Sulfadiazine's photodegradation using a novel magnetic and reusable carbon based photocatalyst: Photocatalytic efficiency and toxic impacts to marine bivalves.

In the present study, waste-based biochar functionalized with titanium dioxide (TiO2) and afterwards magnetized by an ex-situ approach, defined as synthetic photosensitizer (SPS), was explored for the photocatalytic degradation of sulfadiazine (SDZ), an antibiotic widely used in the aquaculture industry, under solar irradiation. The use of the SPS enhanced the photodegradation efficiency, with a half-life time (t1/2) reduction from 12.2 ± 0.1 h (without SPS) to 5.6 ± 0.4 h. The applied magnetization procedure allowed to obtain a SPS with good reusability for SDZ photodegradation even after five consecutive cycles. To evaluate the effects on marine bivalves of SDZ, before and after photodegradation and in presence or absence of the SPS, a typical bioindicator species, the mussel Mytilus galloprovincialis, was used and different biochemical markers were analysed. Results obtained indicated that the exposure to SDZbefore irradiation, both in absence and presence of SPS, caused an increase in mussels' metabolism and defence mechanisms, evidencing great biochemical impacts. However, after irradiation (in the absence and presence of SPS), biochemical responses were similar to those observed in organisms exposed to control conditions, without SDZ. Therefore, this work provided a promising eco-friendly treatment for the removal of SDZ from aquaculture effluents.

Effects of Carbamazepine in Bivalves: A Review.

Carbamazepine (CBZ) is among the ten most frequent pharmaceuticals that occur in the aquatic systems, with known effects on inhabiting organisms, including bivalves. Bivalves are important species in coastal ecosystems, often exhibiting a dominant biomass within invertebrate communities. These organisms play a major role in the functioning of the ecosystem and particularly in food webs (as suspension-feeders) and represent a significant fraction of the fisheries resource. They also have strong interactions with the environment, water and sediment and are considered good bioindicator species. The present paper reviews the known literature on the impacts of CBZ in biological endpoints of marine bivalves exposed to environmentally and non-environmentally relevant concentrations, highlighting differences in terms of biological responses, associated with exposure period, concentrations tested, and species used. Overall, the literature available showed that CBZ induces individual and sub-individual effects in marine bivalves (adults and life stages) and the most common effect reported was the induction of oxidative stress.

Solidified floating organic drop microextraction (SFODME) for the simultaneous analysis of three non-steroidal anti-inflammatory drugs in aqueous samples by HPLC.

In this work, a liquid-liquid microextraction methodology using solidified floating organic drop (SFODME) was combined with liquid chromatography and UV/Vis detection to determine non-steroidal anti-inflammatory drugs (NSAIDs) naproxen (NPX), diclofenac (DCF), and mefenamic acid (MFN) in tap water, surface water, and seawater samples. Parameters that can influence the efficiency of the process were evaluated, such as the type and volume of the extractor and dispersive solvents, effect of pH, agitation type, and ionic strength. The optimized method showed low detection limits (0.09 to 0.25 µg L-1), satisfactory recovery rates (90 to 116%), and enrichment factors in the range between 149 and 199. SFODME showed simplicity, low cost, speed, and high concentration capacity of the analytes under study. Its use in real samples did not demonstrate a matrix effect that would compromise the effectiveness of the method, being possible to apply it successfully in water samples with different characteristics.

How temperature can alter the combined effects of carbon nanotubes and caffeine in the clam Ruditapes decussatus?

Nowadays, multi-walled carbon nanotubes are considered to be emerging contaminants and their impact in ecosystem has drawn special research attention, while other contaminants, such as caffeine, have more coverage in literature. Despite this, the effects of a combination of the two has yet to be evaluated, especially considering predicted temperature rise. In the present study a typical bioindicator species for marine environment, the clam Ruditapes decussatus, and classical tools, such as biomarkers and histopathological indices, were used to shed light on the species' response to these contaminants, under actual and predicted warming scenarios. The results obtained showed that both contaminants have a harmful effect at tissue level, as shown by higher histopathological index, especially in digestive tubules. Temperatures seemed to induce greater biochemical impacts than caffeine (CAF) and -COOH functionalized multi-walled carbon nanotubes (f-MWCNTs) when acting alone, namely in terms of antioxidant defences and energy reserves content, which were exacerbated when both contaminants were acting in combination (MIX treatment). Overall, the present findings highlight the complex response of clams to both pollutants, evidencing the role of temperature on clams' sensitivity, especially to mixture of pollutants.

Biochar-TiO2 magnetic nanocomposites for photocatalytic solar-driven removal of antibiotics from aquaculture effluents.

Contamination of surrounding waters with antibiotics by aquaculture effluents can be problematic due to the possible increase of bacterial resistance, making it crucial the efficient treatment of those effluents before their release into the environment. In this work, the application of waste-based magnetic biochar/titanium dioxide (BC/TiO2) composite materials on the photodegradation of two antibiotics widely used in aquaculture (sulfadiazine (SDZ) and oxolinic acid (OXA)) was assessed. Four materials were synthesized: BCMag (magnetized BC), BCMag_TiO2 (BCMag functionalized with TiO2), BC_TiO2_MagIn and BC_TiO2_MagEx (BC functionalized with TiO2 and afterwards magnetized by in-situ and ex-situ approaches, respectively). SDZ half-life time (t1/2) noticeably decreased 3.9 and 3.4 times in presence of BCMag_TiO2 and BC_TiO2_MagEx, respectively. In the case of OXA, even though differences were not so substantial, the produced photocatalysts also allowed for a decrease in t1/2 (2.6 and 1.7 times, in presence of BCMag_TiO2 and BC_TiO2_MagEx, respectively). Overall, the here synthesized BC/TiO2 magnetic nanocomposites through a circular economy process are promising photocatalysts for a sustainable solar-driven removal of antibiotics from aquaculture effluents.

Monitoring pharmaceuticals in the aquatic environment using enzyme-linked immunosorbent assay (ELISA)-a practical overview.

The presence of pharmaceuticals, which are considered as contaminants of emerging concern, in natural waters is currently recognized as a widespread problem. Monitoring these contaminants in the environment has been an important field of research since their presence can affect the ecosystems even at very low levels. Several analytical techniques have been developed to detect and quantify trace concentrations of these contaminants in the aquatic environment, namely high-performance liquid chromatography, gas chromatography, and capillary electrophoresis, usually coupled to different types of detectors, which need to be complemented with time-consuming and costly sample cleaning and pre-concentration procedures. Generally, the enzyme-linked immunosorbent assay (ELISA), as other immunoassay methodologies, is mostly used in biological samples (most frequently urine and blood). However, during the last years, the number of studies referring the use of ELISA for the analysis of pharmaceuticals in complex environmental samples has been growing. Therefore, this work aims to present an overview of the application of ELISA for screening and quantification of pharmaceuticals in the aquatic environment, namely in water samples and biological tissues. The experimental procedures together with the main advantages and limitations of the assay are addressed, as well as new incomes related with the application of molecular imprinted polymers to mimic antibodies in similar, but alternative, approaches. Graphical Abstract.

Photodegradation of sulfadiazine in different aquatic environments - Evaluation of influencing factors.

The presence of antibiotics, such as sulfadiazine (SDZ), in the aquatic environment contributes to the generation of antimicrobial resistance, which is a matter of great concern. Photolysis is known to be a major degradation pathway for SDZ in surface waters. Therefore, influencing factors affecting SDZ photodegradation in different aquatic environments were here evaluated in order to have a better knowledge about its persistence in the environment. Photodegradation of SDZ was found to be more efficient at higher pH (t1/2 = 6.76 h, at pH = 7.3; t1/2 = 12.2 h, at pH = 6.3), in the presence of humic substances (HS) (t1/2 between 1.76 and 2.42 h), as well as in the presence of NaCl (t1/2 = 1.00 h) or synthetic sea salts (t1/2 = 0.78 h). Using ˙OH and 1O2 scavengers, it was possible to infer that direct photolysis was the main pathway for SDZ photodegradation in ultrapure water. Furthermore, results under N2 purging confirmed that 1O2 was not relevant in the phototransformation of SDZ. Then, the referred observations were used for the interpretation of results obtained in environmental matrices, namely the final effluent of a sewage treatment plant (STPF), fresh and brackish water (t1/2 between 2.3 and 3.48 h), in which SDZ photodegradation was found to be much faster than in ultrapure water (t1/2 = 6.76 h).

Determination of estrone and 17α-ethinylestradiol in digested sludge by ultrasonic liquid extraction and high-performance liquid chromatography with fluorescence detection.

Estrone, 17ß-estradiol and 17α-ethinylestradiol are increasingly recognised as important micropollutants to be monitored in wastewater treatment plants. These estrogens are retained onto sludge due to their high adsorption and since they are largely used in land applications, the monitoring of these chemicals in sludge samples is of great importance. This study describes a method for the determination of estrone and 17α-ethinylestradiol in fresh sludge samples. After spiking fresh digested sludge with estrone and 17α-ethinylestradiol and maintaining in contact during 5, 30 and 60 min, the freeze-dried samples were subjected to ultrasonic liquid extraction, with methanol and acetone, and analysed by high-performance liquid chromatography with fluorescence detection. The average recoveries obtained for estrone and 17α-ethinylestradiol using the different contact times were 103 ± 3 and 97 ± 4%, respectively. Fresh sludge samples from one waste water treatment plant located in Portugal were analysed and estrone was detected in primary fresh sludge, anaerobic digested sludge and dehydrated sludge at a concentration in the range of 1-4.8 µg/g. The method here developed does not require any sample clean-up, being fast and simple, reliable and inexpensive, making possible its application for monitoring the contamination of sludge with these estrogens.

Single and multi-component adsorption of psychiatric pharmaceuticals onto alternative and commercial carbons.

This work describes the adsorptive removal of three widely consumed psychiatric pharmaceuticals (carbamazepine, paroxetine and oxazepam) from ultrapure water. Two different adsorbents were used: a commercial activated carbon and a non-activated waste-based carbon (PS800-150-HCl), produced by pyrolysis of primary paper mill sludge. These adsorbents were used in single, binary and ternary batch experiments in order to determine the adsorption kinetics and equilibrium isotherms of the considered pharmaceuticals. For the three drugs and both carbons, the equilibrium was quickly attained (with maximum equilibrium times of 15 and 120 min for the waste-based and the commercial carbons, respectively) even in binary and ternary systems. Single component equilibrium data were adequately described by the Langmuir model, with the commercial carbon registering higher maximum adsorption capacities (between 272 ± 10 and 493 ± 12 µmol g-1) than PS800-150-HCl (between 64 ± 2 and 74 ± 1 µmol g-1). Multi-component equilibrium data were also best fitted by the single component Langmuir isotherm, followed by the Langmuir competitive model. Overall, competitive effects did not largely affect the performance of both adsorbents. Binary and ternary systems maintained fast kinetics, the individual maximum adsorption capacities were not lower than half of the single component systems and both carbons presented improved total adsorption capacities for multi-component solutions.

Photosensitized Degradation of 17ß-estradiol and 17α-ethinylestradiol: Role of Humic Substances Fractions.

Photodegradation of 17α-ethinylestradiol (EE2) and 17ß-estradiol (E2) was investigated under simulated solar radiation. Photodegradation kinetics in the absence and presence of humic substances (HSs) fractions (humic acids [HAs], fulvic acids [FAs], and XAD-4), were compared. Although all three fractions were responsible for a noticeable increase on photodegradation rates, the effects were greater for FA and XAD-4. Half-life time decreased from 46 and 94 h (direct photodegradation) for EE2 and E2, respectively, to 6.4, 2.1, and 2.7 h (for EE2) and 5.7, 2.9, and 3.1 h (for E2) in the presence of HAs, FAs, and XAD-4, respectively. The XAD-4 fraction results were similar to those of FAs, which is considered the most photochemically active fraction of HSs. Studies were also conducted in organic matter-rich environmental water matrices. After 5 h, photodegradation ranged from 44 to 94% for EE2 and from 27 to 95% for E2, compared with 16% for EE2 and 6% for E2 in ultrapure water. The maximum photodegradation was obtained in an estuarine water sample, known to be rich in FAs and XAD-4 fractions and poor in HAs, showing that not only is the presence of organic matter an important factor for the photodegradation increase, as also the type of organic matter is determinant.

Adsorptive removal of pharmaceuticals from water by commercial and waste-based carbons.

This work describes the single adsorption of seven pharmaceuticals (carbamazepine, oxazepam, sulfamethoxazole, piroxicam, cetirizine, venlafaxine and paroxetine) from water onto a commercially available activated carbon and a non-activated carbon produced by pyrolysis of primary paper mill sludge. Kinetics and equilibrium adsorption studies were performed using a batch experimental approach. For all pharmaceuticals, both carbons presented fast kinetics (equilibrium times varying from less than 5 min to 120 min), mainly described by a pseudo-second order model. Equilibrium data were appropriately described by the Langmuir and Freundlich isotherm models, the last one giving slightly higher correlation coefficients. The fitted parameters obtained for both models were quite different for the seven pharmaceuticals under study. In order to evaluate the influence of water solubility, log Kow, pKa, polar surface area and number of hydrogen bond acceptors of pharmaceuticals on the adsorption parameters, multiple linear regression analysis was performed. The variability is mainly due to log Kow followed by water solubility, in the case of the waste-based carbon, and due to water solubility in the case of the commercial activated carbon.

Evaluation of different functionalization methodologies for improving the removal of three target antibiotics from wastewater by a brewery waste activated carbon.

This work aims to increase the efficiency of an activated carbon produced from brewery waste (AC) in the removal of three target antibiotics (sulfamethoxazole (SMX), trimethoprim (TMP), and ciprofloxacin (CIP)) by surface incorporation of oxygen, nitrogen or sulfur groups. AC was produced using spent brewery grains (the most abundant waste from the brewing industry) as raw material, K2CO3 as activating agent and microwave energy for pyrolysis. Then, seven different functionalized AC were prepared, characterized for their physicochemical properties, and tested for adsorption (%) of SMX, TMP and CIP from three different matrices (ultrapure water (pH ~5-6), buffered ultrapure water (pH 8), and effluent from a municipal wastewater treatment plant (WWTP effluent (pH 8)), under batch operation. Based on the obtained results, an oxygen functionalized AC was selected for further characterization and studies on the adsorption of the target antibiotics from the WWTP effluent. Kinetic results fitted the pseudo-second order model and the equilibrium isotherms were adequately described by the Langmuir model, reaching maximum adsorption capacities (qm) of 124 ± 1 µmol g-1, 315 ± 2 µmol g-1 and 201 ± 5 µmol g-1 for SMX, TMP and CIP, respectively. The selected functionalization increased qm by up to 58 % in comparison with the non-functionalized AC. The oxygen modified AC produced from a biomass waste remarkably improved its performance for an efficient application in the removal of antibiotics from wastewater.

Surface coupling of molecularly imprinted polymers as strategy to improve sulfamethoxazole removal from water by carbons produced from spent brewery grain.

This work aims to assess the surface coupling of molecularly imprinted polymers (MIP) on carbon adsorbents produced from spent brewery grain, namely biochar (BC) and activated carbon (AC), as a strategy to improve selectivity and the adsorptive removal of the antibiotic sulfamethoxazole (SMX) from water. BC and AC were produced by microwave-assisted pyrolysis, and MIP was obtained by fast bulk polymerization. Two different methodologies were used for the molecular imprinting of BC and AC, the resulting materials being tested for SMX adsorption. Then, after selecting the most favourable molecular imprinting methodology, different mass ratios of MIP:BC or MIP:AC were used to produce and evaluate eight different materials. Molecular imprinting was shown to significantly improve the performance of BC for the target application, and one of the produced composites (MIP1-BC-s(1:3)) was selected for further kinetic and equilibrium studies and comparison with individual MIP and BC. The kinetic behaviour was properly described by both the pseudo-first and pseudo-second order models. Regarding equilibrium isotherms, they fitted the Freundlich and Langmuir models, with MIP1-BC-s(1:3) reaching a maximum adsorption capacity (qm) of 25 ± 1 µmol g-1, 19 % higher than BC. In comparison with other seven pharmaceuticals, the adsorption of SMX onto MIP1-BC-s(1:3) was remarkably higher, as for the specific recognition of this antibiotic by the coupled MIP. The pH study evidenced that SMX removal was higher under acidic conditions. Regeneration experiments showed that MIP1-BC-s(1:3) provided good adsorption performance, which was stable during five regeneration-reutilization cycles. Overall, this study has demonstrated that coupling with MIP may be a suitable strategy to improve the adsorption properties and performance of biochar for antibiotics removal from water, increasing its suitability for practical applications.

Development of ELISA methodologies for the direct determination of 17ß-estradiol and 17α-ethinylestradiol in complex aqueous matrices.

This study comprises the development of enzyme-linked immunosorbent assays (ELISAs) for the quantification of 17ß-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 0.03-200 µg L(-1) and 0.02-10 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.

Ex-situ magnetic activated carbon for the adsorption of three pharmaceuticals with distinct physicochemical properties from real wastewater.

Pharmaceuticals are able to evade conventional wastewater treatments and therefore, are recurrently found in the environment with proven potential to cause harm to human and wildlife. Adsorption onto activated carbon (AC) is a promising complement. However, AC production from non-renewable resources and its difficult after-use recuperation are prohibitive. Hence, a waste-based magnetic activated carbon (MAC) was produced from paper mill sludge, via an ex-situ synthesis, for the adsorptive removal of carbamazepine (CBZ), sulfamethoxazole (SMX) and ibuprofen (IBU) from ultrapure water and wastewater. The MAC was obtained through the promotion of electrostatic interactions between magnetic and activated carbon particles in a water suspension at controlled pH between the points of zero charge of both surfaces. The optimized condition (MACX3) presented remarkable properties regarding specific surface area (SBET=795 m2 g-1) and saturation magnetization (MS=19 emu g-1). Kinetic and equilibrium adsorption studies were performed under batch conditions. Adsorption equilibrium was reached in up to 30 min for all pharmaceuticals in both matrices, proving the low dependence on the adsorbate and the broad applicability of MACX3 in pharmaceutical adsorption. Regarding equilibrium experiments, high Langmuir maximum adsorption capacities (qm) were achieved in ultrapure water (up to 711 ± 40 µmol g-1). Equilibrium studies in wastewater revealed a decay in qm when compared to ultrapure water: 28% for CBZ (468 ± 20 µmol g-1 (111 ± 5 mg g-1)), 78% for SMX (145 ± 10 µmol g-1 (37 ± 3 mg g-1)) and 62% for IBU (273 ± 8 µmol g-1 (56 ± 2 mg g-1)), attributed to the wastewater pH, which dictates the speciation of the pharmaceuticals and controls electrostatic interactions between pharmaceuticals and MAC, and to competition effects by organic matter. It was demonstrated the promising applicability of a waste-based ex-situ MAC, rapidly retrievable from water, as an alternative tertiary wastewater treatment for pharmaceuticals removal.

Toxic effects of a mixture of pharmaceuticals in Mytilus galloprovincialis: The case of 17α-ethinylestradiol and salicylic acid.

The impact of pharmaceuticals on marine invertebrates has been a topic of rising concern, with an increasing number of studies regarding the impacts on bivalves. However, very few investigated the toxicity of mixtures of pharmaceuticals. This knowledge gap was investigated in the present study, where the toxicity of 17α-ethinylestradiol (EE2) and salicylic acid (SA) mixture was evaluated. To this end, Mytilus galloprovincialis mussels were chronically subjected to both pharmaceuticals, acting alone and in combination, and the effects at the cellular level were measured. The Independent Action (IA) model was performed aiming to compare obtained with predicted responses. The integrated biomarker response (IBR) index was used to assess the overall biochemical response given by mussels. The results obtained revealed that the most stressful condition was caused by the combined effect of EE2 and SA, with the highest metabolic capacity, antioxidant (catalase activity) and biotransformation (carboxylesterases activity) activation and cellular damage in organisms exposed to the mixture of both drugs in comparison to responses observed when each drug was acting alone. Predicted responses obtained from the IA model indicate that caution should be paid as frequent deviations to observed responses were found. This study highlights the need for future studies considering the mixture of pollutants, mimicking the actual environmental conditions.

Adsorption of the antiepileptic carbamazepine onto agricultural soils.

Carbamazepine is an antiepileptic pharmaceutical which is commonly found in environmental matrices. It passes through wastewater treatment plants (WWTPs) almost completely unaffected and has been found to be highly persistent in the environment. The application of sludge in agricultural fields and the use of WWTP effluents for irrigation constitute a potential source of soil contamination. Consequently, the assessment of the interaction between carbamazepine and soils is of crucial importance to understand its fate in the environment. To monitor the sorption behavior of carbamazepine onto agricultural soils, batch equilibrium experiments were performed using soils subjected to distinct long-term fertilizations. In order to follow the adsorption experiments, an UV spectral deconvolution methodology was applied and the results compared with those from micellar electrokinetic chromatography. The results obtained by both methods did not present significant statistical differences at 95% confidence level. Therefore, it was proven that, in the context of adsorption studies, UV spectral deconvolution is a valid alternative to common chromatographic methods, with the major advantage of being a simple and fast procedure. The adsorption of carbamazepine onto the selected soils was satisfactorily described by the Freundlich model. The obtained Freundlich parameters (K(F)) (between 1.79 ± 0.07 and 4.8 ± 0.2 mg kg(-1) (mg L(-1))(-N)) indicate that the adsorption behavior of carbamazepine is dependent on the soil fertilization. Also, it is not extensively sorbed, indicating that carbamazepine present in soils can be a potential source of contamination of surface and ground waters through run-off and infiltration.

Salinity-dependent impacts on the effects of antiepileptic and antihistaminic drugs in Ruditapes philippinarum.

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 µg/L) and the antihistamine cetirizine (CTZ, 0.6 µg/L), when acting individually and combined (CBZ + CTZ), in the edible clam Ruditapes philippinarum. After 28 days of exposure, drugs concentrations, bioconcentration factors and biochemical parameters, related to clam's metabolic capacity and oxidative stress were evaluated. The results showed that clams 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 clams, since they caused higher levels of cellular damage. It stands out that salinity changes altered the impact of pharmaceutical drugs on marine bivalves.

Multivariable optimization of activated carbon production from microwave pyrolysis of brewery wastes - Application in the removal of antibiotics from water.

This study aimed at optimizing the one-step chemical activation and microwave pyrolysis of an agro-industrial waste to obtain a microporous activated carbon (AC) with superior textural and adsorptive properties by a fast, low-reagent and low-energy process. Spent brewery grains were used as precursor, and the antibiotics sulfamethoxazole (SMX), trimethoprim (TMP) and ciprofloxacin (CIP) were considered as target adsorbates. A fractional factorial design was applied to evaluate the effect of the main factors affecting the preparation of AC (activating agent, activating agent:precursor ratio, pyrolysis temperature and residence time) on relevant responses. Under optimized conditions (K2CO3 activation, pyrolysis at 800 °C during 20 min and a K2CO3:precursor ratio of 1:2), a microporous AC with specific surface area of 1405 m2 g-1 and large adsorption of target antibiotics (82-94%) was obtained and selected for further studies. Equilibrium times up to 60 min and maximum Langmuir adsorption capacities of 859 µmol g-1 (SMX), 790 µmol g-1 (TMP) and 621 µmol g-1 (CIP) were obtained. The excellent textural and adsorptive properties of the selected material were achieved with a very fast pyrolysis and low load of activating agent, highlighting the importance of optimization studies to decrease the environmental and economic impact of waste-based AC.

Metabolic and oxidative status alterations induced in Ruditapes philippinarum exposed chronically to estrogen 17α-ethinylestradiol under a warming scenario.

The presence of pharmaceuticals in the aquatic environment is an ongoing concern. However, the information regarding their effects under different climate change scenarios is still scarce. 17α-ethinylestradiol (EE2) is widely present in different aquatic systems showing negative impacts on aquatic organisms even when present at trace concentrations (≈1 ng/L). Nevertheless, its impact on bivalves is poorly understood, especially considering the influence of climate change factors. This study aimed to assess the toxicological impacts of EE2 under current and predicted warming scenarios, in the edible clam Ruditapes philippinarum. For this, clams were exposed for 28 days to different EE2 concentrations (5, 25, 125, 625 ng/L), under two temperatures (17 °C (control) and 21 °C). Drug concentrations, bioconcentration factors and biochemical parameters, related to oxidative stress and energy metabolism, were evaluated. Results showed that under actual and predicted temperature scenarios EE2 concentrations led to a disturbance in redox homeostasis of the clams, characterized by an increase in oxidized glutathione in contaminated organisms compared to control ones. Nevertheless, clams were capable to cope with the stressful conditions, activating their defence mechanisms (especially at the highest exposure concentration and in particular at increased temperature), and no oxidative damage occured. Although limited effects were observed, the present findings indicate that under both temperatures contaminated clams altered their biochemical performance, which can impair their sensitivity and protection capacity to respond to other environmental changes and/or affect their capacity to grow and reproduce. The results presented here highlight the need for further research on this thematic, considering that climate change is an ongoing problem, and the levels of some pharmaceutical drugs will continue to increase in marine/estuarine environments.