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.     

Simulation of a Hazardous and Noxious Substances (HNS) spill in the marine environment: Lethal and sublethal effects of acrylonitrile to the European seabass

Despite the extensive maritime transportation of Hazardous and Noxious Substances (HNS), there is a current lack of knowledge on the effects posed by HNS spills on the marine biota. Among the HNS identified as priority, acrylonitrile was selected to conduct ecotoxicological assays. We assessed the acute and subletal effects of acrylonitrile in seabass, followed by a recovery phase to simulate the conditions of a spill incident. The work aimed at testing a broad range of biological responses induced by acrylonitrile. Sublethal exposure to the highest two doses increased the fish mortality rate (8.3% and 25% mortality in 0.75 and 2 mg L⁻¹ acrylonitrile concentrations), whereas no mortality were observed in control and 0.15 mg L⁻¹ treatments. Additionally, important alterations at sub-individual level were observed. Acrylonitrile significantly induced the activities of Catalase– CAT and Glutathione S-Transferase – GST; and the levels of DNA damage were significantly increased. Conversely, Superoxide Dismutase– SOD – activity was found to be significantly inhibited and no effects were found on Lipid Peroxidation– LPO and ethoxyresorufin O-deethylase – EROD – activity. Following a 7 d recovery period, the levels of CAT, GST and EROD fell to levels at or below those in the control. In the 2 mg L⁻¹ group, SOD remained at the levels found during exposure phase. This study has gathered essential information on the acute and subletal toxicity of acrylonitrile to seabass. It also demonstrated that 7 d recovery allowed a return of most endpoints to background levels. These data will be useful to assist relevant bodies in preparedness and response to HNS spills.     

One-Component Spray Polyurethane Foam from Liquefied Pinewood Polyols: Pursuing Eco-Friendly Materials

The use of petroleum-derived products should be avoided regarding the principles of green and sustainable chemistry. The work reported herein, is aimed at the liquefaction of pine shavings for the production of an environmentally-friendly polyol suitable to be used in the formulations of sprayable polyurethane foams. The biopolyols were obtained in high yield and were used to replace those derived from fossil sources, to produce more “greener” polyurethane foams and therefore, less dependent on petroleum sources, since the polyol component was substituted by products resulting from biomass liquefaction. The partial and fully exchange of the polyols was accomplished, and the results compared with a reference foam. The foams were afterward, chemical, physical, morphological, and mechanically characterized. The complete replacement of polyether polyol and polyol polyester has presented some similar characteristics as that used as a reference, validating that the path chosen for the development of more sustainable materials is on the right track for the contribution to a cleaner world.     

Glyphosate input modifies microbial community structure in clear and turbid freshwater systems

Since it was commercially introduced in 1974, glyphosate has been one of the most commonly used herbicides in agriculture worldwide, and there is growing concern about its adverse effects on the environment. Assuming that glyphosate may increase the organic turbidity of water bodies, we evaluated the effect of a single application of 2.4?±?0.1 mg l^?1 of glyphosate (technical grade) on freshwater bacterioplankton and phytoplankton (pico, micro, and nanophytoplankton) and on the physical and chemical properties of the water. We used outdoor experimental mesocosms under clear and oligotrophic (phytoplanktonic chlorophyll a?=?2.04 μg l^?1; turbidity?=?2.0 NTU) and organic turbid and eutrophic (phytoplanktonic chlorophyll a?=?50.3 μg l^?1; turbidity?=?16.0 NTU) scenarios. Samplings were conducted at the beginning of the experiment and at 1, 8, 19, and 33 days after glyphosate addition. For both typologies, the herbicide affected the abiotic water properties (with a marked increase in total phosphorus), but it did not affect the structure of micro and nanophytoplankton. In clear waters, glyphosate treatment induced a trend toward higher bacteria and picoeukaryotes abundances, while there was a 2 to 2.5-fold increase in picocyanobacteria number. In turbid waters, without picoeukaryotes at the beginning of the experiment, glyphosate decreased bacteria abundance but increased the number of picocyanobacteria, suggesting a direct favorable effect. Moreover, our results show that the impact of the herbicide was observed in microorganisms from both oligo and eutrophic conditions, indicating that the impact would be independent of the trophic status of the water body.     

A spatial-statistical approach for modeling the effect of non-point source pollution on different water quality parameters in the Velhas river watershed--Brazil

In this article, a methodology for evaluating the effect of land use/land cover on the quality of nearby stream water in a semiarid environment is described and tested on a large watershed in Southeastern Brazil. The approach aims at identifying the width of the riparian area having the strongest effect on different water quality parameters. The land use/land cover data were generated from remotely sensed data while water quality point data were supplied by a government agency. Testing was conducted for both the rainy and dry seasons in an effort to understand the direct effect of surface runoff. The approach combines cartographic modelling using a geographical information system (GIS) and statistics to establish the strength of the relationship between water quality, land use and the distance from the stream. Results suggest a strong relationship between land use/land cover and turbidity, nitrogen and fecal coliforms. They also suggest that each of these parameters has a unique behavior when distance from the stream is considered. Finally, although it was expected that the models would apply better during the wet season, some parameters had the opposite behavior and displayed a better fit during the dry season.     

Traffic and catalytic converter - related atmospheric contamination in the metropolitan region of the city of Rio de Janeiro, Brazil

In this work, 24-h PM10 samples were collected in Rio de Janeiro, Brazil, and analysed for trace elements (Cd, Ce, Cu, La, Mo, Ni, Pb, Pd, Rh, Sb and Sn). The sampling was carried out at five locations (Bonsucesso; Centro, downtown city; Copacabana; Nova Igua?u and Sumaré) with different traffic densities and anthropogenic activities. An analytical method based on the EPA method for the determination of trace elements in airborne particulate matter (PM), using ultrasonic-assisted extraction and inductively coupled plasma mass spectrometry (ICP-MS) was applied. Our results suggest that vehicular traffic is the most important source of environmental pollution at the studied sites. The presence of Mo, Pd and Rh in the analysed filters reflects an additional source of pollution caused by the erosion and deterioration of automotive catalytic converters.     

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.     

Biochemical effects of clomazone herbicide on piava (Leporinus obtusidens)

This study aims to verify the effects of the clomazone concentration used in rice fields on acetylcholinesterase (AChE), thiobarbituric acid reactive substances (TBARS), protein carbonyl and catalase activity in tissues of piava (Leporinus obtusidens). LC(50)-96h was 5.0 mg L(-1) and the fish were exposed to 1/10 of LC(50)-96 h: 0.5 mg L(-1) of clomazone for 96 and 192h. The same parameters were also assayed after a recovery period of 192 h in clean water. AChE activity was reduced only in the brain and heart of fish exposed for 96 h. AChE activity was decreased in the brain, muscle and heart tissues after 192 h of exposure. After 192 h of recovery period, AChE activity remained diminished in brain and muscle and showed a decrease in eye. However, after 192 h of recovery, AChE activity in heart was recovered. Fish showed increased TBARS levels in brain at all experimental periods. TBARS levels decreased in liver and muscle tissues after 192 h of exposure. The increase in muscle TBARS persisted in fish transferred to clean water. Protein carbonyl in the liver was increased in all periods studied including the recovery period. Catalase activity was reduced during all periods. The present study demonstrates the occurrence of disorders in AChE, TBARS, protein carbonyl and catalase activity in piava. The results also show changes in fish after exposure to an environmentally relevant concentration of clomazone. Most effects observed persisted after the recovery period. Thus, these parameters may be used to monitor clomazone toxicity in fish.     

Large and mesoscale meteo-oceanographic patterns in local responses of biogeochemical concentrations

Investigations surrounding the variability of productivity in upwelling regions are necessary for a better understanding the physical-biological coupling in these regions by monitoring systems of environmental impacts according to the needs of the regional coastal management. Using a spatial and temporal database from National Centers for Environmental Prediction (NCEP) and National Center for Atmospheric (NCAR) Research reanalysis, Quick Scatterometer vector wind, and surface stations from the Southeast coast of Brazil, we investigate the meteorological influences due to the large-scale systems in the variability of the nutrient and larvae concentration, and chlorophyll a, describing statistically relationships between them in upwelling regions. In addition, we used multivariate analysis, such as PCA and clustering to verify spatial and temporal variances and describe more clear the structure and composition of the ecosystem. Correlation matrix analyses were applied for different water masses present in the study area to identify the relations between physical and biogeochemical parameters in a region, where frequently upwelling occur. Statistical approaches and seasonal variability show that the period of November to March is more sensitive to nutrients (1.20?mg/m(3) for chlorophyll a, 2.20?μmol/l for total nitrogen and 5.5?ml/l for DO) and larvae concentrations (120 org/m(3) for most of the larvae, except for cirripedia that presented values around 370 org/m(3)) relating to the influence of large and mesoescale meteorological patterns. The spatial and temporal variables analyzed with multivariate approach show meaningful seasonality variance of the physical and biological samples, characterizing the principal components responsible for this variance in spring and summer (upwelling period), emphasizing the monitoring of species as crustaceans and mussels that are present in the local economy. Then, the spring and summer season are characterized by high productivity due to the occurrence of upwelling in this period.     

Biodegradation or simple adsorption to the support material? Development of a simple, fast and low-cost technique

Biofilms are present in several areas and are studied in microbiology, medical sciences, biology and, of course, sanitary engineering. Biofilms are used for the treatment of municipal wastewater, and their application was even before the invention of the activated sludge process. The main objective of this work was to develop a simple, fast and low-cost technique to evaluate the nature of the first decay in the concentration of an organic compound in the presence of a solid material. Though simple, the technique developed has allowed the clarification of whether the initial concentration decay is due to adsorption to the support material or a result of biodegradation. The results show that, with two different support materials, adsorption does not take place, and the biodegradation processes are responsible for the first decay in the organic concentration. The technique used offers a fast and low-cost way of studying the existence of adsorption. Two feed concentration solutions and two different support materials were used.