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Organisationseinheit der BAM
Ocean acidification and increasing discharges of pharmaceutical contaminants into aquatic systems are among key and/or emerging drivers of environmental change affecting marine ecosystems. A growing body of evidence demonstrates that ocean acidification can have direct and indirect impacts on marine organisms although combined effects with other stressors, namely with pharmaceuticals, have received very little attention to date. The present study aimed to evaluate the impacts of the pharmaceutical drug Carbamazepine and pH 7.1, acting alone and in combination, on the clamScrobicularia plana. For this, a long-termexposure (28 days)was conducted and a set of oxidative stress markers was investigated. The results obtained showed that S. plana was able to develop mechanisms to prevent oxidative damage when under low pH for a long period, presenting higher survival when exposed to this stressor compared to CBZ or the combination of CBZ with pH 7.1. Furthermore, the toxicity of CBZ on S. plana was synergistically increased under ocean acidification conditions (CBZ + pH 7.1): specimens survival was reduced and oxidative stress was enhanced when compared to single exposures. These findings add to the growing body of evidence that ocean acidification will act to increase the toxicity of CBZ to marine organisms,which has clear implications for coastal benthic ecosystems suffering chronic pollution from pharmaceutical drugs.
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.
Cetirizine (CTZ) is an antihistaminic drug present in the aquatic environment, with limited information on its toxicity to organisms inhabiting this system. This study intended to evaluate the effects of CTZ on oxidative stress and energy metabolism biomarkers in the edible clam Ruditapes philippinarum after a 28 days exposure to environmentally relevant CTZ concentrations (0.0, 0.3, 3.0, 6.0 and 12.0 mu g/L). The results obtained showed that CTZ was accumulated by clams reaching maximum concentrations (up to similar to 22 ng/g FW) at the highest CTZ exposure concentrations (6.0 and 12.0 mu g/L). The bioconcentration factor (average maximum values of similar to 5) decreased at 12.0 mu g/L reflecting a reduction in clams uptake or increase of excretion capacity at this condition. The present study revealed that, in general, clams decreased the metabolic potential after exposure to CTZ (decrease in electron transport system activity), a response that led to the maintenance of glycogen content in organisms exposed to CTZ in comparison to control values. Our findings also showed that, CTZ did not exert significant levels of oxidative injury to clams. However, comparing the control with the highest exposure concentrations (6.0 and 12.0 mu g/L) a significant increase of the antioxidant enzyme superoxide activity (similar to 53 and similar to 44%) was observed in clams exposed to CTZ. Moreover, a tendency to increase lipid peroxidation (similar to 14 and similar to 9%) and carbonyl groups on proteins (similar to 11 and similar to 3%) was observed in clams exposed to CTZ (6.0 and 12.0 mu g/L) compared to control condition. Overall the present study suggests that toxic impacts may be induced in R. philippinarum if exposed for longer periods or higher CTZ concentrations.
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.
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.
Several works evaluated the toxicity of pharmaceutical drugs and climate related changes in invertebrates but few explored the combined effects of both stressors, namely considering their mode of action (MoA). Carbamazepine (CBZ) and cetirizine (CTZ) are pharmaceutical drugs detected in the environment and the toxicity derived from the combined effects of these drugs with ocean acidification (OA) is poorly explored. Thus, the present study investigated the biochemical parameters related to an oxidative stress response and the transcription of genes related to the MoA of CBZ (1.0 mg/L) and CTZ (0.6 mg/L) in the clam Ruditapes philippinarum chronically exposed (28 days) to control (7.8) and low (7.5) pH conditions. The results obtained showed that despite the clams accumulated both drugs, at low pH the clams exposed to CTZ decreased drug concentration and BCF values (CTZ uptake: 2.0 ± 0.5 ng/g fresh weight; BCF: 3.8 ± 0.9) in comparison with clams exposed to control pH (CTZ uptake: 2.9 ± 0.3 ng/g fresh weight; BCF: 5.5 ± 0.6). No oxidative stress was induced by the exposure to CBZ or CTZ at each pH level, but the transcription of several genes related with the MoA (neurotransmission, immunity and biomineralization) was altered by low pH, drug exposure and the combination of both stressors. At both pH conditions, CBZ increased the transcription of GABA receptor gene (neurotransmission) and CTZ led to a decrease of Perlucin gene (biomineralization) transcription. The transcription of MyD88 gene (immunity) decreased at low pH (7.5) combined with drug exposure (CBZ or CTZ). Thus, it was highlighted that the interaction of drug exposure and low pH conditions can change bivalves’ sensitivity to drugs or alter drugs toxicity.
Recent studies have become increasingly focused on the assessment of pharmaceuticals occurrence in aquatic ecosystems, however the potential toxicity to non-target organisms is still largely unknown. The antihistamine cetirizine is a commonly used pharmaceutical, already detected in surface waters of marine aquatic systems worldwide. In the present study Mytilus galloprovincialis mussels were exposed to a range of cetirizine concentrations (0.3, 3.0, 6.0 and 12.0 mu/L), resembling moderate to highly contaminated areas, over 28 days. The responses of different biochemical markers were evaluated in mussels whole soft tissue, and included energy-related parameters (glycogen content, GLY; protein content, PROT; electron transport system activity, ETS), and oxidative stress markers (superoxide dismutase activity, SOD; catalase activity, CAT; glutathione S-transferases activity, GSTs; lipid peroxidation levels, LPO; reduced (GSH) and oxidized (GSSG) glutathione content). The results obtained demonstrated that with the increase of exposure concentrations mussels tended to increase their energy reserves and maintain their metabolic potential, which was significantly higher only at the highest concentration. Our findings clearly revealed that cetirizine inhibited the activity of GSTs and although induced the activity of antioxidant enzymes (SOD and CAT) mussels were not able to prevent cellular damages observed through the increase of LPO associated to the increase of exposure concentrations. Thus, this study confirmed that cetirizine induces toxic effects in Mytilus galloprovincialis, which, considering their trophic relevance, wide use as bioindicator and wide spatial distribution of this species, can result in ecological and economic negative impacts at a large scale.
Caffeine is known to be one of the most consumed psychoactive drugs. For this reason, caffeine is continuously released into the environment with potential impacts on inhabiting organisms. The current study evaluated the biochemical alterations induced in the clam species Ruditapes philippinarum after exposure for 28 days to caffeine (0.5, 3.0 and 18.0 mg/L). The results obtained showed that, with the increasing caffeine concentrations, an increase in clams defense mechanisms (such as antioxidant and biotransformation enzymes activity) was induced which was accompanied by an increase in protein content. Nevertheless, although an increase on defense mechanisms was observed, clams were not able to prevent cells from lipid peroxidation that increased with the increase of caffeine concentration. Furthermore, with the increase of exposure concentrations, clams increased their metabolic activity (measured by electron transport activity), reducing their energy reserves (glycogen content), to fight against oxidative stress. Overall, the present study demonstrated that caffeine may impact bivalves, even at environmentally relevant concentrations, inducing oxidative stress in organisms. The present study is an important contribution to address knowledge gaps regarding the impacts of long-term exposures to pharmaceuticals since most of the studies assessed the effects after acute exposures, most of them up to 96 h.
In Coastal Systems, pollutants as pharmaceutical drugs exert changes from the molecular to the organism level in marine bivalves. Besides pollutants, Coastal Systems are prone to changes in environmental Parameters, as the alteration of salinity values because of Climate Change. Together, these Stressors (pharmaceutical drugs and salinity changes) can exert different threats than each Stressor acting individually; for example, salinity can change the physical-chemical properties of the drugs and/or the sensitivity of the organisms to them. However, limited Information is available on this subject, with variable results, and for this reason, this study aimed to evaluate the impacts of salinity changes (15,25 and 35) on the effects of the antiepileptic carbamazepine (CBZ, 1 (ig/L) and the antihistamine cetirizine (CTZ, 0.6 pg/L), when acting individually and combined (CBZ + CTZ), in the edible clam Ruditapes philippinarum. After 28 days ofexposure, drugs concentrations, bioconcentration factors and biochemical parameters, related to clam's metabolic caparity and oxidative stress were evaluated. The results showed that dams under low salinity suffered more changes in metabolic, antioxidant and biotransformation activities, in comparison with the remaining salinities under study. However, limited impacts were observed when comparing drug effects at low salinity. Indeed, it seemed that CTZ and CBZ + CTZ, under high salinity (salinity 35) were the worst exposure conditions for the dams, since they caused higher leveis of cellular damage. It Stands out that salinity changes altered the impact of pharmaceutical drugs on marine bivalves.
In coastal systems, organisms are exposed to amultitude of stressors whose interactions and effects are poorly studied. Pharmaceutical drugs and Climate Change consequences, such as lowered pH, are examples of stressors affecting marine organisms, as bivalves. Although a vast literature is available for the effects of these stressors when acting individually, very limited information exists on the impacts that the combination of both can have on marine bivalves. For this reason, this study aimed to evaluate the impacts of a simulated ocean acidification scenario (control pH, 8.0; lowered pH, pH 7.6) on the effects of the antiepileptic carbamazepine (CBZ, 1 μg/L) and the antihistamine cetirizine (CTZ, 0.6 μg/L), when acting individually and combined (CBZ + CTZ), on the edible clam Ruditapes philippinarum. After 28 days of exposure, drug concentrations, bioconcentration factors and biochemical parameters related to the clams' metabolic capacity and oxidative stress were evaluated. The results showed that R. philippinarum clams responded differently to pharmaceutical drugs depending on the pH tested, influencing both bioconcentration and biological responses. In general, drug combined treatments showed fewer impacts than drugs acting alone, and acidification seemed to activate at a higher extension the elimination processes that were not activated under control pH. Also, lowered pH per se exerted negative impacts (e.g., cellular damage) on R. philippinarum and the combination with pharmaceutical drugs did not enhance the toxicity.
The negative effects induced in marine organisms by Climate Change related abiotic factors consequences, namely ocean warming, are well-known. However, few works studied the combined impacts of ocean warming and contaminants, as pharmaceutical drugs. Carbamazepine (CBZ) and cetirizine (CTZ) occur in the marine environment, showing negative effects in marine organisms. This study aimed to evaluate the impacts of Ocean warming on the effects of CBZ and CTZ, when acting individually and combined (drug vs drug), in the edible clam Ruditapes philippinarum. For that, drugs concentration, bioconcentration factors and biochemical parameters, related with clam’s metabolic capacity and oxidative stress, were evaluated after 28 days exposure to environmentally relevant scenarios of these stressors. The results showed limited impacts of the drugs (single and combined) at control and warming condition. Indeed, it appeared that warming improved the oxidative status of contaminated clams (higher reduced to oxidized glutathione ratio, lower lipid peroxidation and Protein carbonylation levels), especially when both drugs were combined. This may result from clam’s defence mechanisms activation and reduced metabolic capacity that, respectively, increased elimination and limited production of reactive oxygen species. At low stress levels, defence mechanisms were not activated which resulted into oxidative stress. The present findings highlighted that under higher stress levels clams may be able to activate defence strategies that were sufficient to avoid cellular damages and loss of redox homeostasis.
Nevertheless, low concentrations were tested in the present study and the observed responses may greatly Change under increased pollution levels or temperatures. Further research on this topic is needed since marine heat waves are increasing in frequency and intensity and pollution levels of some pharmaceuticals are also increasing in coastal systems.
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.
Carbamazepine (CBZ) is an antiepileptic drug commonly detected in aquatic systems, with toxic effects to inhabiting organisms. Limited information is known on stress response biomarkers associated to bioconcentration and depuration of CBZ in aquatic organisms. Moreover, few studies addressed if the response and recovery of organisms to a contaminant can change when they are collected in a contaminated site. This study intended to understand the bioconcentration and depuration of CBZ combined with its toxicological impact in Scrobicularia plana clams collected from two contrasting areas (MIRA, Mira channel, non-contaminated and LAR, Laranjo bay, arithropogenically impacted) from the Ria de Aveiro (Portugal). The clams were exposed for 14 days to environmentally relevant CBZ concentrations (0.0, 4.0 and 8.0 mu g/L), followed by a 14 day depuration period. CBZ concentrations in S. plana tissues were rapidly bioconcentrated during the exposure period. In the depuration period CBZ was eliminated, in some extent. The main toxic effects occurred at the highest concentration (8.0 mu g/L) after 14 days of exposure in which the clams from LAR accumulated ahigher CBZ concentration (LAR: similar to 10 ng/g FW) than clams from MIRA (MIRA: similar to 7 ng/g FW). LAR clams exhibited higher oxidative damage at this concentration, demonstrated by higher LPO levels over time (increase of similar to 1.4% relative to control) and, in comparison with MIRA clams (LAR: 17.7 nmol/g FW; MIRA: 11.4 nmol/g FW). After the depuration period, LAR clams recovered from the stress induced by CBZ. A decrease in LPO for LAR (decrease of similar to 40% in relation to the end of the exposure period) was accompanied by a decrease in CBZ tissue concentrations (decrease of similar to 61% relative to the end of the exposure period). MIRA clams were not oxidatively injured (low LPO levels remained unchanged after the depuration and CBZ decreased similar to 80% relative to the end of the exposure period).
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.
In the aquatic environment, organisms are exposed to complex mixtures of contaminants which may alter the toxicity profile of each compound, compared to its toxicity alone. Pharmaceutical drugs (e.g. carbamazepine (CBZ) and cetirizine (CTZ)) and metals (e.g. cadmium (Cd)) are among those contaminants that co-occur in the environment. However, most studies concerning their toxicity towards aquatic species are based on single exposure experiments. Thus, the present study aimed to evaluate single and combined effects of Cd and CBZ or CTZ (single conditions: Cd, CTZ, CBZ; combined conditions: CTZ+Cd, CBZ+Cd) on biomarkers related to oxidative stress and energy metabolism in the edible clam Ruditapes philippinarum, by exposing the organisms for 28 days to environmentally relevant concentrations of these contaminants. The biomarkers studied were: i) the electron transport system activity, protein and glycogen contents (indicators of organisms’ metabolic status and energy reserves); ii) lipid peroxidation and the ratio between reduced and oxidized glutathione (indicators of oxidative stress); iii) superoxide dismutase and catalase activities (enzymes indicators of antioxidant defence) and iv) activity of glutathione S-transferases (family of enzymes indicators of biotransformation capacity). Results obtained showed that the uptake of Cd and CBZ was not affected by the combined presence of the contaminants.
However, for CTZ, the uptake was higher in the presence than in the absence of Cd. Concerning toxicity data, in general, the combined exposures (CTZ+Cd, CBZ+Cd) had lower biological effects than the contaminants alone. Nevertheless, our data showed that despite the low concentrations tested, they were enough to exert biological effects that differed between single and combined treatments, evidencing the need to conduct more co-exposure studies to increase the environmental relevance of the gathered data.
Carbamazepine is a psychiatric pharmaceutical widely detected in aquatic environments. Due to its generalized occurrence and environmental persistence it might be considered as an anthropogenic pollution indicator. In this research, a previously developed enzyme-linked immunosorbent assay (ELISA), based on a commercial monoclonal antibody, was applied to the quantification of carbamazepine in ground, surface and wastewaters and results were validated by liquid chromatographytandem mass spectrometry (LCMS/MS).
The performance of the applied ELISA methodology was tested in the presence of high concentrations of sodium chloride and dissolved organic matter. The method was not significantly affected by matrix effects, being adequate for the quantification of carbamazepine in environmental samples, even without sample pre-treatment. This method allows the quantification of carbamazepine in the range of 0.0310 µg L-1, with a relative error lower than 30%. Due to a pH dependent cross-reactivity with cetirizine, an antihistaminic drug, the assay also enabled the quantification of cetirizine in the samples.
The application of the developed method to the quantification of carbamazepine was performed by using environmental samples with very different matrices, collected in the geographical area of Ria de Aveiro, an estuarine system located in the North of Portugal. Carbamazepine was detected in all analyzed wastewater samples and in one surface water with concentrations between 0.1 and 0.7 µg L-1. Validation with LCMS/MS revealed that results obtained by ELISA are 228% overestimated, which was considered highly satisfactory due to the absence of sample pre-treatments.
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.
Sulfamethoxazol (SMX),a sulfonamide, is a widely used bacteriostatic antibiotic and therefore a promising marker for the entry of anthropogenic Pollution in the environment. SMX is frequently found in wastewater and surface water. This study presents the production of high affinity and selective polyclonal antibodies for SMX and the development and Evaluation of a direct competitive enzyme-linked immunosorbent assay(ELISA)for the quantification of SMX in environmental watersamples. The crystal structures of the cross-reacting compounds sulfamethizole, N4-acetyl-SMX andsuccinimidyl-SMX were determined by x-ray diffraction aiming to explain their high cross-reactivity. These crystal structures are described for the first time. The quantification range of the ELISA is 0.82–63 µg/L. To verify our results, the SMX concentration in 20 environmental samples,including wastewater and surfacewater,was determined by ELISA and tandem mass spectrometry(MS/MS).A good Agreement of the measured SMX concentrations was found with average recoveries of 97–113%for the results of ELISA compared to LC-MS/MS.
Sulfamethoxazol (SMX),a sulfonamide, is a widely used bacteriostatic antibiotic and therefore a promising marker for the entry of anthropogenic Pollution in the environment. SMX is frequently found in wastewater and surface water. This study presents the production of high affinity and selective polyclonal antibodies for SMX and the development and Evaluation of a direct competitive enzyme-linked immunosorbent assay(ELISA)for the quantification of SMX in environmental watersamples. The crystal structures of the cross-reacting compounds sulfamethizole, N4-acetyl-SMX andsuccinimidyl-SMX were determined by x-ray diffraction aiming to explain their high cross-reactivity. These crystal structures are described for the first time. The quantification range of the ELISA is 0.82–63 µg/L. To verify our results, the SMX concentration in 20 environmental samples,including wastewater and surfacewater,was determined by ELISA and tandem mass spectrometry(MS/MS).A good Agreement of the measured SMX concentrations was found with average recoveries of 97–113%for the results of ELISA compared to LC-MS/MS.
The antimicrobial photodynamic approach has been demonstrated as an efficient and sustainable process for the eradication of microbial pathogens. In this work, silica-coated Magnetite nanoparticles (NPs) were used as carriers of glycosylated porphyrins and phthalocyanines. Their subsequent cationization
resulted in the production of stable antimicrobial photosensitizing materials, effective against E. coli. Suspensions of the photocatalysts in water present bimodal size distributions formed by big clusters and small NPs with hydrodynamic diameters between 8 and 38 nm. The presence of small NPs in the suspensions is related to an effective photodynamic inactivation (PDI) of E. coli cells. Glycosylation of the PS showed a positive effect on the PDI performance, which could be related to a higher accumulation of the photocatalyst over the bacterial cell membrane. In addition, these biocidal agents proved to be photostable and their photoactive performance decreased only between 23% and 28% upon 5 PDI cycles, mostly because of the loss of material between cycles, which makes them promising materials for water disinfection purposes.
The aim of this work was to investigate the effects of long-term application of different organic fertilizers (sewage sludge, farmyard manure, compost) as compared to mineral fertilizer on the structure of the soil organic matter. Capillary electrophoresis was employed for the quantification of monosaccharides and phenolic compounds, whereas NMR and FT-IR were used for the overall characterization of the soils organic matter. Application of farmyard manure results in a higher content of organic matter derived from angiosperms, suggested by the higher levels of syringic and vanillic phenols. Spectroscopic studies show an increase of lignin and lignin-like products in the organic matter of the soil, which may be derived from the cereal straw supplied with farmyard manure. According to spectroscopic analysis, 13C CPMAS-NMR and FT-IR spectra, higher contents of methylene groups ( CH2) from proteins and protein-like compounds, as well as higher levels of carbohydrates, were found in the soil supplied with compost. The monosaccharide (rhamnose, xylose, glucose, mannose, arabinose, fucose and galactose) content was not significantly influenced by the different organic fertilizers, suggesting that the type of amendment used does not affect any of these six studied monomers. Comparing the three organic amendments the most significant differences were observed after long-term application of farmyard manure, with an increase in lignin and lignin-like products in the soil organic matter, and compost, which appears to contribute to an increase of protein and protein-like, as well as carbohydrates content on soil organic matter. The knowledge of such changes can be essential to understand the sorption and bioavailability of pollutants, as well as establish/unestablish ways to recycling organic residues as organic fertilizers.
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.
During the last two decades, studies related to the occurrence and fate of emerging contaminants in the aquatic environment have received great attention from the international scientific community. The monitoring of the presence of these compounds is particularly important since they are known to induce adverse effects in aquatic environments, even at extremely low concentrations. This work aimed to apply a simple and effective methodology, such as enzyme-linked immunosorbent assay (ELISA), in the monitoring of 17a-ethinylestradiol (EE2) and 17b-estradiol (E2) (a synthetic and a natural hormone, respectively), carbamazepine (CBZ, an antiepileptic), cetirizine (CET, an antihistamine) and caffeine (CAF, a stimulant) in water matrices with differing salinity and organic matter contents. ELISA was proven to be a valid and practical tool, especially for screening purposes in contrast to traditional chromatographic techniques which are prohibitively expensive for an application on a broader base. The main originality of this work was to establish seasonal and spatial effects on the occurrence of the referred contaminants by using the effectiveness of ELISA to screen those compounds in samples with different characteristics.
This work reports both the seasonal and spatial quantification of the referred contaminants in the aquatic environment of the central region of Portugal, with concentrations ranging as follows: 5–87 ng L-1, for
E2, 2–17 ng L-1, for EE2, 10–1290 ng L-1, for CBZ, 10–190 ng L-1, for CET, and 62–6400 ng L-1, for CAF.
The transport and fate of hydrophobic organic contaminants in the environment involve complex phenomena that are influenced by many processes that include sorption by soil components. Sorption behavior of EE2 molecules onto different soil samples was studied and results correlated with the content and type of organic matter present. The highest Κ value, among all soils presented in this study, was obtained for soil fertilized with compost (1.22) which presented the highest organic carbon content. Also the sorption behavior depends greatly on the soil specific organic matter characteristics. A strong positive correlation was observed between aromatic and carboxylic units and ΚOC values. The results also suggested an association of the EE2 aromatic nuclei face to face with the surface and/or another EE2 molecule and also sorbentsorbate interactions due to hydrogen or covalent bonding, likely to occur due to the presence of phenolic function at C-3 and hydroxyl function at C-17 of the EE2 molecules that can react with carboxylic functional groups of soil organic matter. The stronger EE2 sorbs to soil organic matter lower is the leaching into drinking water resources and runoff to rivers and surface water, minimizing its residual toxicity.
The implementation of the Water Framework Directive (2000/60/EC) requires the establishment of monitoring programs. However, conventional procedures for sample preparation prior to chromatographic analysis are rather expensive and time consuming, being the development of cost-effective and easy tool a necessity. The aim of this work was to develop an enzyme-linked immunosorbent assay (ELISA) able to determine atrazine in water samples. Matrix effects evaluation showed that the increase of humic acid (HA) concentration leads to flattened calibration curves and to the loss of the sigmoidal shape. However, such interference was overcome, by the presence of an environmental sample buffer, incubated together with the samples. Recoveries from 88.5 to 119.2 % were obtained in the presence of HA concentrations up to 20 mg-1. An analytical range from 0.003 to 1 µgL-1 was obtained, and atrazine was detected in a sewage treatment plant with concentrations ranging from 14 to 52 ngL-1.
Towards the standardization of biochar analysis: the COST action TD1107 interlaboratory comparison
(2016)
Biochar produced by pyrolysis of organic residues is increasingly used for soil amendment and many other applications. However, analytical methods for its physical and chemical characterization are yet far from being specifically adapted, optimized, and standardized. Therefore, COST Action TD1107 conducted an interlaboratory comparison in which 22 laboratories from 12 countries analyzed three different types of biochar for 38 physical–chemical parameters (macro- and microelements, heavy metals, polycyclic aromatic hydrocarbons, pH, electrical conductivity, and specific surface area) with their preferential methods. The data were evaluated in detail using professional interlaboratory testing software. Whereas intralaboratory repeatability was generally good or at least acceptable, interlaboratory reproducibility was mostly not (20% < mean reproducibility standard deviation < 460%). This paper contributes to better comparability of biochar data published already and provides recommendations to improve and harmonize specific methods for biochar analysis in the future.
In the aquatic environment, pharmaceutical drugs are submitted to degradation processes, where pho-todegradation is one of the most important mechanisms affecting the fate, persistence and toxicity of thecompounds. Carbamazepine, a widely used antiepileptic, is known to suffer photodegradation in waterbodies and generate photoproducts, some of them with higher potential toxicity than the parent com-pound. Therefore, to evaluate the toxic effects of CBZ when combined with its photoproducts, an acuteexposure (96 h) with the edible clam Scrobicularia plana was performed using environmental concentra-tions of CBZ (0.00–9.00 µg/L) irradiated (and non-irradiated) with simulated solar radiation. The analysisof the irradiated CBZ solutions by mass spectrometry revealed the formation of 5 photoproducts, includ-ing acridine (a compound known to be carcinogenic). Oxidative stress results showed that the exposureto CBZ photoproducts did not increase the toxicity to clams, by comparison with the parent compound.
Estrogens, such as 17β-estradiol (E2) and 17α-ethinylestradiol (EE2), are the major responsible for endocrine-disrupting effects observed in aquatic environments due to their high estrogenic potency, even at concentrations ranging from pg L-1 to ng L-1. Thus, it is essential to develop analytical methodologies suitable for monitoring their presence in water samples. Dispersive liquidliquid microextraction (DLLME) was used as a pre-concentration step prior to the quantification of E2 and EE2 by enzyme-linked immunosorbent assay (ELISA). First, an evaluation of the effect of DDLME on the E2 and EE2 ELISA calibration curves was performed. Since the extraction procedure itself had an influence on the ELISA optical density (OD), it became necessary to subject, not only the samples, but also all the standards to the DLLME process. Working ranges were determined, being between 1.2 and 8000 ng L-1, for E2, and between 0.22 and 1500 ng L-1, for EE2. The influence of organic matter, both in the extraction and quantification, was evaluated and it was observed that its presence in the solution did not affect considerably the calibration curve. Recovery rates were also determined, ranging from 77% to 106% for ultrapure water and from 104% to 115% for waste water samples, the most complex ones in what concerns matrix effects. Results obtained when applying the proposed method to real water samples can be considered quite satisfying. Moreover, the obtained working ranges encompass values generally reported in literature, confirming the practical use of the method for environmental samples.
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.
This study comprises the development of enzyme-linked immunosorbent assays (ELISAs) for the quantification of 17β-estradiol (E2) and 17α-ethinylestradiol (EE2) in complex aqueous matrices without any sample clean-up procedures. Salinity and dissolved organic matter were selected as potential interfering agents in the analysis of E2 and EE2. The optimization was performed in order to (i) overcome matrix effects, and to (ii) increase sensitivity. The addition of a sample buffer containing bovine serum albumin (BSA) prior to the sample was found to decrease the influence of matrix effects. Moreover, adjustments of this buffer's pH together with the optimization of tracer (T) dilution and incubation time were undertaken in order to lower the quantification range. The optimized methods allowed the quantification of E2 and EE2 in the ranges 0.03200 µg L-1 and 0.0210 µg L-1, respectively. The assays were applied to real aqueous samples. It was possible to do a first approach to the levels of E2 in Portuguese surface and waste waters; however, it was not feasible to detect EE2 in the samples tested.
Pesticides may contaminate ground and surface waters and one of the major factors governing this property is soil sorption. Sorption can be assessed by batch equilibrium technique which produces lots of extracts with high dissolved organic carbon concentration in which the pesticide concentration has to be determined. We developed an ELISA procedure to analyse atrazine based on polyclonal antibodies (C193) for which tracer structure and dilutions of immunochemical reagents were adapted to fit the purpose. After a 1000-fold dilution (or after an SPE clean-up procedure) extracts of a sewage-sludge amended luvisol (used as an example application of the methodology developed) could be reliably analysed. The Freundlich model is able to describe adsorption for this system (r² = 0.977) delivering a distribution coefficient KF of 1.6 ± 0.2 (mg kg-1) (mg L-1)-N and an isotherm nonlinearity factor N of 0.70 ± 0.09.
Sorption of atrazine on soils subjected to three different organic amendments was measured using a batch equilibrium technique. A higher KF value (2.20 kg-1(mg L-1)-N) was obtained for soil fertilized with compost, which had a higher organic matter (OM) content. A correlation between the KFOC values and the percentage of aromatic carbon in OM was observed. The highest KFOC value was obtained for the soil with the highest aromatic content. Higher aromatic content results in higher hydrophobicity of OM, and hydrophobic interactions play a key role in binding of atrazine. On the other hand, the soil amended with farmyard manure had a higher content of carboxylic units, which could be responsible for hydrogen bonding between atrazine and OM. Dominance of hydrogen bonds compared to hydrophobic interactions can be responsible for the lower desorption capacity observed with the farmyard manure soil. The stronger hydrogen bonding can reduce the leaching of atrazine into drinking water resources and runoff to rivers and other surface waters.