RESUMEN

The photocatalytic and mechanical performance of TiO2 nanotubular coatings obtained by anodic oxidation of commercial titanium, using an NH4F and 3.5% v/v water in ethylene glycol solution as electrolyte was investigated. After the anodization, the coatings were thermally treated at 450 °C for 2 h. The effects of the anodizing voltage (40-80 V) and NH4F concentration (0.06, 0.15, 0.27 M) on the formation of the nanotube arrays were evaluated. Nanotube diameters (57 to 114 nm), wall thicknesses (4 to 13 nm), and lengths (5 to 17 µm) increased with the anodizing voltage and the NH4F concentration. The photocatalysts were characterized by scanning electron microscopy, glancing incidence X-ray diffraction, and UV-Vis diffuse reflectance spectroscopy. The mechanical properties of the photocatalysts were determined: adhesion using the tape test (ASTM D3359) and erosion resistance through a 3 h accelerated test. The photocatalytic activity of the nanotubes under UV irradiation was evaluated using hexavalent chromium (Cr(VI)) in the presence of ethylenediaminetetraacetic acid (EDTA), using a 1.25 EDTA/Cr(VI) molar ratio solution at pH 2. A complete Cr(VI) transformation after 3 h of irradiation was obtained for all samples, with a better performance than that of an immobilized P25 sample. The photocatalyst obtained with 0.27 M NH4F at 40 V presented a good behavior in adherence and erosion resistance, together with a very good photocatalytic activity. This novel analysis, combining photocatalytic and mechanical tests, proved that the new TiO2 nanotubular coatings could be successfully used as immobilized photocatalysts in photoreactors for water treatment.

Asunto(s)

RESUMEN

The catalytic performance of a perovskite-type lanthanum ferrite LaFeO3 to remove arsenic from water has been investigates for the first time. LaFeO3 was prepared by citrate auto-combustion of dry gel obtained from a solution of the corresponding nitrates poured into citric acid solution. Kinetic studies were performed in the dark with As(V) and in the dark and under UV-C irradiation at pH 6-7 with As(III) (both 1 mg L-1 ), and As : Fe molar ratios (MR) of 1 : 10 and 1 : 100 using the LaFeO3 catalyst. As(V) was removed from solution after 60 min in the dark in 7 % and in 47 % for MR=1 : 10 and MR=1 : 100, respectively, indicating the importance of the amount of the iron material on the removal. Oxidation of As(III) in the dark was negligible after 60 min in contact with the solid sample, but complete removal of As(III) was observed within 60 min of irradiation at 254 nm, due to As(III) photooxidation to As(V) and to As(III) sorption to a minor extent. Morphological and microstructural studies of the catalyst complement the catalytic testing. This work demonstrates that LaFeO3 can be used for the removal of As(III) from highly arsenic contaminated water.

RESUMEN

The sonochemical (850 kHz) Cr(VI) reduction (0.30 mM, pH 2) in the presence of citric acid (Cit, 2 mM) was analyzed under different working atmospheres: reactor open to air without sparging (ROAWS), and Ar, O2, air and N2 sparging. Hydrogen peroxide formation in pure water at pH 2 and KI dosimetry were also measured. Zero-order kinetics was observed in all cases. A complete Cr(VI) reduction after 180 min insonation was obtained with the ROAWS and under Ar, while a lower Cr(VI) reduction efficiency was achieved under the other conditions. The Cr(VI) reduction and H2O2 formation rates followed the order ROAWS â‰… Ar > air â‰… O2 ≫ N2, while for KI dosimetry the order was ROAWS â‰« O2 â‰… air > Ar â‰« N2. This indicates that H2O2 formation rate is a better measure of the system reactivity for Cr(VI) reduction. For air, O2 and N2, once the sparging was stopped, Cr(VI) reduction rate increased up to approximately the same value obtained for the ROAWS, suggesting that the sparging decreased the generation of reactive species and, thus, the Cr(VI) reduction rate. Nitrate production was measured at low concentrations (micromolar range) in the ROAWS, air and N2 systems. Formic and acetic acids were detected as Cit degradation products. Reaction mechanisms were proposed. It can be concluded that the best condition for Cr(VI) removal is with the ROAWS because of a higher Cr(VI) reduction rate, no atmosphere control is required, and it is a less expensive system.

Asunto(s)

RESUMEN

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.

RESUMEN

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.

Asunto(s)

RESUMEN

Iron-based nanoparticles were synthesized by a rapid method at room temperature using yerba mate (YM) extracts with FeCl3 in different proportions. Materials prepared from green tea (GT) extracts were also synthesized for comparison. These materials were thoroughly characterized by chemical analyses, XRD, magnetization, SEM-EDS, TEM-SAED, FTIR, UV-Vis, Raman, Mössbauer and XANES spectroscopies, and BET area analysis. It was concluded that the products are nonmagnetic iron complexes of the components of the extracts. The applicability of the materials for Cr(VI) (300 µM) removal from aqueous solutions at pH 3 using two Cr(VI):Fe molar ratios (MR), 1:3 and 1:0.5, has been tested. At Cr(VI):Fe MR = 1:3, the best YM materials gave complete Cr(VI) removal after two minutes of contact, similar to that obtained with commercial nanoscale zerovalent iron (N25), with dissolved Fe(II), and with a likewise prepared GT material. At a lower Cr(VI):Fe MR (1:0.5), although Cr(VI) removal was not complete after 20 min of reaction, the YM nanoparticles were more efficient than N25, GT nanoparticles and Fe(II) in solution. The results suggest that an optimal Cr(VI):Fe MR ratio could be reached when using the new YM nanoparticles, able to achieve a complete Cr(VI) reduction, and leaving very low Cr and Fe concentrations in the treated solutions. The rapid preparation of the nanoparticles would allow their use in removal of pollutants in soils and groundwater by direct injection of the mixture of precursors.

Asunto(s)

RESUMEN

The sonochemical (850 kHz) reduction of Cr(VI) (0.3 mM, pH 2, reactor open to air) was analyzed in the presence of different additives. The effects on Cr(VI) reduction efficiency of added formic acid (FA, 10 mM), citric acid (Cit, 2 mM), ethylenediaminetetraacetic acid (EDTA, 1 mM), methanol (MeOH, 0.1 M), ethanol (EtOH, 0.1 M), 2-propanol (2-PrOH, 0.1 M), tert-butanol (t-BuOH, 0.1 M), phenol (PhOH, 2 mM) and sodium lauryl sulfate (SLS, 1 mM) have been evaluated in comparison with the system in the absence of additives. Complete Cr(VI) reduction was obtained only when using EDTA (at 120 min) and Cit (at 180 min). Cr(III) complexes with these compounds or with their degradation products were detected as final products. For EDTA, Cit, t-BuOH, FA and SLS, the Cr(VI) decay could be adjusted to a zero-order kinetics; in the cases of MeOH, EtOH and 2-PrOH, there was a deviation from the zero-order kinetics. The Cr(VI) conversion increased in the order SLS (very low) < no additive ≅ MeOH ≅ EtOH ≅ 2-PrOH < FA < t-BuOH < PhOH < Cit < EDTA. The role of EDTA and Cit in stabilizing intermediate Cr(V) peroxo compounds and enhancing their direct transformation into different Cr(III) species is considered a major factor in the acceleration of Cr(VI) reduction processes. Mechanistic pathways are proposed.

RESUMEN

Reactive Black 5, RB5, has been used as a model azo dye to evaluate the removal efficiency of sorption on Macrocystis pyrifera biomass (Mpyr) and commercial zerovalent iron nanoparticles (nZVI) in individual and combined treatments. The best conditions for the treatment with the isolated materials were first determined, and then, in series and combined treatments were performed under these conditions, achieving removal efficiencies higher than 80% of the initial dye concentration. Strengths and weaknesses of all removal strategies (individual, in series and combined) are analyzed regarding the application on real effluents. Mpyr efficiently adsorbed RB5, but also increased the total organic content by partial dissolution of components of the algal biomass. Removal experiments with commercial nZVI were also efficient but liberated Fe to the solution, and sulfanilic acid was observed after the treatment as a product of RB5 degradation. In contrast, after the Mpyr treatment, no sulfanilic acid was detected, suggesting that sulfanilic acid is efficiently adsorbed by the biomass. The best condition was the integrated use of Mpyr and nZVI, with a remarkable removal efficiency (69-80%) obtained after only 1 h of treatment. Finally, nZVI were successfully immobilized in Mpyr, and the hybrid material was used to remove RB5 in continuous flow experiments at pH 3, obtaining a removal capacity of 39.9 mg RB5 g-1 after a total processed volume of 630 mL of [RB5]0 = 100 mg L-1.

Asunto(s)

RESUMEN

The dynamics of the transfer of electrons stored in TiO2 nanoparticles to As(III) , As(V) , and uranyl nitrate in water was investigated by using the stopped-flow technique. Suspensions of TiO2 nanoparticles with stored trapped electrons (etrap (-) ) were mixed with solutions of acceptor species to evaluate the reactivity by following the temporal evolution of etrap (-) by the decrease in the absorbance at λ=600 nm. The results indicate that As(V) and As(III) cannot be reduced by etrap (-) under the reaction conditions. In addition, it was observed that the presence of As(V) and As(III) strongly modified the reaction rate between O2 and etrap (-) : an increase in the rate was observed if As(V) was present and a decrease in the rate was observed in the presence of As(III) . In contrast with the As system, U(VI) was observed to react easily with etrap (-) and U(IV) formation was observed spectroscopically at λ=650 nm. The possible competence of U(VI) and NO3 (-) for their reduction by etrap (-) was analyzed. The inhibition of the U(VI) photocatalytic reduction by O2 could be attributed to the fast oxidation of U(V) and/or U(IV) .

RESUMEN

Toxicity of a Cr(VI) solution before and after treatment by TiO2 heterogeneous photocatalysis (HP) was performed with AMPHITOX bioassay. Changes in toxicity on Rhinella arenarum larvae for 10-d were monitored after exposure to an untreated Cr(VI) solution and to the same solution after HP treatment. The HP treatment of a 41.60 mg L(-1) Cr(VI) solution reduced to 37.5% the concentration of the metal ion. A 10-fold reduction in toxicity at acute exposure (72 h) and 150-fold reduction in toxicity after 240 h was found. Further, the LOEC value increased from 0.001% for the untreated solution to 0.153% after HP treatment. Moreover, the safe concentration in untreated solution corresponded to 0.0001% sample, and it was 0.01% after the treatment, i.e., 100 times higher. A saving of water of about 100,000 L per L of effluent would be possible through dilution to allow safer concentrations for discharge; the saving would reach the highest value (1,000,000 L per L) at 240 h. Sub-lethal effects were completely absent in larvae exposed to the treated solution. The AMPHITOX test allowed to detect chronic effects at low Cr concentrations, i.e. at environmentally relevant levels.

Asunto(s)

RESUMEN

Four million people in Argentina are exposed to arsenic contamination from drinking waters of several center-northern provinces. A systematic review to examine the geographical distribution of arsenic-related diseases in Argentina was conducted, searching electronic databases and gray literature up to November 2013. Key informants were also contacted. Of the 430 references identified, 47 (mostly cross-sectional and ecological designs) referred to arsenic concentration in water and its relationship with the incidence and mortality of cancer, dermatological diseases and genetic disorders. A high percentage of the water samples had arsenic concentrations above the WHO threshold value of 10µg/L, especially in the province of Buenos Aires. The median prevalence of arsenicosis was 2.6% in exposed areas. The proportion of skin cancer in patients with arsenicosis reached 88% in case-series from the Buenos Aires province. We found higher incidence rate ratios per 100µg/L increment in inorganic arsenic concentration for colorectal, lung, breast, prostate and skin cancer, for both genders. Liver and skin cancer mortality risk ratios were higher in regions with medium/high concentrations than in those with low concentrations. The relative risk of mortality by skin cancer associated to arsenic exposure in the province of Buenos Aires ranged from 2.5 to 5.2. In the north of this province, high levels of arsenic in drinking water were reported; however, removal interventions were scarcely documented. Arsenic contamination in Argentina is associated with an increased risk of serious chronic diseases, including cancer, showing the need for adequate and timely actions.

Asunto(s)

RESUMEN

The dynamics of the transfer of electrons stored in TiO2 nanoparticles to Cr(VI) in aqueous solution have been investigated using the stopped flow technique. TiO2 nanoparticles were previously irradiated under UV light in the presence of formic acid, and trapped electrons (e(trap)(-)) were made to react with Cr(VI) as acceptor species; other common acceptor species such as O2 and H2O2 were also tested. The temporal evolution of the number of trapped electrons was followed by the decrease in the absorbance at 600 nm, and the kinetics of the electron-transfer reaction was modeled. Additionally, the rate of formation of the surface complex between Cr(VI) and TiO2 was determined with the stopped flow technique by following the evolution of the absorbance at 400 nm of suspensions of nonirradiated TiO2 nanoparticles and Cr(VI) at different concentrations. An approximately quadratic relationship was observed between the maximum absorbance of the surface complex and the concentration of Cr(VI), suggesting that Cr(VI) adsorbs onto the TiO2 surface as dichromate. The kinetic analyses indicate that the electron transfer from TiO2 to Cr(VI) does not require the previous formation of the Cr(VI)-TiO2 surface complex, at least the complex detected here through the stopped flow experiments. When previously irradiated TiO2 was used to follow the evolution of the Cr(VI)-TiO2 complex, an inhibition of the formation of the complex was observed, which can be related to the TiO2 deactivation caused by Cr(III) deposition.

RESUMEN

Numerous articles have reported the occurrence of arsenic in drinking water in Argentina, and the resulting health effects in severely affected regions of the country. Arsenic in drinking water in Argentina is largely naturally occurring due to elevated background content of the metalloid in volcanic sediments, although, in some regions, mining can contribute. While the origin of arsenic release has been discussed extensively, the problem of drinking water contamination has not yet been solved. One key step in progress towards mitigation of problems related with the consumption of As-containing water is the availability of simple detection tools. A chemical test kit and the ARSOlux biosensor were evaluated as simple analytical tools for field measurements of arsenic in the groundwater of Rafaela (Santa Fe, Argentina), and the results were compared with ICP-MS and HPLC-ICP-MS measurements. A survey of the groundwater chemistry was performed to evaluate possible interferences with the field tests. The results showed that the ARSOlux biosensor performed better than the chemical field test, that the predominant species of arsenic in the study area was arsenate and that arsenic concentration in the studied samples had a positive correlation with fluoride and vanadium, and a negative one with calcium and iron.

Asunto(s)

RESUMEN

As previous studies have shown, the photocatalytic reduction of Cr(VI) to Cr(III) in the presence of 4-chlorophenol can be carried out efficiently under visible irradiation using TiO2 modified with hydroxoaluminum-tricarboxymonoamide phthalocyanine (AlTCPc) in spite of the high aggregation tendency of the dye. In the present work, photocurrent and absorption spectra of AlTCPc modified TiO2 films are studied together with absorption and fluorescence of the dye in solution as a function of the concentration of the dye to clarify (a) the role of aggregates and the nature of the species responsible for electron injection into the semiconductor and (b) the reasons why, as reported earlier, the photocatalytic activity is nearly independent of dye loading at constant TiO2 mass. Results are consistent with the presence of AlTCPc clusters with similar properties both on the TiO2 surface and in H2O-DMSO solution. The actual photoactive species is the monomeric dye electronically coupled to the semiconductor. Monomer concentration depends only slightly on AlTCPc analytical concentration, in a way similar to surfactant monomers in micellar equilibrium, thus explaining the independence of photocatalytic activity on dye concentration.

RESUMEN

UV irradiation of an ethanolic sol of TiO2 nanoparticles produces a trapped Ti(III) centre and a noticeable Burstein shift. Direct evidence that the accumulated charges can drive the otherwise forbidden reduction of As(V) by conduction band electrons is presented.

RESUMEN

Heterogeneous photocatalytic reduction of As(V) and As(III) at different concentrations over TiO(2) under UV light in deoxygenated aqueous suspensions is described. For the first time, As(0) was unambiguously identified together with arsine (AsH(3)) as reaction products. As(V) reduction requires the presence of an electron donor (methanol in the present case) and takes place through the hydroxymethyl radical formed from methanol oxidation by holes or hydroxyl radicals. On the contrary, As(III) reduction takes place through direct reduction by the TiO(2)-conduction band electrons. Detailed mechanisms for the photocatalytic processes are proposed. Although reduction to solid As(0) is convenient for purposes of As removal from water as a deposit on TiO(2), attention must be paid to formation of AsH(3), one of the most toxic forms of As, and strategies for AsH(3) treatment should be considered.

Asunto(s)

RESUMEN

Small-scale and household low-cost technologies to provide water free of arsenic for drinking purposes, suitable for isolated rural and periurban areas not connected to water networks in Latin America are described. Some of them are merely adaptation of conventional technologies already used at large and medium scale, but others are environmentally friendly emerging procedures that use local materials and resources of the affected zone. The technologies require simple and low-cost equipment that can be easily handled and maintained by the local population. The methods are based on the following processes: combination of coagulation/flocculation with adsorption, adsorption with geological and other low-cost natural materials, electrochemical technologies, biological methods including phytoremediation, use of zerovalent iron and photochemical processes. Examples of relevant research studies and developments in the region are given. In some cases, processes have been tested only at the laboratory level and there is not enough information about the costs. However, it is considered that the presented technologies constitute potential alternatives for arsenic removal in isolated rural and periurban localities of Latin America. Generation, handling and adequate disposal of residues should be taken into account in all cases.

Asunto(s)

RESUMEN

Use of natural geological materials for arsenic (As) removal is an emerging solution at a household level for poor people in remote rural settlements, especially when the materials are locally available and can be collected by the local population. Their low or zero cost makes these materials very attractive compared with synthetic or commercial materials. Sometimes, this may be the only option to provide safe water to very poor settlements. Their suitability for As removal from water is mainly due to adsorption, co-precipitation and ion exchange processes involving Fe- and Al-rich minerals and clay minerals present in the soils or sediments. In the present study, various clay-rich soils from the Santiago del Estero province (SDE, NW Argentina) and, for comparison, a laterite from the Misiones province have been tested as adsorbents for As in shallow naturally contaminated groundwaters of the Río Dulce alluvial aquifer in SDE. Batch adsorption experiments showed higher As(V) removal for the Misiones laterite sample (99 %) as compared with the soils from SDE (40-53 %), which can be related to lower contents of water-soluble and oxalate extractable Al and Fe in the last samples. These results suggest the application of the Misiones laterite soil as an alternative for As removal. However, high transportation costs from Misiones to SDE can be an economical restriction for the low-income population of SDE.

Asunto(s)

RESUMEN

At present, 70 countries worldwide are affected by groundwater contamination by arsenic (As) released from predominantly geogenic sources. Consequently, the As problem is becoming a global issue. The option to target As-safe aquifers, which uses geological, geochemical, hydrogeological, morphological and climatic similarities to delimit As-safe aquifers, appears as a sustainable mitigation option. Two pilot areas, Meghna Flood Plain in Matlab Upazila, representative of Bengal Delta in Bangladesh, and Río Dulce Alluvial Cone, representing a typical aquifer setting in the Chaco-Pampean Plain in Argentina groundwater As occurrence, were compared. In rural Bangladesh, As removal techniques have been provided to the population, but with low social acceptance. In contrast, "targeting As-safe aquifers" was socially accepted in Bangladesh, where sediment color could be used to identify As-safe aquifer zones and to install safe wells. The investigation in Argentina is more complex because of very different conditions and sources of As. Targeting As-safe aquifers could be a sustainable option for many rural areas and isolated peri-urban areas.

Asunto(s)

RESUMEN

Considering the toxic effects of arsenic, the World Health Organization recommends a maximum concentration of 10 microg L(-1) of arsenic in drinking water. Latin American populations present severe health problems due to consumption of waters with high arsenic contents. The physicochemical properties of surface and groundwaters are different from those of other more studied regions of the planet, and the problem is still publicly unknown. Methods for arsenic removal suitable to be applied in Latin American waters are here summarized and commented. Conventional technologies (oxidation, coagulation-coprecipitation, adsorption, reverse osmosis, use of ion exchangers) are described, but emphasis is made in emergent decentralized economical methods as the use of inexpensive natural adsorbents, solar light technologies or biological treatments, as essential to palliate the situation in poor, isolated and dispersed populations of Latin American regions.

Asunto(s)