Homogeneous and heterogeneous degradation of caffeic acid using photocatalysis driven by UVA and solar light.

Waste water from the wine industry is characterized by a high concentration of dissolved organic matter and the presence of natural phenolic compounds with low biodegradability. High concentrations of phenolic compounds may cause environmental pollution and risks to human health. In this article caffeic acid (CA) was used as a model compound of wine effluent because it is refractory to the conventional wastewater treatments. The oxidation of caffeic acid in water solution (0.01 g L(-1)) by heterogeneous photocatalysis and photo-Fenton reaction was studied using UVA. The optimal conditions for each treatment were performed by multivariate experimental design. The optimal conditions for heterogeneous photocatalysis were pH 5.3 and 0.9 g L(-1) TiO2. In the case of photo-Fenton treatment, optimized variable were 82.4 µmol L(-1) of Fe(2+) and 558.6 µmol L(-1) of H2O2. The degradation profiles of CA were monitored by UV-Vis, HPLC, TOC and COD. To reach 90% of CA removal, 40 and 2 min of reaction, respectively, were required by heterogeneous and photo-Fenton processes, respectively. For comparison purposes, the reactions were also performed under solar light. The use of solar light does not change the efficiency of the photo-Fenton reaction, yet the performance of the heterogeneous process was significantly improved, reaching 90% of degradation in 15 min.

Urinary arsenic speciation profile in ethnic group of the Atacama desert (Chile) exposed to variable arsenic levels in drinking water.

Ethnic groups from the Atacama Desert (known as Atacameños) have been exposed to natural arsenic pollution for over 5000 years. This work presents an integral study that characterizes arsenic species in water used for human consumption. It also describes the metabolism and arsenic elimination through urine in a chronically exposed population in northern Chile. In this region, water contained total arsenic concentrations up to 1250 µg L(-1), which was almost exclusively As(V). It is also important that this water was ingested directly from natural water sources without any treatment. The ingested arsenic was extensively methylated. In urine 93% of the arsenic was found as methylated arsenic species, such as monomethylarsonic acid [MMA(V)] and dimethylarsinic acid [DMA(V)]. The original ingested inorganic species [As(V)], represent less than 1% of the total urinary arsenic. Methylation activity among individuals can be assessed by measuring primary [inorganic As/methylated As] and secondary methylation [MMA/DMA] indexes. Both methylation indexes were 0.06, indicating a high biological converting capability of As(V) into MMA and then MMA into DMA, compared with the control population and other arsenic exposed populations previously reported.

Efecto del aumento de la temperatura, frecuencia de alimentación y ración de alimento en el crecimiento de juveniles de turbot psetta maxima / Effect of increased temperature, frequency and feed ration on growth of juvenile turbot psetta maxima

Se determina la influencia del aumento de la temperatura (17 a 20°C), la ración (2,5 por ciento a 3,5 por ciento del peso día) y la frecuencia de alimentación (4 a 6 veces día), en el crecimiento y la supervivencia de juveniles de turbot (Psetta maxima) en un sistema productivo comercial durante 35 días. Los resultados muestran que el crecimiento de los juveniles provenientes del nuevo protocolo de cultivo experimental ensayado es mayor y muestra una tasa específica de crecimiento, significativamente diferente respecto a los cultivados con el protocolo base, sin afectar la supervivencia, la que se mantiene en 99,8 por ciento. Se sugiere realizar mayores estudios para aislar o definir exactamente el efecto sinérgico de las variables definidas, así como complementar los resultados obtenidos con un estudio econométrico que evalúe su real aporte económico dentro de la cadena productiva del cultivo...

The influence of water temperature (17 and 20°C), frequency (4 and 6) and feed ration level (2.5 percent and 3.5 percent) on the growth and survival of juvenile turbot (Psetta maxima) in a commercial productive system was investigated over 35 days. The results indicate that fish from the experimental protocol exhibited better growth and significant difference in specific growth rate than those raised with basic protocol, without affecting survival that remains at 99.8 percent. It is suggested further studies to isolate or define exactly the synergistic effect of the variables defined and complement the results obtained with an econometric study which evaluate their real economic contribution within the productive chain of culture...

Arsenic in volcanic geothermal fluids of Latin America.

Numerous volcanoes, hot springs, fumaroles, and geothermal wells occur in the Pacific region of Latin America. These systems are characterized by high As concentrations and other typical geothermal elements such as Li and B. This paper presents a review of the available data on As concentrations in geothermal systems and their surficial discharges and As data on volcanic gases of Latin America. Data for geothermal systems in Mexico, Guatemala, Honduras, El Salvador, Nicaragua, Costa Rica, Ecuador, Bolivia, and Chile are presented. Two sources of As can be recognized in the investigated sites: Arsenic partitioned into volcanic gases and emitted in plumes and fumaroles, and arsenic in rocks of volcanic edifices that are leached by groundwaters enriched in volcanic gases. Water containing the most elevated concentrations of As are mature Na-Cl fluids with relatively low sulfate content and As concentrations reaching up to 73.6 mg L⁻¹ (Los Humeros geothermal field in Mexico), but more commonly ranging from a few mg L⁻¹ to tens of mg L⁻¹. Fluids derived from Na-Cl enriched waters formed through evaporation and condensation at shallower depths have As levels of only a few µg L⁻¹. Mixing of Na-Cl waters with shallower meteoric waters results in low to intermediate As concentrations (up to a few mg L⁻¹). After the waters are discharged at the ground surface, As(III) oxidizes to As(V) and attenuation of As concentration can occur due to sorption and co-precipitation processes with iron minerals and organic matter present in sediments. Understanding the mechanisms of As enrichment in geothermal waters and their fate upon mixing with shallower groundwater and surface waters is important for the protection of water resources in Latin America.

One century of arsenic exposure in Latin America: a review of history and occurrence from 14 countries.

The global impact on public health of elevated arsenic (As) in water supplies is highlighted by an increasing number of countries worldwide reporting high As concentrations in drinking water. In Latin America, the problem of As contamination in water is known in 14 out of 20 countries: Argentina, Bolivia, Brazil, Chile, Colombia, Cuba, Ecuador, El Salvador, Guatemala, Honduras, Mexico, Nicaragua, Peru and Uruguay. Considering the 10 µg/L limit for As in drinking water established by international and several national agencies, the number of exposed people is estimated to be about 14 million. Health effects of As exposure were identified for the first time already in the 1910s in Bellville (Córdoba province, Argentina). Nevertheless, contamination of As in waters has been detected in 10 Latin American countries only within the last 10 to 15 years. Arsenic is mobilized predominantly from young volcanic rocks and their weathering products. In alluvial aquifers, which are water sources frequently used for water supply, desorption of As from metal oxyhydroxides at high pH (>8) is the predominant mobility control; redox conditions are moderate reducing to oxidizing and As(V) is the predominant species. In the Andes, the Middle American cordillera and the Transmexican Volcanic Belt, oxidation of sulfide minerals is the primary As mobilization process. Rivers that originate in the Andean mountains, transport As to more densely populated areas in the lowlands (e.g. Rímac river in Peru, Pilcomayo river in Bolivia/Argentina/Paraguay). In many parts of Latin America, As often occurs together with F and B; in the Chaco-Pampean plain As is found additionally with V, Mo and U whereas in areas with sulfide ore deposits As often occurs together with heavy metals. These co-occurrences and the anthropogenic activities in mining areas that enhance the mobilization of As and other pollutants make more dramatic the environmental problem.

Small-scale and household methods to remove arsenic from water for drinking purposes in Latin America.

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.

Arsenic in the human food chain: the Latin American perspective.

Many regions of Latin America are widely reported for the occurrence of high arsenic (As) in groundwater and surface water due to a combination of geological processes and/or anthropogenic activities. In this paper, we review the available literature (both in English and Spanish languages) to delineate human As exposure pathways through the food chain. Numerous studies show that As accumulations in edible plants and crops are mainly associated with the presence of high As in soils and irrigation waters. However, factors such as As speciation, type and composition of soil, and plant species have a major control on the amount of As uptake. Areas of high As concentrations in surface water and groundwater show high As accumulations in plants, fish/shellfish, livestock meat, milk and cheese. Such elevated As concentrations in food may result in widespread health risks to local inhabitants, including health of indigenous populations and residents living close to mining industries. Some studies show that As can be transferred from the water to prepared meals, thereby magnifying the As content in the human diet. Arsenic speciation might also change during food preparation, especially during high temperature cooking, such as grilling and frying. Finally, the review of the available literature demonstrates the necessity of more rigorous studies in evaluating pathways of As exposure through the human food chain in Latin America.

Emerging mitigation needs and sustainable options for solving the arsenic problems of rural and isolated urban areas in Latin America - a critical analysis.

In this work, current information about the contamination of ground- and surface-water resources by arsenic from geogenic sources in Latin America is presented together with possible emerging mitigation solutions. The problem is of the same order of magnitude as other world regions, such as SE Asia, but it is often not described in English. Despite the studies undertaken by numerous local researchers, and the identification of proven treatment methods for the specific water conditions encountered, no technologies have been commercialized due to a current lack of funding and technical assistance. Emerging, low-cost technologies to mitigate the problem of arsenic in drinking water resources that are suitable for rural and urban areas lacking centralized water supplies have been evaluated. The technologies generally use simple and low-cost equipment that can easily be handled and maintained by the local population. Experiences comprise (i) coagulation/filtration with iron and aluminum salts, scaled-down for small community- and household-scale-applications, (ii) adsorption techniques using low-cost arsenic sorbents, such as geological materials (clays, laterites, soils, limestones), natural organic-based sorbents (natural biomass), and synthetic materials. TiO(2)-heterogeneous photocatalysis and zerovalent iron, especially using nanoscale particles, appear to be promising emergent technologies. Another promising innovative method for rural communities is the use of constructed wetlands using native perennial plants for arsenic rhizofiltration. Small-scale simple reverse osmosis equipment (which can be powered by wind or solar energy) that is suitable for small communities can also be utilized. The individual benefits of the different methods have been evaluated in terms of (i) size of the treatment device, (ii) arsenic concentration and distribution of species, chemical composition and grade of mineralization in the raw water, (iii) guidelines for the remaining As concentration, (iv) economical constrains, (v) complexity of installation and maintenance, and infrastructure constraints (e.g. electricity needs).

In field arsenic removal from natural water by zero-valent iron assisted by solar radiation.

An in situ arsenic removal method applicable to highly contaminated water is presented. The method is based in the use of steel wool, lemon juice and solar radiation. The method was evaluated using water from the Camarones River, Atacama Desert in northern Chile, in which the arsenic concentration ranges between 1000 and 1300 microg L(-1). Response surface method analysis was used to optimize the amount of zero-valent iron (steel wool) and the citrate concentration (lemon juice) to be used. The optimal conditions when using solar radiation to remove arsenic from natural water from the Camarones river are: 1.3 g L(-1) of steel wool and one drop (ca. 0.04 mL) of lemon juice. Under these conditions, removal percentages are higher than 99.5% and the final arsenic concentration is below 10 microg L(-1). This highly effective arsenic removal method is easy to use and inexpensive to implement.

Evaluation of boron removal from water by hydrotalcite-like compounds.

Layered double hydroxides (LDHs) or hydrotalcite (HT)-like compounds with different kinds of metal ions (Mg-Al and Mg-Fe) in the brucite-like sheets were prepared and their adsorption properties were studied in the boron removal from aqueous solution under laboratory conditions. The hydrotalcites were synthesized by the coprecipitation method and were characterized by chemical analyses, X-ray diffraction (XRD), Fourier Transform infrared spectroscopy (FTIR) and specific surface area measurements (BET). The affinity of these materials with a mixture of B(OH)(3) and B(OH)(4)(-) was studied as a function of contact time, initial pH of the solutions, HT quantity and B concentration (adsorption isotherms). It was found that 120 min is enough time for the equilibrium state to be reached in boron adsorption. Boron removal was independent of the initial pH of the solutions because of the high buffering capacity of the LDHs. On the other hand, the adsorption capacity increases with increasing the adsorbent quantity. The adsorption isotherms, described by the Langmuir model, are of L-type, suggesting that B(OH)(4)(-) is adsorbed preferentially on HT-like materials. Besides, Mg-Al hydrotalcites showed higher adsorption capacity than Mg-Fe. We proposed that in Mg-Al hydrotalcites, the boron removal occurs by both adsorption on external surface and ion exchange, whereas for Mg-Fe it occurs only by surface adsorption. After treatment of a solution containing 5.2 mgBl(-1) with Mg-Al hydrotalcites the final boron concentration reached the recommended limit by WHO for drinking water (0.5 mgl(-1)).

Arsenic speciation in human hair: a new perspective for epidemiological assessment in chronic arsenicism.

The analysis for arsenic in hair is commonly used in epidemiological studies to assess exposure to this toxic element. However, poor correlation between total arsenic concentration in hair and water sources have been found in previous studies. Exclusive determination of endogenous arsenic in the hair, excluding external contamination has become an analytical challenge. Arsenic speciation in hair appears as a new possibility for analytical assessing in As-exposure studies. This study applied a relative simple method for arsenic speciation in human hair based on water extraction and HPLC-HG-ICP-MS. The concentration of arsenic species in human hair was assessed in chronically As(V)-exposed populations from two villages (Esquiña and Illapata) of the Atacama Desert, Chile. The arsenic concentrations in drinking water are 0.075 and 1.25 mg L(-1), respectively, where As(V) represented between 92 and 99.5% of the total arsenic of the consumed waters. On average, the total arsenic concentrations in hair from individuals of Esquiña and Illapata were 0.7 and 6.1 microg g(-1), respectively. Four arsenic species, As(III), DMA(V), MMA(V) and As(V), were detected and quantified in the hair extracts. Assuming the found species in extracts represent the species in hair, more than 98% of the total arsenic in hair corresponded to inorganic As. On average, As(III) concentrations in hair were 0.25 and 3.75 microg g(-1) in Esquiña and Illapata, respectively; while, the As(V) average concentrations were 0.15 and 0.45 microg g(-1) in Esquiña and Illapata, respectively. Methylated species represent less than 2% of the extracted As (DMA(V)+ MMA(V)) in both populations. As(III) in hair shows the best correlation with chronic exposure to As(V) in comparison to other species and total arsenic. In fact, concentrations of As(total), As(III) and As(V) in hair samples are correlated with the age of the exposed individuals from Illapata (R= 0.65, 0.69, 0.57, respectively) and with the time of residence in this village (R= 0.54, 0.71 and 0.58, respectively).

Remoción de arsénico de aguas del rio Camarones, Arica, Chile

Describe la remoción de arsénico en aguas sintéticas y naturales de la región de Camarones (Arica, norte de Chile). En el estudio se emplearon soluciones preparadas tanto de As (III) como de As(V), irradiando con una lámpara de 360 nm. Los análisis de arsénico se realizaron mediante absorción atómica con generación de hidruros