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Organisationseinheit der BAM
Carbamazepine (CBZ), an antiepileptic drug, is one of the most commonly detected pharmaceutical drugs in aquatic ecosystems, and is used as a marker of urban pollution. Since CBZ is designed to exert a biological effect, when it reaches aquatic environment high probability exist for toxic effects on non-target organisms. The present study evaluated the acute toxicity of environmentally relevant concentrations of CBZ (0.00, 0.03, 0.30, 3.00, 9.00 µg/L) in the edible clams Venerupis decussata (a native species) and Venerupis philippinarum (an invasive species) collected from the Ria de Aveiro. The effects on both species were assessed through the use of a battery of biomarkers mainly related with health status and oxidative stress. Furthermore, in this work an alternative and promising tool, the direct competitive immunoassay ELISA, for the direct CBZ quantification in clam's tissues, was applied.
The results of the present work showed that CBZ in clam's tissues increased with the exposure concentration and V. decussata gave slightly higher values than V. philippinarum. Although the clams accumulated lower levels of CBZ than the concentration of exposure, these concentrations were enough to impair the health status and induce oxidative stress. However, a different response to CBZ was observed in the two species. While in V. philippinarum the lipid peroxidation levels increased at the highest CBZ concentration (9.00 µg/L), in V. decussata a significant decrease was seen. Moreover, glutathionse S-transferase activity was stimulated in V. decussata and decreased in V. philippinarum. Nevertheless, an induction of glutathione reductase, superoxide dismutase and cytochrome P450 3A4 activities was found in both species as a result of the exposure. The results indicate that, probably, V. philippinarum have a less efficient antioxidant system than V. decussata, and are therefore less capable to neutralize oxidative stress and consequently more sensitive to CBZ. The risk quotient determined for the Ria de Aveiro was higher than 1 indicating that a ecotoxicological risk is suspected. Furthermore, bioaccumulation of CBZ in clams should be taken into consideration since this chemical might be transferred along the food chain and affect non-target organisms.
The bivalve Mytilus galloprovincialis collected in the Ria de Aveiro, was selected to evaluate the acute and chronic effects of carbamazepine (CBZ) at environmentally relevant concentrations. CBZ is an antiepileptic drug widely found in the aquatic environment with toxic effects to inhabiting organisms. However, few studies evaluated the acute and chronic toxicity of this drug. The experiment was performed 'by exposing mussels to 0.0, 0.3, 3.0, 6.0 and 9.0 CBZ mu g/L, for 96 h and 28 days. To assess the toxicity of the drug, a battery of biomarkers related to mussels general physiological health status and oxidative stress was applied. CBZ was quantified in mussel tissues by an Enzyme-Linked Immunosorbent Assay (ELISA). The results obtained show that CBZ did not induce oxidative stress. However, our findings,demonstrated that the drug was taken up by mussels even though presenting low bioconcentration factor (BCF) values (up to 2.2). Furthermore, our results demonstrated that after a chronic exposure the physiological parameters, namely the condition and gonadosomatic indices, were negatively affected which may impair organisms' reproductive capacity with consequences to population sustainability.
Photodegradation of organic pollutants in water by immobilized porphyrins and phthalocyanines
(2016)
New methods for water treatment are required as a result from an increasing awareness in the reduction of the pollution impact in the environment. In the perspective of the photo-oxidation of organic pollutants present in water, the principal incentive for the preparation of heterogeneous photocatalysts is their easy recovery from the reaction mixture, which allows their reuse in successive runs, minimizing the loss of their original photocatalytic properties. Different types of supports can be used in the immobilization of photoactive species, such as porphyrins (Pors) and phthalocyanines (Pcs). This mini-review will consider the different methodologies for the immobilization of Pors and Pcs and their photocatalytic performance in the photodegradation of organic pollutants in water, addressing also their recycling ability in successive water treatments.
The preparation of porphyrins and phthalocyanines covalently attached onto nanostructured magnetic supports consisting of magnetite nanoparticles coated with an amorphous silica shell is reported. The easy recovery of these heterogeneous photocatalysts, just by applying an external magnetic field, allows their reuse in multiple treatment cycles. The photocatalytic activity of the non-immobilized photosensitizers and the obtained hybrid materials was evaluated in the degradation of 17 beta-estradiol, as a model organic pollutant present in water, using batch and flow mode treatment systems, assisted by visible light radiation (4 mW cm(-2)). The flow mode system potentiated the photocatalytic capacity of these novel hybrid materials. In order to improve the process, further studies based on different photocatalyst concentration and pH conditions were performed. Reuse capacity of these materials was investigated upon three photocatalytic cycles.
The toxicity induced in non-target organisms by pharmaceutical drugs has been the focus of several studies. In the aquatic environment, most of the studies have been devoted to fish and bivalves, while little is known on the impacts induced in polychaetes. The present study evaluated the impacts of carbamazepine and caffeine on the regenerative capacity of Diopatra neapolitana, a polychaete species with high ecological and economic relevance. Under laboratory controlled conditions polychaetes were exposed, during 28 days, to carbamazepine (Ctl-0.0; 0.3; 3.0; 6.0; 9.0 mg/L) and caffeine (Ctl-0.0; 0.5; 3.0; 18.0 mg/L). During the experiment, at days 11, 18, 25, 32, 39 and 46 after amputation, for each specimen, the percentage of the body width regenerated was determined and the number of new segments was counted. The regenerative capacity was assessed considering the number of days needed to achieve full regeneration and the total number of new segments. The obtained results revealed that with the increase of drugs concentrations organisms regenerated less new segments and took longer to completely regenerate.
In the last decade studies have reported the presence of several pharmaceutical drugs in aquatic environments worldwide and an increasing effort has been done to understand the impacts induced on wildlife. Among the most abundant drugs in the environment is caffeine, which has been reported as an effective chemical anthropogenic marker. However, as for the majority of pharmaceuticals, scarce information is available on the adverse effects of caffeine on marine benthic organisms, namely polychaetes which are the most abundant group of organisms in several aquatic ecossystems. Thus, the present study aimed to evaluate the biochemical alterations induced by environmentally relevant concentrations of caffeine on the polychaete species Diopatra neapolitana and Arenicola marina. The results obtained demonstrated that after 28 days exposure oxidative stress was induced in both species, especially noticed in A. marina, resulting from the incapacity of antioxidant and biotransformation enzymes to prevent cells from lipid peroxidation. The present study further revealed that D. neapolitana used glycogen and proteins as energy to develop defense mechanisms while in A. marina these reserves were maintained independently on the exposure concentration, reinforcing the low capacity of this species to fight against oxidative stress.
The effects of long-term application of different organic amendments, as compared to mineral fertilizer, on Zn, Cu and Pb content and leachability in a luvisol derived from loess were assessed. The organic fertilizers, applied since 1962, were compost (COM) – from green organic household waste, sewage sludge (SLU) – from municipal water treatment facilities, farmyard manure (FYM) and the doses applied since 1997 were 90 t ha-1, 10 t ha-1 and 9 t ha-1, once in 3 years, respectively. The kinetics of metals extraction with 0.05 mol dm-3 EDTA at pH 6.0 has been studied. The two first-order reactions model was fitted to the kinetic data and allowed to distinguish two pools for each metal: a 'labile' fraction (Q1), quickly extracted with a rate constant k1, and a 'moderately labile' fraction (Q2), more slowly extracted, with a rate constant k2. Simultaneously, the pseudo-total metal contents in the soil samples were determined after digestion with aqua regia (3:1 HCl + HNO3). The obtained parameters Q1, k1, Q2, k2, for the kinetics of extraction of each metal in the three replicates of each fertilization mode, as well as the pseudo-total metal contents, were statistically analysed. COM and SLU application resulted in an increase of the total contents of Pb, Zn and Cu in soil. Further, the percentage of labile Zn and Pb also increased in consequence of the application of those amendments, particularly COM. The increase was more noticeable for Zn. FYM, despite not increasing the total content of Pb, Zn or Cu, did also have an effect on the leachability of Zn and Pb, increasing their labile fraction in soil. These results point to a potential risk of increasing metals mobility in soil, mainly Zn, associated to the use of organic amendments, particularly COM or SLU.
In the present study, the bivalve Scrobicularia plana, collected from two contrasting areas (pristine location and mercury contaminated area), was selected to assess the biochemical alterations imposed by pH decrease, carbamazepine (an antiepileptic) and the combined effect of both stressors. The effects on oxidative stress related biomarkers after 96 h exposure revealed that pH decrease and carbamazepine induced alterations on clams, with greater impacts on individuals from the contaminated area which presented higher mortality, higher lipid peroxidation and higher glutathione S-transferase activity. These results emphasize the risk of extrapolating results from one area to another, since the same species inhabiting different areas may be affected differently when exposed to the same stressors. Furthermore, the results obtained showed that, when combined, the impact of pH decrease and carbamazepine was lower than each stressor acting alone, which could be related to the defence mechanism of valves closure when bivalves are under higher stressful conditions.
Several environmental stressors have been identified as key and/or emerging drivers of habitat change that could significantly influence marine near-shore ecosystems. These include increasing discharges of pharmaceutical contaminants into the aquatic coastal systems. Pharmaceutical drugs are often detected in aquatic environments but still information on their toxicity impacts on inhabiting species is scarce, especially when acting in combination. Furthermore, almost no information is available on the impacts of pharmaceuticals in polychaetes, often the most abundant taxon in benthic communities and commonly used as indicator species of environmental conditions. Therefore, the present study aimed to evaluate the biochemical alterations induced in the polychaete Hediste diversicolor, from a low contaminated area at the Ria de Aveiro lagoon (Portugal), by the antiepileptic drug carbamazepine (0.0 - control, 0.3, 3.0, 6.0 and 9.0 μg/L) and the stimulant caffeine (0.0 - control, 0.5, 3.0, and 18.0 μg/L), acting alone and in combination (0.3 CBZ + 0.5 CAF and 6.0 CBZ + 3.0 CAF). Glutathione Stransferases (GSTs), superoxide dismutase (SOD) and catalase (CAT) activities was determined in Hediste diversicolor from each condition. Lipid peroxidation (LPO), glutathione reduced and oxidized (GSH and GSSG), glycogen and electron transport system (ETS) were also measured. The results obtained clearly revealed that both drugs induced oxidative stress in H. diversicolor, shown by the increase on LPO levels and decrease on total glutathione and GSH/GSSG ratio with the increase of exposure concentrations. Furthermore, the present findings demonstrated that polychaetes biotransformation capacity as well as antioxidant defense mechanisms were not sufficiently efficient to fight against the excess of reactive oxygen species (ROS) leading to LPO when organisms were exposed to both drugs. Our results also demonstrated that polychaetes tended to decrease the activity of ETSwhen exposed to drugs, avoiding energy expenditurewhich may prevent them fromgreater damages. The present study further revealed that the impacts induced by the combination of both drugswere similar to those obtained at the highest drugs concentrations acting alone.
This study comprises the development of an enzyme-linked immunosorbent assay (ELISA) for the quantification of caffeine in complex aqueous matrices without any sample clean-up procedure. Salinity and dissolved organic matter were selected as potential interfering agents. The addition of a sample buffer containing bovine serum albumin (BSA) prior to the sample was found to decrease the influence of those interfering agents. The working range of the developed method was 0.1–100 µg L- 1. Quantification of caffeine was possible in 43 out of 51 real aqueous samples, at values between < LOD and 15 µg L- 1. Results correlate well with those obtained by LCMS/MS. To the best of our knowledge this is the first study dealing with the quantification of caffeine in Portugal's surface waters.