PS and clinical response. Eighty-two advanced stage cancer patients and 36 healthy individuals used as controls were included in the study. Our findings show that SOD activity was significantly higher in cancer patients than in controls and GPx activity was significantly lower in cancer patients than in controls. Serum values of IL-6, TNF␣ and CRP were significantly higher in patients than in controls. Serum leptin values of cancer patients were significantly lower than controls. SOD activity increased significantly from Stage II/ECOG 0-1 to Stage IV/ECOG 0 -1, whereas it decreased significantly in Stage IV/ECOG 3. GPx activity decreased significantly in Stage IV/ECOG 2-3. An inverse correlation between ECOG PS and serum leptin levels was found. Serum levels of IL-2 decreased from Stage II/ECOG 0 -1 to Stage IV/ECOG 2-3. A direct correlation between Stage/ECOG PS and serum levels of both IL-6 and CRP was observed. Cisplatin administration induced a significant increase of GPx after 24 hr. In conclusion, this is the first study that shows that several "biological" parameters of cancer patients such as antioxidant enzyme activity, cytokines, leptin and CRP strictly correlate with the most important clinical parameters of disease such as Stage and ECOG PS.

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The chloride content at the reinforcement is one of the decisive factors for the initiation and propagation of localised corrosion in concrete structures. A monitoring technique for the chloride concentration which is accurate, non-destructive and continuous would thus be highly desirable. For this reason, the performance of ion selective electrodes (ISEs) was investigated both in alkaline solutions and embedded in mortar. The Ag/AgCl electrodes used in this work showed Nernstian behaviour with a slope of -59 ± 1 mV per decade and a detection limit for chloride ions below 10 -2 mol dm -3 even at pH close to 14; the selectivity coefficient for hydroxide interference was estimated at k pot Cl À ;OH À % 4 Á 10 À3 . The Ag/AgCl membranes show good long-term stability over more than 6 months even in highly alkaline solutions as long as chloride ions are present; in the complete absence of chloride the measured potentials were affected by the pH of the solution. The sensors are, however, able to recover fast as soon as they come into contact with chloride. When using ISEs embedded in concrete, diffusion potentials between the reference electrode and the ISE, as arising e.g. from gradients in pH, significantly affect the potential measurement and present a most important error source for the application of direct potentiometry to concrete. To minimise such errors, the reference electrode has to be positioned as close to the ISE as possible.

Electroless Ni-P alloys are produced as coatings on a broad variety of substrates. They exhibit a corrosion resistance that is superior to pure nickel but do not form a NiO oxide film (passive film) as pure nickel does. Despite the fact that many mechanisms have been proposed to explain this superior corrosion behaviour, no consensus has yet been reached. In this work electrochemical and XPS surface analytical methods have been combined in order to gain a deeper insight into the mechanisms underlying the corrosion resistance of electroless deposited Ni-P alloys with phosphorus content between 18 and 22 at.%. The anodic polarization curves in acidic and neutral solutions confirm a broad current plateau followed by a region with increasing current density. During potentiostatic polarization in the plateau region the current decays according to a power law with exponent ca. -0.5 indicating diffusion-limited dissolution of nickel. XPS/XAES measurements performed after potentiostatic polarization show that phosphorus is present in three different chemical environments. Based on the Auger parameter concept and on the chemical state plot, the three phosphorus states were assigned to phosphorus in the bulk alloy, phosphates and an intermediate phosphorus compound attributed to elemental phosphorus. Angle-resolved XPS analysis has shown that the elemental phosphorus is enriched at the interface between the alloy and the outermost surface in contact with the corrosive solution. These results suggest the following conclusions: the high corrosion resistance of electroless deposited Ni-P alloys can be explained by a strong enrichment of elemental phosphorus at the interface which limits the dissolution of nickel via a diffusion mechanism. A complementary explanation--not yet advanced--for the high corrosion resistance may lie in the electronic state of nickel in the Ni-P alloys.

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