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.

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.

Sludge from paper mill effluent treatment as raw material to produce carbon adsorbents: An alternative waste management strategy.

Pulp and paper industry produces massive amounts of sludge from wastewater treatment, which constitute an enormous environmental challenge. A possible management option is the conversion of sludge into carbon-based adsorbents to be applied in water remediation. For such utilization it is important to investigate if sludge is a consistent raw material originating reproducible final materials (either over time or from different manufacturing processes), which is the main goal of this work. For that purpose, different primary (PS) and biological sludge (BS) batches from two factories with different operation modes were sampled and subjected to pyrolysis (P materials) and to pyrolysis followed by acid washing (PW materials). All the materials were characterized by proximate analysis, total organic carbon (TOC) and inorganic carbon (IC), attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR) and N2 adsorption isotherms (specific surface area (SBET)and porosity determination). Sludge from the two factories proved to have distinct physicochemical properties, mainly in what concerns IC. After pyrolysis, the washing step was essential to reduce IC and to considerably increase SBET, yet with high impact in the final production yield. Among the materials here produced, PW materials from PS were those having the highest SBET values (387-488 m2 g-1). Overall, it was found that precursors from different factories might originate final materials with distinct characteristics, being essential to take into account this source of variability when considering paper mill sludge as a raw material. Nevertheless, for PS, low variability was found between batches, which points out to the reliability of such residues to be used as precursors of carbon adsorbents.

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.

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.

Amitriptyline ecotoxicity in Danio rerio (Hamilton, 1822) embryos - similar toxicity profile in the presence of nanoplastics.

Interaction of nanoplastics (NPls) with other environmental contaminants could affect their uptake by the organisms and their toxicity. Thus, the present study aims to investigate the polystyrene NPls (44 nm) interaction with the antidepressant amitriptyline (AMI) and its toxicity to Danio rerio embryos. A similar toxicological profile for NPls + AMI exposure was found for most of the evaluated endpoints, comparing with AMI single exposure, showing that the presence of NPls did not modulate the AMI toxicity. However, the behavioral assessment showed a different pattern with hypoactivity for the NPls + AMI exposure (NPls - hyperactivity; AMI - no effect). Interaction effects between NPls and AMI were also found in the protein contents (antagonism) and in the total glutathione content (synergism). This study highlights the complexity and unpredictability of NPls interaction with pharmaceuticals, important for an accurate environmental risk assessment and for the developing of effective strategies and interventions against plastic pollution.

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.

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.

Cocktail effects of emerging contaminants on zebrafish: Nanoplastics and the pharmaceutical diphenhydramine.

Nanoplastics (NPLs) became ubiquitous in the environment, from the air we breathe to the food we eat. One of the main concerns about the NPLs risks is their role as carrier of other environmental contaminants, potentially increasing their uptake, bioaccumulation and toxicity to the organisms. Therefore, the main aim of this study was to understand how the presence of polystyrene NPLs (∅ 44 nm) will influence the toxicity (synergism, additivity or antagonism) of the antihistamine diphenhydramine (DPH), towards zebrafish (Danio rerio) embryos, when in dual mixtures. After 96 hours (h) exposure, at the organismal level, NPLs (0.015 or 1.5 mg/L) + DPH (10 mg/L) induced embryo mortality (90%) and malformations (100%) and decreased hatching (80%) and heartbeat rates (60%). After 120 h exposure, NPLs (0.015 or 1.5 mg/L) + DPH (0.01 mg/L) decreased larvae swimming distance (30-40%). At the biochemical level, increased glutathione S-transferases (55-122%) and cholinesterase (182-343%) activities were found after 96 h exposure to NPLs (0.015 or 1.5 mg/L) + DPH (0.01 mg/L). However, catalase (CAT) activity remained similar to the control group in the mixtures, inhibiting the effects detected after the exposure to 1.5 mg/L NPLs alone (increased 230% of CAT activity). In general, the effects of dual combination - NPLs + DPH (even at concentrations as low as 10 µg/L of DPH) - were more harmful than the correspondent individual exposures, showing the synergistic interactions of the dual mixture and answering to the main question of this work. The obtained results, namely the altered toxicity patterns of NPLs + DPH compared with the individual exposures, show the importance of an environmental risk assessment considering NPLs as a co-contaminant due to the potential NPLs role as vector for other contaminants.

Nanoplastics increase the toxicity of a pharmaceutical, at environmentally relevant concentrations - A mixture design with Daphnia magna.

In aquatic environments, nanoplastics (NPls) can adsorb pharmaceuticals. However, throughout the scientific community, there is scarce knowledge about the interactive effects of the mixture nanoplastics (NPls) with pharmaceuticals to aquatic organisms. Therefore, this study aimed to investigate if the pharmaceutical diphenhydramine (DPH) toxicological effects alters when in presence of polystyrene NPls (PSNPls). To achieve this, Daphnia magna immobilization and different biochemical biomarkers (48-hours exposure) were assessed. Synergistic interactions occurred at environmentally relevant concentrations, PSNPls+DPH induced oxidative damage, whereas no effect was observed at single exposures. With the increase of PSNPls concentration, the DPH concentration causing 50% of effect (EC50) for organisms' immobilization decreased to 0.001 mg/L. In silico analysis suggested that the DPH toxicity to D. magna occurs via the sodium-dependent serotonin transporter. The results showed interactive effects between PSNPls and DPH (implying harmful effects on D. magna), allowing more thoughtful decisions by society and policymakers regarding plastics and pharmaceuticals.

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.

The role of nanoplastics on the toxicity of the herbicide phenmedipham, using Danio rerio embryos as model organisms.

Once in the aquatic ecosystems, nanoplastics (NPls) can interact with other contaminants acting as vectors of transport and altering their toxicological effects towards organisms. Thus, the present study aims to investigate how polystyrene NPls (44 nm) interact with the herbicide phenmedipham (PHE) and affect its toxicity to zebrafish embryos. Single exposures to 0, 0.015, 0.15, 1.5, 15 and 150 mg/L NPls and 0.02, 0.2, 2 and 20 mg/L PHE were performed. Embryos were also exposed to the binominal combinations: 0.015 mg/L NPls + 2 mg/L PHE, 0.015 mg/L NPls + 20 mg/L PHE, 1.5 mg/L NPls + 2 mg/L PHE and 1.5 mg/L NPls + 20 mg/L PHE. Due to the low solubility of PHE in water, a solvent control was performed (0.01% acetone). PHE was quantified. Mortality, heartbeat and hatching rate, malformations appearance, locomotor behavior and biomarkers related to oxidative stress, neurotransmission and energy budgets were analyzed. During 96 h, NPls and PHE single and combined exposures did not affect embryos development. After 120 h, NPls induced hyperactivity and PHE induced hypoactivity. After 96 h, NPls increased catalase activity and PHE increased glutathione S-transferases activity. On the combination 0.015 mg/L NPls + 20 mg/L PHE, hyperactivity behavior was found, similar to 0.015 mg/L NPls, and cholinesterase activity was inhibited. Additionally, the combination 1.5 mg/L NPls + 20 mg/L PHE increased both catalase and glutathione S-transferases activities. The combination NPls with PHE affected more biochemical endpoints than the single exposures, showing the higher effect of the binominal combinations. Dissimilar interactions effects - no interaction, synergism and antagonism - between NPls and PHE were found. The current study shows that the effects of NPls on bioavailability and toxicity of other contaminants (e.g. PHE) cannot be ignored during the assessment of NPls environmental behavior and risks.

Responses of Ruditapes philippinarum to contamination by pharmaceutical drugs under ocean acidification scenario.

In coastal systems, organisms are exposed to a multitude 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.

Assessment of diphenhydramine toxicity - Is its mode of action conserved between human and zebrafish?

The main aim of the study is to evaluate the effects of the pharmaceutical diphenhydramine (DPH) on embryo-larvae Danio rerio across distinct levels of organization - individual and subcellular - and correlate those effects with the DPH mode of action (MoA) assessed by in silico analysis. An embryos heartbeat rate reduction was observed at 10 mg/L DPH, but 0.001 to 10 mg/L did not significantly affect the zebrafish survival, hatching and morphology. Larvae swimming distance decreased (hypoactivity) at 1 and 10 mg/L DPH. Moreover, the straightforward movements decrease and the increase in the zigzag movements or movements with direction changes, shown an erratic swimming behavior. Energy budgets decreased for lipid (0.01 mg/L DPH) and carbohydrate (10 mg/L DPH) contents. Cholinesterase (neural function) and glutathione S-transferase (Phase II biotransformation/antioxidant processes) increased their activities at 10 mg/L DPH, where a decrease in the total glutathione content (antioxidant system) was observed. DNA damage was found at 0.01 and 10 mg/L DPH. However, a DNA repair occurred after subsequent 72 h in clean media. The in silico study revealed a relevant conservation between human and zebrafish DPH target molecules. These data provide a valuable ecotoxicological information about the DPH effects and MoA to non-target organisms.

Noise normalisation in capillary electrophoresis using a diode array detector.

When using capillary electrophoresis with a diode array detector, the wavelength at maximum absorbance is often chosen to quantify a given analyte. However, the background noise for every wavelength should be taken into account as it is by maximising the signal to noise ratio that the lowest limit of detection will be obtained. Here, we proposed an algorithm allowing to correct an electropherogram from its background absorption and to estimate the background noise. Applying it to all the electropherograms obtained in each wavelength channel allows obtaining the background noise as a function of the wavelength, which can be used to calculate the signal to noise ratio. This not only allows selecting the best wavelength to maximise the limit of detection of a given analyte, but also to generate a noise normalised base peak electropherogram (nn-BPE). It is shown that the noise normalised base peak electropherograms substantially improve the peaks visualisation. The algorithm is part of a graphic user interface that runs under MatLab environment; it does not require any programming knowledge and is freely available.

Optimizing microwave-assisted production of waste-based activated carbons for the removal of antibiotics from water.

This work aimed at the microwave-assisted production of activated carbon (AC) from primary paper mill sludge (PS) for the adsorption of antibiotics from water. Production conditions, namely pyrolysis temperature, pyrolysis time and activating agent (KOH):PS ratio, were optimized as a function of product yield, specific surface area (SBET), total organic carbon (TOC) content and adsorptive removal percentage of two target antibiotics (amoxicillin (AMX) and sulfamethoxazole (SMX)). Under the optimized conditions (pyrolysis at 800 °C during 20 min and a KOH:PS ratio of 1:5), a microporous AC (MW800-20-1:5, with SBET = 1196 m2 g-1, TOC = 56.2% and removal of AMX and SMX = 85% and 72%, respectively) was produced and selected for further kinetic and equilibrium adsorption studies. The obtained results were properly described by the Elovich reaction-based kinetic model and the Langmuir equilibrium isotherm, with maximum adsorption capacities of 204 ± 5 mg g-1 and 217 ± 8 mg g-1 for AMX and SMX, respectively. Considering the satisfactory comparison of these results with the performance of commercial and alternative AC produced by conventional pyrolysis, this work demonstrated the feasibility of the microwave-assisted production of environmentally and energetically sustainable waste-based AC to be applied in the efficient removal of antibiotics from water.