Prediction of ozone concentrations in Oporto city with statistical approaches

The performance of three statistical methods: time-series, multiple linear regression and feedforward artificial neural networks models were compared to predict the daily mean ozone concentrations. The study here reported was based on data from one urban site with traffic influences and one rural background site. The studies were performed for the year 2002 and the respective four trimesters separately. In the multiple linear regression and feedforward artificial neural network models, the concentrations of ozone, the concentrations of its precursors (nitrogen oxides) and some meteorological variables for one and two days before the prediction day were used as predictors. For the application of these models in the validation step, the inputs of ozone concentration for one and two days before were replaced by the ozone concentrations predicted by the models. The results showed that time-series modelling was not profitable. In the development step, similar performances were obtained with multiple linear regression and feedforward artificial neural network. Better performance indexes were achieved with feedforward artificial neural network models in validation step. Concluding, feedforward artificial neural network models were more efficient to predict ozone concentrations.     

Changes in amino acid profile and metal content in seeds of Cicer arietinum L. (chickpea) grown under various fly-ash amendments

Seeds of Cicer arietinum L. plants are edible and a valuable source of protein. Accumulation of toxic metals in the edible part of the plant, grown in fields close to fly-ash (FA) landfills, may pose a threat to human health. In the present study, the effects of FA and its amendments with different ameliorants viz., garden soil (GS), press mud (PM) and saw dust (SD), on total soluble protein contents, amino acid composition and metal accumulation in seeds were investigated in var. CSG-8962 and var. C-235 of C. arietinum. Plants accumulated adequate amounts of essential metals viz. Fe, Cu, Zn in seeds, while the toxic metals such as Cd and Cr were taken up in smaller quantities. The accumulation of Cr and Cd was less in var. C-235 than var. CSG-8962. Amendment of FA with PM enhanced the amount of soluble protein and amino acids in both varieties and was found to be superior among all tested ameliorants. Both quantitative and qualitative analysis of amino acids showed better response in var. C-235 as compared to var. CSG-8962. Thus var. C-235 seems to be suitable for cultivation in FA contaminated areas due to more accumulation of essential metals and less accumulation of toxic metals in seeds. Application of PM may further improve the growth of plants and nutritional quality of seeds.     

Bagasse-assisted bioremediation of ammonia from shrimp farm wastewater.

Development of new economically feasible ecofriendly products from agricultural wastes or byproducts for shrimp farm wastewater treatment is the objective of our continued research. Ammonia is a nitrogenous toxicant, which is commonly found in wastewater from shrimp farms. In the present study, we explored the possibility of the use of simply and inexpensively prepared bagasse products so that this abundant crop byproduct could be used to remove ammonia from shrimp farm wastewater. Bagasse, a natural highly fibrous lignocellulosic byproduct of sugarcane, was converted into five different products. Experimental results have shown that ammonia is efficiently removed from wastewater by four bagasse products with a dose of 1 to 6 g/L within 24 hours. The effect of bagasse products on other water quality parameters and growth kinetics of biofilm bacteria onto bagasse fiber have also been studied. Efficacies of products were compared by using statistical analysis. Products developed from bagasse are useful and economical.     

Contribution of anthropogenic pollutants to the increase of tropospheric ozone levels in the Oporto Metropolitan Area, Portugal since the 19th century

The main purpose of this study was to evaluate the contribution of anthropogenic pollutants to the increase of tropospheric ozone levels in the Oporto Metropolitan Area (Portugal) since the 19th century. The study was based on pre-industrial and recent data series, the results being analyzed according to the atmospheric chemistry. The treatment of ozone and meteorological data was performed by classical statistics and by time-series analysis. It was concluded that in the 19th century the ozone present in the troposphere was not of photochemical origin, being possible to consider the respective concentrations as reference values. For recent data a cycle of 8h for ozone concentrations could be related to traffic. Compared to the 19th century, the current concentrations were 147% higher (252% higher in May) due to the increased photochemical production associated with the increased anthropogenic emissions.     

Calcite-seeded crystallization of calcium phosphate for phosphorus recovery

For phosphorus recovery from wastewater, the present paper aims at understanding the crystallization of calcium phosphate by using calcites (Juraperle and Coccolith) as seeds from hard water. Synthetic hard water with 60 mgCl(-1) carbonate and 10 mgPl(-1) phosphate was prepared and used in the batch experiments of calcite-seeded crystallization. The solution composition was measured throughout the batch crystallization process, and the corresponding saturation indices with respect to the minerals were calculated with PHREEQC Program. The surface of the calcite seeds was observed and measured with environmental scanning electron microscopy (ESEM), Fourier transform infrared (FTIR) and BET method. The studies show that both calcites are effective seeds for the crystallization of calcium phosphate from hard water; the used calcites are more efficient than the original ones because newly formed crystals with calcium phosphate have covered their surfaces. The studies show that the calcite seeds can be used for phosphorus recovery from hard waters.     

Fine route for an efficient removal of 2,4-dichlorophenoxyacetic acid (2,4-D) by zeolite-supported TiO2

Zeolites HY, Hbeta and HZSM-5 with different physico-chemical properties were chosen as support for TiO2 to illustrate their adsorption, dispersion and electronic structure in photocatalysis. The extent of TiO2 loading was monitored by XRD and BET surface area measurements. The adsorption capacity of HY zeolite was found to be high and hence chosen for further modification to continue the investigation. Photodegradation kinetics were carried out with 2,4-dichlorophenoxyacetic acid (2,4-D) in aqueous solution. The extent of 2,4-D degradation on TiO2/HY loading revealed the importance of adsorption in photocatalysis. Mineralisation studies on all three zeolites with 1 wt.% TiO2 loading demonstrated the good dispersion properties of TiO2/HY. Its photocatalytic activity was found to be excellent with formulated 2,4-D. Comparison of relative photonic efficiencies demonstrated that supported photocatalysts exhibited higher activity than some of the commercial photocatalysts. The high activity of supported TiO2 is due to synergistic effects of improved adsorption of 2,4-D and efficient delocalisation of photogenerated electrons by zeolite support.     

Uranium transport around the reactor zone at Bangombé and Okélobondo (Oklo): examples of hydrogeological and geochemical model integration and data evaluation

The sites at Bangombé and Okélobondo (Oklo) in Gabon provide a unique opportunity to study the behaviour of products from natural nuclear reactions in the vicinity of reactor zones which were active around two billion years ago. The Commission of the European Communities initiated the Oklo Natural Analogue Programme. One of the principal aims was to study indications of present time migration of elements from the reactor zones under ambient conditions. The hydrogeological and hydrochemical data from the Oklo sites were modelled in order to better understand the geochemical behaviour of radionuclides in the natural system, by using independent models and by comparing the modelling outcome. Two modelling approaches were used: M3 code (hydrochemical mixing and mass balance model), developed by the Swedish Nuclear Fuel and Waste Management Company (SKB) and HYTEC (reactive transport model) developed by Ecole des Mines de Paris. Two different reactor zones were studied: Bangombé, a shallow site, the reactor being at 11 m depth, and OK84 at Okélobondo, situated at about 450 m depth, more comparable with a real repository location. This allowed the validation of modelling tools in two different sedimentary environments: one shallow, with a more homogeneous layering situated in an area of meteoric alteration, and the other offering the opportunity to study radionuclide migration from the reaction zone over a distance of 450 m through very heterogeneous sedimentary layers. The modeling results indicate that the chemical reactions retarding radionuclide transport are very different at the two sites. At Bangombé, the decomposition of organic material consumes oxygen and at Okélobondo the oxygen is consumed by inorganic reactions resulting, in both cases, in uranium retardation. Both modelling approaches (statistic with M3 code and deterministic with HYTEC code) could describe this situation. The goal of this exercise is to test codes which can help to describe and understand the processes taking place at the sites, validate the models with in situ data, and thus build confidence in the tools used for future site characterization. Ultimately, this allows identifying and selecting processes and parameters that can be used as input into repository performance assessment calculations and modelling exercises.     

Sorption of As(V) ions by akaganéite-type nanocrystals

A priority pollution problem, the removal of arsenate oxyanions from dilute aqueous solutions by sorption onto synthetic akaganéite (beta-FeO(OH)) was the aim of the present study. This is an innovative inorganic adsorbent material prepared in the laboratory, following a new method of preparation. The effect of akaganéite and arsenate concentration, the contact time, temperature, solution pH value, and ionic strength variation on the treatment process was mainly investigated during this study. Typical adsorption isotherms were determined, which were found to fit sufficiently the typical Langmuir equation. The mechanism of sorption was examined by electrokinetic, X-ray diffraction, Fourier transmission infrared and scanning electron microscopy measurements. Promising results were obtained, due to the favourite characteristics of the adsorbent applied.