Exploring potooxidative degradation pathways of harmol and harmalol alkaloids in water: effects of pH, excitation sources and atmospheric conditions.

This work explores the photochemical degradation of cationic species of 7-hydroxy-1-methyl-2H-pyrido[3,4-b]indole or harmol (1C) and the corresponding partially hydrogenated derivative 7-hydroxy-1-methyl-3,4-dihydro-2H-pyrido[3,4-b]indole or harmalol (2C) in aqueous solution. UV-visible absorption and fluorescence emission spectroscopy coupled with multivariate data analysis (MCR-ALS and PARAFAC), HPLC and HRESI-MS techniques were used for both quantitative and qualitative analysis. The formation of hydrogen peroxide reactive oxygen species (ROS) was quantified, and the influence of pH, oxygen partial pressure and photoexcitation source on the photochemical degradation of both compounds was assessed. The potential implications on the biosynthesis of ßCs and their biological role in living systems are discussed.

Screening of neoplastic diseases by statistical analysis of urine fluorescence spectroscopic data. Application of multivariate techniques for enhancing classification.

The composition of human fluids is modified during the course of neoplastic diseases. Urine analysis offers the advantage of being a noninvasive method for which samples are easily and routinely collected from patients. In this work, urine fluorescence spectra recorded upon excitation at 405 nm were obtained from healthy volunteers and individuals with different oncologic pathologies. A large number of indexes, i.e., parameters obtained from spectral data which assist spectral features characterization, were developed to classify healthy and pathological populations. The discrimination ability of simple predictive indexes, obtained from spectra pretreated with different normalization procedures and by taking their derivatives, was statistically assessed. In addition, multivariate methods, such as principal component analysis and multivariate curve resolution by alternating least squares, were used to develop more elaborate indexes for distinguishing between healthy and pathological populations. All indexes were systematically evaluated on a statistical basis by in lab-developed routines capable of detecting outliers, judging the normal distribution of the indexes, evaluating variance homogeneity, testing the difference between the means of healthy and pathological populations, as well as performing a receiver operator curve analysis to assess the classification power of each index. Those indexes with the best performances were further combined to perform a linear discriminant analysis, which yielded a powerful classification algorithm with an area under the receiver operator curve of 0.986, a sensitivity of 97.7%, a specificity of 100%, and an overall accuracy of 98.8%. The present study shows that the statistical analysis of urine fluorescence data with a proper combination of multivariate techniques bears a high potential to develop massive screening tests for the early detection of oncologic pathologies.

Photophysics and photochemistry of carminic acid and related natural pigments.

Carminic acid (CA) and other related compounds have been widely used as dyes in cultural heritage, cosmetics and the food industry. Therefore, the study of their properties upon photoexcitation is particularly important. In this work, the photophysical and photochemical properties of CA, carminic lake and other related pigments in aqueous solutions are revisited. Novel quantitative information regarding the fate of the photoexcited states is provided including the efficiency of reactive oxygen species (ROS) photosensitized production (i.e., singlet oxygen and hydrogen peroxide) as well as the efficiency of nonradiative deactivation pathways. Laser-induced optoacoustic spectroscopy (LIOAS) data revealed that for all the investigated compounds, almost all the absorbed energy is released as prompt heat to the media. This is in agreement with the fact that other deactivation pathways, including fluorescence (ΦF ∼ 10-3-10-5), photochemical degradation (ΦR ∼ 10-4) and/or photosensitized ROS formation (ΦH2O2 < 10-5 and ΦΔ âˆ¼ 0), are negligible or null. In addition, a comprehensive investigation of the photodegradation of CA and lake is herein reported. The influence of different experimental parameters such as irradiation wavelength and oxygen partial pressure was evaluated. UV-vis absorption and fluorescence emission spectroscopy in combination with chemometric data analysis were used to elucidate the relevant aspects of the photodegradation mechanism involved and the spectroscopic features of the photoproducts generated. In aqueous media, CA follows an O2-dependent photochemical degradation when subject to elapsed photoexcitation in the UVB, UVA and visible regions. The photoproduct profile depends on the excitation wavelength giving rise to quite distinctive spectroscopic profiles. With respect to lake, our data suggest that upon photoexcitation, this pigment releases a CA-like chromophore that follows a similar fate to CA.

Carbamazepine Degradation Mediated by Light in the Presence of Humic Substances-Coated Magnetite Nanoparticles.

The use of iron-based nanomaterials for environmental remediation processes has recently received considerable attention. Here, we employed core-shell magnetite-humic acids nanoparticles as a heterogeneous photosensitizer and iron source in photo-Fenton reaction for the degradation of the psychiatric drug carbamazepine (CBZ). CBZ showed low photodegradation rates in the presence of the magnetic nanoparticles, whereas the addition of hydrogen peroxide at pH = 3 to the system drastically increased the abatement of the contaminant. The measured Fe2+ and Fe3+ profiles point to the generation of Fe3+ at the surface of the nanoparticles, indicating a heterogeneous oxidation of the contaminant mediated by hydroxyl radicals. Products with a higher transformation degree were observed in the photo-Fenton procedure and support the attack of the HO• radical on the CBZ molecule. Promising results encourage the use of the nanoparticles as efficient iron sources with enhanced magnet-sensitive properties, suitable for applications in photo-Fenton treatments for the purification of wastewater.

Light-induced full aromatization and hydroxylation of 7-methoxy-1-methyl-3,4-dihydro-2H-pyrido[3,4-b]indole alkaloid: Oxygen partial pressure as a key modulator of the photoproducts distribution.

Full-aromatic and partially hydrogenated ß-carboline (ßC) derivatives constitute a group of alkaloids widely distributed in a great variety of living systems. In plants and bacteria, tetrahydro-ßCs are the primary product of the Pictet-Spengler enzymatically catalyzed condensation. Tetrahydro-ßC skeleton is further modified giving rise to the formation of a vast set of derivatives including dihydro- and full-aromatic ßCs. However, in most of the cases, the later processes still remain unclear and other sources, such as photo-triggered reactions, deserve to be explored. In this context, the photophysic and photochemistry of 7-methoxy-1-methyl-3,4-dihydro-2H-pyrido[3,4-b]indole or harmaline (Hlina) in aqueous solution is reported herein. UV-visible absorption and fluorescence emission spectroscopy coupled with multivariate data analysis (PARAFAC), HPLC and HRESI-MS techniques were used for both quantitative and qualitative analysis. The formation singlet oxygen and hydrogen peroxide reactive oxygen species (ROS) was quantified and their role together with the influence of pH and oxygen partial pressure on the photochemical degradation of HlinaH+ was assessed. We report herein the first study on photochemical full-aromatization of a dihydro-ßC derivative. These results can shed some light on the ßCs biosynthesis and role in living systems.

Arsenic in Argentina: Technologies for arsenic removal from groundwater sources, investment costs and waste management practices.

An overview about the presence of arsenic (As) in groundwaters of Argentina, made by a transdisciplinary group of experts is presented. In this second part, the conventional and emerging technologies for As removal, management of wastes, and the initial investment costs of the proposed technologies, with emphasis on developments of local groups are described. Successful examples of real application of conventional and emerging technologies for As removal in waters for human consumption, for medium, small and rural and periurban communities are reported. In the country, the two most applied technologies for arsenic removal at a real scale are reverse osmosis and coagulation-adsorption-filtration processes using iron or aluminum salts or polyelectrolytes as coagulants. A decision tree to evaluate the possible technologies to be applied, based on the population size, the quality of the water and its intended use, is presented, including preliminary and indicative investment costs. Finally, a section discussing the treatment and final disposal of the liquid, semiliquid and solid wastes, generated by the application of the most used technologies, is included. Conclusions and recommendations, especially for isolated rural and periurban regions, have been added.

Arsenic in Argentina: Occurrence, human health, legislation and determination.

An overview about the presence of arsenic (As) in groundwaters of Argentina, made by a transdisciplinary group of experts is presented. Aspects on As occurrence, effects of As on human health, regulations regarding the maximum allowable amount of As in drinking water as well as bottled water, and analytical techniques for As determination are presented. The most affected region in Argentina is the Chaco-Pampean plain, covering around 10 million km2, where approximately 88% of 86 groundwater samples collected in 2007 exceeded the World Health Organization (WHO) guideline value. In the Salí river basin, As concentrations ranged from 11.4 to 1660 µg/L, with 100% of the samples above the WHO guideline value. In the Argentine Altiplano (Puna) and Subandean valleys, 61% of 62 samples collected from surface and groundwaters exceeded the WHO limit. Thus, it can be estimated that, at present, the population at risk in Argentina reaches around four million people. Pathologies derived from the chronic consumption of As, the metabolism of As in the human body and the effects of the different As chemical forms, gathered under the name HACRE (hidroarsenicismo crónico regional endémico in Spanish, for chronic regional endemic hydroarsenicism) are described. Regarding the regulations, the 10 µg/L limit recommended by the WHO and the United States Environmental Protection Agency has been incorporated in the Argentine Food Code, but the application is still on hold. In addition, there is disparity regarding the maximal admitted values in several provinces. Considerations about the As concentrations in bottled water are also presented. A survey indicates that there are several Argentine laboratories with the suitable equipment for As determination at 10 µg/L, although 66% of them are concentrated in Buenos Aires City, and in the Santa Fe, Córdoba and Buenos Aires provinces. Conclusions and recommendations of this first part are provided.

Photodynamic Therapy in HeLa Cells Incubated with Riboflavin and Pectin-coated Silver Nanoparticles.

Riboflavin (Rf) is an endogenous photosensitizer, which can participate in Type I and Type II processes. We have recently shown that the yield of the triplet excited states of Rf is enhanced in the presence of pectin-coated silver nanoparticles (Pec@AgNP) due to formation of a complex between Rf and Pec@AgNP (Rf-Pec@AgNP). Consequently, under aerobic conditions, the amounts of singlet molecular oxygen and superoxide radical anion generated are also larger in the presence of the nanoparticles. This result made us suspect that the nanoparticles could have a beneficial effect in Rf-based PDT. To prove this hypothesis, we here compared the photodamage in HeLa cells incubated with Rf in the presence and in the absence of Pec@AgNP applying several optical assays. We used fluorescence imaging of irradiated HeLa cells incubated with Annexin V and propidium iodide to evaluate the occurrence of apoptosis/necrosis, the reduction of the tetrazolium dye MTT to formazan and neutral red uptake to prove cell viability, as well as synchrotron infrared microscopy of single cells to evaluate possible structural changes of DNA and nuclear proteins. The enhanced photodamage observed in the presence of Pec@AgNP seems to indicate that Rf enters into the cells complexed with the nanoparticles.

DNA damage photo-induced by chloroharmine isomers: hydrolysis versus oxidation of nucleobases.

Photodynamic therapy (PDT) is an emerging clinical treatment currently being used against a wide range of both cancerous and noncancerous diseases. The search for new active photosensitizers as well as the development of novel selective delivery systems are the major challenges faced in the application of PDT. We investigated herein three chloroharmine derivatives (6-, 8- and 6,8-dichloroharmines) with quite promising intrinsic photochemical tunable properties and their ability to photoinduce DNA damage in order to elucidate the underlying photochemical mechanisms. Data revealed that the three compounds are quite efficient photosensitizers. The overall extent of photo-oxidative DNA damage induced by both 8-chloro-substituted ß-carbolines is higher than that induced by 6-chloro-harmine. The predominant type of lesion generated also depends on the position of the chlorine atom in the ß-carboline ring. Both 8-chloro-substituted ß-carbolines mostly oxidize purines via type I mechanism, whereas 6-chloro-harmine mainly behaves as a "clean" artificial photonuclease inducing single-strand breaks and site of base loss via proton transfer and concerted (HO--mediated) hydrolytic attack. The latter finding represents an exception to the general photosensitizing reactions and, to the best of our knowledge, this is the first time that this process is well documented. The controlled and selective production of different oxygen-independent lesions could be fine-tuned by simply changing the substituent groups in the ß-carboline ring. This could be a promising tool for the design and development of novel photo-therapeutic agents aimed to tackle hypoxic conditions shown in certain types of tumours.

Humic like substances for the treatment of scarcely soluble pollutants by mild photo-Fenton process.

Humic-like substances (HLS) extracted from urban wastes have been tested as auxiliaries for the photo-Fenton removal of thiabendazole (TBZ) under simulated sunlight. Experimental design methodology based on Doehlert matrices was employed to check the effects of hydrogen peroxide concentration, HLS amount as well as TBZ loading; this last parameter was studied in the range 25-100 mg/L, to include values below and above the limit of solubility at pH = 5. Very satisfactory results were reached when TBZ was above solubility if HLS and H2O2 amounts were high. This could be attributed to an interaction of HLS-TBZ that enhances the solubility of the pollutant. Additional evidence supporting the latter interaction was obtained by fluorescence measurements (excitation emission matrices) and parallel factor analysis (PARAFAC).

Imidazole and beta-carotene photoprotection against photodynamic therapy evaluated by synchrotron infrared microscopy.

In order to better understand the role of ß-carotene and imidazole on the Photodynamic Therapy (PDT) mechanism, synchrotron infrared microscopy was used to detect the associated intracellular biochemical modifications following the visible light irradiation of HeLa cells incubated with these compounds as typical hydrophobic and hydrophilic singlet oxygen quenchers, respectively. For this purpose, PDT was performed employing the hydrophilic sensitizer 5,10,15,20-Tetrakis (1-methyl-4-pyridinio) porphyrin tetra (p-toluenesulfonate), TMPyP, and the hydrophobic sensitizer 5-(4-Methoxycarboxyphenyl)-10,15,20-triphenyl-21H,23H-porphyrin. The single cell IR spectra of PDT-treated, PDT plus quencher-treated and control HeLa cells were recorded at the SOLEIL Synchrotron Infrared SMIS beamline targeting specifically the cell nucleus. Principal Component Analysis (PCA) was used to assess the IR spectral changes. PCA revealed that there is a frequency shift of the protein Amide I vibrational band for the assays with the TMPyP sensitizer, indicating changes in the protein secondary structures of the PDT-treated cancer cells compared to the controls. In addition, the scores in those cells treated with both quenchers appear to be similar to the controls indicating a photoprotective effect. Comparative experiments carried out with SKMEL-28 and HaCat cells showed non- significant photoprotective effects of ß-carotene and imidazole.

Soybean peroxidase immobilized onto silica-coated superparamagnetic iron oxide nanoparticles: Effect of silica layer on the enzymatic activity.

Peroxidase immobilization onto magnetic supports is considered an innovative strategy for the development of technologies that involves enzymes in wastewater treatment. In this work, magnetic biocatalysts were prepared by immobilization of soybean peroxidase (SBP) onto different silica-coated superparamagnetic iron oxide nanoparticles. The obtained magnetic biocatalysts were tested for the degradation of malachite green (MG), a pollutant often found in industrial wastewaters and with significant drawbacks for the human and environmental health. A deep physicochemical characterization of the materials was performed by means of X-ray diffraction (XRD), Fourier Transform Infrared Spectroscopy (FTIR), High Resolution-Transmission Electron Microscope (HR-TEM) and magnetization measurements among others techniques. Results showed high immobilization yield of SBP onto nanomaterials with excellent properties for magnetic recoverability. A partial loss of activity with respect to free SBP was observed, compatible with the modification of the conformational structure of the enzyme after immobilization. The structural modification depended on the amount (and thickness) of silica present in the hybrid materials and the activity yield of 43% was obtained for the best biocatalyst. Thermal stability and reusability capacity were also evaluated.

Photophysical and Photochemical Properties of Naturally Occurring normelinonine F and Melinonine F Alkaloids and Structurally Related N(2)- and/or N(9)-methyl-ß-carboline Derivatives.

In the present work, we have synthesized and fully characterized the photophysical and photochemical properties of a selected group of N-methyl-ß-carboline derivatives (9-methyl-ß-carbolines and iodine salts of 2-methyl- and 2,9-dimethyl-ß-carbolinium) in aqueous solutions, in the pH range 4.0-14.5. Moreover, despite the quite extensive studies reported in the literature regarding the overall photophysical behavior of N-unsubstituted ßCs, this work constitutes the first full and unambiguous characterization of anionic species of N-unsubstituted ßCs (norharmane, harmane and harmine), present in aqueous solution under highly alkaline conditions (pH > 13.0). Acid dissociation constants (Ka ), thermal stabilities, room temperature UV-visible absorption and fluorescence emission and excitation spectra, fluorescence quantum yields (ФF ) and fluorescence lifetimes (τF ), as well as quantum yields of singlet oxygen production (Ð¤Δ ) have been measured for all the studied compounds. Furthermore, for the first time to our knowledge, chemometric techniques (MCR-ALS and PARAFAC) were applied on these systems, providing relevant information about the equilibria and species involved. The impact of all the foregoing observations on the biological role, as well as the potential biotechnological applications of these compounds, is discussed.

Determining the molecular basis for the pH-dependent interaction between 2'-deoxynucleotides and 9H-pyrido[3,4-b]indole in its ground and electronic excited states.

Interaction between norharmane and three different 2'-deoxynucleotides (dNMP) (2'-deoxyguanosine 5'-monophosphate (dGMP), 2'-deoxyadenosine 5'-monophosphate (dAMP) and 2'-deoxycytidine 5'-monophosphate (dCMP)), in aqueous solution, was studied in the ground state by means of UV-vis and (1)H-NMR spectroscopy and in the first electronic excited state using steady-state and time-resolved fluorescence spectroscopy. In all cases, the norharmane-dNMP interaction dependence on the pH was examined. Possible mechanisms for the interaction of both ground and electronic excited states of norharmane with nucleotides are discussed. Spectroscopic, molecular modeling and chemometric analysis were performed to further characterize the chemical structure of the complexes formed and to get additional information concerning the interaction between dNMPs and norharmane.

Evaluation of the Hg2+ binding potential of fulvic acids from fluorescence excitation-emission matrices.

The effect of Hg(2+) on the fluorescence intensity of three fulvic acids (Pahokee Peat, Pony Lake and Suwannee River) was studied. The fluorescence intensity decreased in the presence of added Hg(2+), while the fluorescence lifetimes were independent of the concentration of Hg(2+) in solution. These results are indicative of ground-states association between the fulvic acids and Hg(2+) with formation of stable non-fluorescent complexes (static quenching process). The analysis of the excitation-emission matrices with the Singular Value Decomposition (SVD) and Multivariate Curve Resolution-Alternating Least Squares (MCR-ALS) methods provided additional valuable information regarding the binding properties between Hg(2+) ions and specific fluorescence components of the fulvic acids. The three fulvic acids were shown to contain the same three groups of fluorophores characterized by excitation/emission pairs in the following regions: (320-330 nm/425-450 nm), (370-375 nm/465-500 nm), (290-295 nm/370-395 nm). These pairs are almost not affected by the change of pH from 2.0 to 7.0. Ryan-Weber and modified Stern-Volmer methods were used to analyze the static fluorescence quenching of the individual components. Similar conditional stability constants of Hg(2+) binding for the three components were found by both methods. The obtained log K values are in the range of 4.4 to 5.4.

On the mechanism of Re(I)-carboxylate bond cleavage by perchloric acid: a kinetic and spectroscopic study.

We have studied the reaction between pz-CO(2)-Re(CO)(3)(bpy) and perchloric acid in acetonitrile by following the UV-vis and IR spectral changes in the reaction mixture. A fast equilibrium was found to be established between solvated protons, pz-CO(2)-Re(CO)(3)(bpy), and the protonated intermediate [pz-C(OH)O-Re(CO)(3)(bpy)](+) which finally yields pz-COOH and Re(CO)(3)(bpy)(CH(3)CN)(+) as reaction products. This intermediate has been characterized by UV-vis and IR spectroscopies and by DFT calculations. The fully optimized DFT/CPCM structures for pz-CO(2)-Re(CO)(3)(bpy) and [pz-C(OH)O-Re(CO)(3)(bpy)](+) were compared with the X-ray structure of pz-CO(2)-Re(CO)(3)(bpy). The structural parameters associated with the carboxyl group in the protonated intermediate are between those of pz-CO(2)-Re(CO)(3)(bpy) and pz-COOH. Multivariate curve resolution methods were employed to obtain the spectrum of the protonated intermediate and the concentration profiles from the full matrix of time-resolved UV-vis spectra. The proposed mechanism was numerically simulated by using Runge-Kutta methods. Model parameters were estimated by nonlinear regression fitting of the concentration profiles, yielding values of log(K) = 4.9 ± 0.3 and k = 0.16 ± 0.03 min(-1) for the formation equilibrium constant and the decay rate constant of the protonated intermediate, respectively.

Nitration of nitrobenzene in Fenton's processes.

Previous studies of nitrobenzene (NB) degradation by Fenton and photo-Fenton technologies have demonstrated the formation and accumulation of 1,3-dinitrobenzene (1,3-DNB) as a highly toxic reaction intermediate. In the present study, we analyze the conditions that favor 1,3-DNB formation during NB degradation by Fe(2+)/H(2)O(2), Fe(3+)/H(2)O(2), UV/Fe(3+)/H(2)O(2) or UV/H(2)O(2) processes. Nitration yields in Fenton, Fenton-like and photo-Fenton techniques were much higher than those observed in UV/H(2)O(2) systems. Besides, several tests showed that 1,3-DNB formation increases with the initial iron concentration and decreases as the initial H(2)O(2) concentration increases. In order to asses the key species involved in NB nitration mechanism, additional experiments were performed in the presence of NO(2)(-)or NO(3)(-). In dark systems, 1,3-DNB yield significantly increased with increasing [NO(2)(-)]_(0), while it was not affected by the presence of NO(3)(-). In contrast, 1,3-DNB yields were higher and more strongly affected by the additive concentration in UV/NO(3)(-) systems than in UV/HNO(2)/NO(2)(-) systems. Dark experiments performed at pH 1.5 in excess of HNO(2) along with UV/NO(3)(-) tests conducted in the presence of 2-propanol show that hydroxyl radicals play an important role in NB nitration since NB molecule does not react with the nitrating agents ONOOH, .NO or .NO(2). The results indicate that, in the experimental domain tested, the prevailing NB nitration pathway involves the reaction between the .OH-NB adduct and .NO(2) radicals.

Kinetics of nitrobenzene and 4-nitrophenol degradation by UV irradiation in the presence of nitrate and nitrite ions.

In the present work we analyze the degradation rates of nitrobenzene (NBE) and 4-nitrophenol (PNP), by using UV irradiation in the presence of HNO(2)/NO(2)(-) or NO(3)(-) added as sources of hydroxyl radicals. With both nitroaromatic substrates pseudo-first-order kinetics were observed for conversion degrees of at least 45% within the analyzed experimental domain. The apparent rate constants (k(app)) were higher for UV/NO(3)(-) systems than for UV/HNO(2)/NO(2)(-) systems at high additive concentrations, whereas the opposite trend was observed for low additive concentrations. In addition, k(app) values were found to decrease with increasing substrate concentration. The analysis of the distribution of the most important products detected by HPLC suggests that reactions involving nitrogen species are likely to play a secondary role in the apparent rate constants measured. NBE and PNP degradation rates induced by HNO(2)/NO(2)(-) photolysis increase to a maximum value and then decrease with increasing additive concentration. On the other hand, substrate degradation rates increase with NO(3)(-) concentrations until a plateau is reached, but no decrease of k(app) is observed even at very high additive concentrations. The results may be quantitatively described by a simplified model that considers two opposite effects. On the one hand, the increase of additive concentrations increases the amount of photons absorbed by the photoactive species in both systems. On the other hand, high additive concentrations significantly decrease the degradation rates in UV/HNO(2)/NO(2)(-) systems where HNO(2) and NO(2)(-) are efficient hydroxyl radical scavengers, whereas this decrease is not observed in UV/NO(3)(-) systems since the scavenging ability of NO(3)(-) is much lower. Inner filter and scavenging effects are discussed and the results are compared with the ones previously reported for UV/H(2)O(2) systems.

Abatimento de arsénico en aguas de consumo mediante el empleo de la técnica de hierro cero valente

El objetivo del trabajo ha sido caracterizar las variables que afectan la producción sostenible de Fe (III), intimamente relacionada con el mecanismo de remoción de arsénico, basado en procesos de remoción adsorción y/o coprecipitación. De acuerdo con los estudios realizados, la superficie de contacto de Fe cero valente, la disponibilidad de oxígeno y la presencia de sales en la matriz acuosa, son las variables que mayor influencia presentan en el proceso heterogéneo inicial de corrosión electroquímica. La segunda parte de este artículo se publica en el No. 93

Abatimento de arsénico en aguas de consumo mediante el empleo de la técnica de hierro cero valente

El objetivo del trabajo ha sido caracterizar las variables que afectan la producción sostenible de Fe (III), intimamente relacionada con el mecanismo de remoción de arsénico, basado en procesos de remoción adsorción y/o coprecipitación. De acuerdo con los estudios realizados, la superficie de contacto de Fe cero valente, la disponibilidad de oxígeno y la presencia de sales en la matriz acuosa, son las variables que mayor influencia presentan en el proceso heterogéneo inicial de corrosión electroquímica. La segunda parte de este artículo se publica en el No. 93