Pilot monitoring study of ibuprofen in surface waters of north of Portugal

Ibuprofen is amongst the most worldwide consumed pharmaceuticals. The present work presents the first data in the occurrence of ibuprofen in Portuguese surface waters, focusing in the north area of the country, which is one of the most densely populated areas of Portugal. Analysis of ibuprofen is based on pre-concentration of the analyte with solid phase extraction and subsequent determination with liquid chromatography coupled to fluorescence detection. A total of 42 water samples, including surface waters, landfill leachates, Wastewater Treatment Plant (WWTP), and hospital effluents, were analyzed in order to evaluate the occurrence of ibuprofen in the north of Portugal. In general, the highest concentrations were found in the river mouths and in the estuarine zone. The maximum concentrations found were 48,720 ng?L^?1 in the landfill leachate, 3,868 ng?L^?1 in hospital effluent, 616 ng?L^?1 in WWTP effluent, and 723 ng?L^?1 in surface waters (Lima river). Environmental risk assessment was evaluated and at the measured concentrations only landfill leachates reveal potential ecotoxicological risk for aquatic organisms. Owing to a high consumption rate of ibuprofen among Portuguese population, as prescribed and non-prescribed medicine, the importance of hospitals, WWTPs, and landfills as sources of entrance of pharmaceuticals in the environment was pointed out. Landfill leachates showed the highest contribution for ibuprofen mass loading into surface waters. On the basis of our findings, more studies are needed as an attempt to assess more vulnerable areas.     

Sediment integrative assessment of the Bay of Cádiz (Spain): An ecotoxicological and chemical approach

This study consisted of the sediment toxicity assessment of the Bay of Cádiz based on two endpoints: growth inhibition for Cylindrotheca closterium (benthic microalgae) and fecundity inhibition for Tisbe battagliai (harpacticoid copepod). A new methodology to eliminate (but not as storage technique) the autochthonous biota present in the sediment samples by immersing them in liquid nitrogen (? 196 °C) was also assessed. Sediment toxicity data showed different toxicity levels for both organisms. In general, T. battagliai was more sensitive; however a good correlation (r = 0.75; p  < 0.05) between sediment toxicity results for both species was found. Data in pore water (pH, redox potential, and toxicity for microalgae and copepod) and sediment (pH, redox potential, organic carbon, and metal concentrations) demonstrated that ultra-freezing did not alter sample characteristics; thus, this technique can be adopted as a pre-treatment in whole-sediment toxicity tests in order to avoid misleading results due to presence of autochthonous biota. Multivariate statistical analysis such as cluster and principal component analysis using chemical and ecotoxicological data were employed. Silt and organic matter percentage and lead concentration were found to be the factors that explain about 77% of sediment toxicity in the Bay of Cádiz. Assay methodology determined in this study for both assayed species is considered adequate to be used in sediment toxicity monitoring programs. Results obtained using both species show that the Bay of Cádiz can be considered a moderately polluted zone.     

Effect of pre-treatment and supporting media on Ni(II), Cu(II), Al(III) and Fe(III) sorption by plant root material

In this work Paspalum notatum root material was used to elucidate the influence of acid leaching pre-treatment and of sorption medium on metal adsorption. Ground P. notatum root was leached with 0.14M HNO(3). Leached root material (LRM) and non-leached root material (NLRM) were employed to flow sorption of Ni(II), Cu(II), Al(III) and Fe(III) in 0.5M CH(3)COONH(4) medium at pH 6.5. For LRM the sorption was also studied in 0.5M KNO(3) medium. The acid pre-treatment increased the sorption capacity (SC) for all ions studied. For the KNO(3) medium, Cu(II) and Fe(III) sorption was higher than in CH(3)COONH(4) and the type of the Ni(II) isotherm's model changed. The Freundlich model was the most representative isotherm model to describe metallic ions sorption. The (1)H NMR spectra showed differences between LRM and NLRM and the acid-basic potentiometric titration elucidated that acid-leaching procedure affected the root material sorption sites once only two predominant sorption sites were found for LRM (phenolic and amine, both able cations sorption) and five sorption sites (two carboxylic, amine and two phenolic) were founded for NLRM.     

Discriminating the pH toxicity to Poecilia reticulata Peters, 1859 in the Dunas Lake (Camaçari, BA, Brazil)

Toxic potential of the pH reduction to fingerlings of Poecilia reticulata, through acute toxicity bioassays, as well as the influence of increased pH on the toxicity were assessed. Acid lake samples (Dunas Lake) were collected during 19 months, and assessed with following treatments: water at local pH (+/-3.0) and samples with modified pH to 3.5, 3.8, 4.0, 4.3, 4.6, 5.0, 5.5, 6.0, and 6.5. Culture water samples with pH reduced to 3.0 were also assessed. Newborn P. reticulata were exposed during 96h, and dead/immobile organisms were counted at various time intervals during exposure (short intervals in the beginning and long towards the end). Mean results of LT(50) and confidence intervals from the Dunas Lake and control water with reduced pH were 1.36 (+/-0.48)h, and 1.03 (+/-0.50)h, respectively, with no statistical difference. Samples with increased pH showed a significant reduction in toxicity, with no toxicity detected at pH 6.0 and higher. Relationship between pH and lethal toxicity for fingerlings of P. reticulata demonstrated that pH exerted a strong effect on the survival of this species at the Dunas Lake, explaining about 80% of the toxicity observed.     

Determination of ametryn in sugarcane and ametryn–atrazine herbicide formulations using spectrophotometric method

A sensitive spectrophotometric method has been developed for determination of ametryn in agricultural samples. The proposed method was based on reaction with pyridine and further coupling with sulfanilic acid to form a colored product. The absorbance was measured at 400 nm with a molar absorptivity of 2.1 × 10⁵ L mol⁻¹ cm⁻¹. The method shows a linear range from 0.2–20 μg mL⁻¹ with limit of detection and limit of quantification 0.16 and 0.54 μg mL⁻¹, respectively. The method has been successfully applied to the determination of ametryn in sugarcane juice and commercial formulations after separation of ametryn from triazine herbicides based on solvent extraction. Recovery values were found to be in the range of 96.0 ± 0.2% to 98.4 ± 0.1%.     

Electronic scraps--recovering of valuable materials from parallel wire cables

Every year, the number of discarded electro-electronic products is increasing. For this reason recycling is needed, to avoid wasting non-renewable natural resources. The objective of this work is to study the recycling of materials from parallel wire cable through unit operations of mineral processing. Parallel wire cables are basically composed of polymer and copper. The following unit operations were tested: grinding, size classification, dense medium separation, electrostatic separation, scrubbing, panning, and elutriation. It was observed that the operations used obtained copper and PVC concentrates with a low degree of cross contamination. It was concluded that total liberation of the materials was accomplished after grinding to less than 3 mm, using a cage mill. Separation using panning and elutriation presented the best results in terms of recovery and cross contamination.     

Photocatalytic degradation of formaldehyde containing wastewater from veterinarian laboratories

The photocatalytic destruction of methanol, formaline (mixture of formaldehyde, methanol and water) and formaline wastes from the preservation of vertinarian physiologic samples has been attempted by two different processes, at high concentrations of reagents and by dossification of reagents, varying pH in both. Experiment evolution has been monitored by measuring the organic matter such as TOC and formaldehyde concentrations [H2CO]. Also, methanol and methanol-formaldehyde interactions with the TiO2 surface have been analysed by FTIR spectroscopy. Results indicate that at high concentrations the catalyst surfacial alterations given by methoxy, formates or carbonates, according to the pH of the sample can profoundly affect catalyst behaviour. It has been established that reagent dossification is advantageous for enhancing photonic efficiency as it minimizes the adsorbate presence that hampers the photocatalytic process.