experimental-protocol-to-determine-chloride-threshold-value-for

Experimental Protocol to Determine the Chloride Threshold Value for Corrosion in Samples Taken from Reinforced Concrete Structures

The aging of reinforced concrete infrastructure in developed countries imposes an urgent need for methods to reliably assess the condition of these ...

ETH Zurich

University of Cagliari

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 TNFalpha), 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, TNFalpha 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.

Quantitative evaluation of oxidative stress, chronic inflammatory indices and leptin in cancer patients: correlation with stage and performance status.

A systematic analytical study using X-ray photoelectron spectroscopy (XPS) and X-ray induced Auger electron spectroscopy (XAES) has been carried out to characterize the chemical state of arsenic in complex environmental samples. The conventional approach, which relies on the chemical shift of the core levels As3d, provides ambiguous results in determining the chemical environment of arsenic. A more accurate approach, based on the Auger parameter and on the Wagner (Chemical State) plot, which combines AsLMM kinetic energy and As3d binding energy, was adopted. This novel method for determining the chemical state of arsenic was employed to completely characterize arsenic in complex environmental samples.

The chemical state of arsenic in minerals of environmental interest--an XPS and an XAES study.

In this work, a multi-technical bulk and surface analytical approach was used to investigate the bioleaching of a pyrite and arsenopyrite flotation concentrate with a mixed microflora mainly consisting of Acidithiobacillus ferrooxidans. X-ray diffraction, X-ray photoelectron spectroscopy (XPS) and X-ray-induced Auger electron spectroscopy mineral surfaces investigations, along with inductively coupled plasma-atomic emission spectroscopy and carbon, hydrogen, nitrogen and sulphur determination (CHNS) analyses, were carried out prior and after bioleaching. The flotation concentrate was a mixture of pyrite (FeS(2)) and arsenopyrite (FeAsS); after bioleaching, 95% of the initial content of pyrite and 85% of arsenopyrite were dissolved. The chemical state of the main elements (Fe, As and S) at the surface of the bioreactor feed particles and of the residue after bioleaching was investigated by X-ray photoelectron and X-ray excited Auger electron spectroscopy. After bioleaching, no signals of iron, arsenic and sulphur originating from pyrite and arsenopyrite were detected, confirming a strong oxidation and the dissolution of the particles. On the surfaces of the mineral residue particles, elemental sulphur as reaction intermediate of the leaching process and precipitated secondary phases (Fe-OOH and jarosite), together with adsorbed arsenates, was detected. Evidence of microbial cells adhesion at mineral surfaces was also produced: carbon and nitrogen were revealed by CHNS, and nitrogen was also detected on the bioleached surfaces by XPS. This was attributed to the deposition, on the mineral surfaces, of the remnants of a bio-film consisting of an extra-cellular polymer layer that had favoured the bacterial action.

Arsenopyrite and pyrite bioleaching: evidence from XPS, XRD and ICP techniques.

Forecasting the life of concrete infrastructures in corrosive environments presents a long-standing and socially relevant challenge in science and engineering. Chloride-induced corrosion of reinforcing steel in concrete is the main cause for premature degradation of concrete infrastructures worldwide. Since the middle of the past century, this challenge has been tackled by using a conceptual approach relying on a threshold chloride concentration for corrosion initiation (Ccrit). All state-of-the-art models for forecasting chloride-induced steel corrosion in concrete are based on this concept. We present an experiment that shows that Ccrit depends strongly on the exposed steel surface area. The smaller the tested specimen is, the higher and the more variable Ccrit becomes. This size effect in the ability of reinforced concrete to withstand corrosion can be explained by the local conditions at the steel-concrete interface, which exhibit pronounced spatial variability. The size effect has major implications for the future use of the common concept of Ccrit. It questions the applicability of laboratory results to engineering structures and the reproducibility of typically small-scale laboratory testing. Finally, we show that the weakest link theory is suitable to transform Ccrit from small to large dimensions, which lays the basis for taking the size effect into account in the science and engineering of forecasting the durability of infrastructures.

Article	Year
Quantitative evaluation of oxidative stress, chronic inflammatory indices and leptin in cancer patients: correlation with stage and performance status. International journal of cancer\| PubMed ID: 11857390	2002
The chemical state of arsenic in minerals of environmental interest--an XPS and an XAES study. Annali di chimica\| PubMed ID: 12650569	2003
Arsenopyrite and pyrite bioleaching: evidence from XPS, XRD and ICP techniques. Analytical and bioanalytical chemistry\| PubMed ID: 21847529	2011
The size effect in corrosion greatly influences the predicted life span of concrete infrastructures. Science advances\| PubMed ID: 28782038	2017

Bernhard Elsener

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