Magnetized vermiculite as a tool for the treatment of produced water generated by oil companies: Effects on aquatic organisms before and after treatment.

Produced water (PW) generated by oil companies is a highly impacting waste that contains chemicals such as metals and organic and inorganic compounds. Given its polluting potential, PW requires effective treatment before being discharged into the environment. Conventional treatments have limited efficiency in removing PW toxicity, so alternative approaches must be developed and standardized. In this context, treatment with adsorbent materials like magnetized vermiculite (VMT-mag) is highlighted. This work aimed to evaluate the efficiency of treatment with VMT-mag in reducing PW toxicity to aquatic biota. For this purpose, three aquatic species (the midge Chironomus riparius, the planarian Girardia tigrina, and the crustacean Daphnia magna) were exposed to untreated PW and to PW treated with VMT-mag at laboratory conditions. The assessed endpoints included mortality, growth, emergence, and developmental time of C. riparius; mortality, locomotion, feeding, and head regeneration of G. tigrina; and intrinsic population growth rate (r) and reproductive output of D. magna. The results showed that all the species exposed to raw PW were impaired: C. riparius had delayed development, G. tigrina had reduced locomotor activity and delayed head regeneration, and D. magna had reduced reproduction and delayed intrinsic population growth rate (r). Most of the analyzed parameters showed that treatment with VMT-mag diminished PW toxicity. Therefore, using VMT-mag to treat PW may be the key to reducing the PW effects on aquatic organisms.

Using 3D printed magnetic platform as support for screen printed electrode applied for p-toluenediamine detection in biological fluid and water samples.

The present work reports the development and application of a new electrochemical sensor for the determination of low concentration levels of p-toluenediamine (PTD) in biological fluids and surface water samples. The proposed sensor was developed using a 3D-printed magnetic device as platform for carbon screen printed electrode (CSPE) modified by magnetic nanoparticles functionalized with carboxylic groups and l-cysteine (MNP-CA-CYS). The results obtained from the morphological and electrochemical characterizations of the sensing platform enabled us to confirm the success of the sensor functionalization with l-cysteine and to have a better understanding of the electrochemical behavior and preconcentration of PTD on the electrode surface. PTD oxidation occurred at 0.24V on MNP-CA-CYS and the mechanism recorded an increase of 51.0% in anodic peak current. Under optimized conditions, the square wave voltammograms obtained for the electrode modified by 40.0 µL MNP-CA-CYS suspension at 1.0 mg mL-1, with accumulation time of 3 min, presented an analytical curve with linear range of 8.00 × 10-7 to 8.00 × 10-5 mol L-1, represented by the equation Iap = (0.383 ± 0.011)[PTD] - (8.112 ± 0.07) × 10-8 (R2 = 0.9994), and detection and quantification limits of 8.53 × 10-8 and 2.56 × 10-7 mol L-1, respectively. Finally, the proposed method was validated through comparison with high performance liquid chromatography coupled to diode array detector (HPLC-DAD) technique and was successfully applied for PTD determination in samples of surface water, tap water, fetal bovine serum and artificial urine.

Assessment of WO3 electrode modified with intact chloroplasts as a novel biohybrid platform for photocurrent improvement.

The present work describes an easy way to prepare a Chloroplast/PDA@WO3 biohybrid platform based on the deposition of chloroplasts on WO3 substrate previously modified with polydopamine (PDA) film as anchoring agent. The use of PDA as an immobilization matrix for chloroplasts, and also as an electron mediator under LED irradiation, resulted in enhanced photocurrents. The use of the chloroplasts amplified the photocurrent, when compared to the bare substrate (WO3). The best electrode performance was obtained using high intensity LED irradiation at 395 nm, for the electrode exposed for 10 min to 150 µg mL-1 of intact chloroplasts. Amperometric curves obtained by on/off cycles using an applied potential of +0.50 V, in PBS electrolyte (pH 7.0), showed that the presence of 0.2 × 10-3 mol L-1 of simazine caused an approximately 50% decrease of the photobiocurrent. Preliminary studies indicated that the synthesized platform based on intact chloroplasts is a good strategy for studying the behavior of photosynthetic entities, using an LED light-responsive WO3 semiconductor substrate. This work contributes to the understanding of photobiocatalysts that emerge as a new class of materials with sophisticated and intricate structures. These are promising materials with remarkably improved quantum efficiency with potential applications in photobioelectrocatalysis.

Modification of Ti/TiO2NT with ZrO2 nanoparticles to enhance photoelectrocatalytic performance in removal of dibutyl phthalate.

This work shows that ZrO2, used as a modifier of TiO2, can be highly effective as a co-catalyst in the photoelectrocatalytic degradation of dibutyl phthalate (DBP). The monoclinic phase of ZrO2 was easily obtained by chemical deposition on TiO2 nanotubes (Ebg ~3.06 eV), increasing the occurrence of hydroxyl groups and acidity on the surface of the material, as observed by electrophoretic mobility measurements. The optimized photoelectrocatalysis conditions were bias potential of 1.5 V, 0.1 M Na2SO4 (initial pH 6) supporting electrolyte, 6 ppm of DBP, and UV/Vis irradiation. These conditions resulted in complete removal of DBP, down to the limit of detection of the chromatographic method used, with up to complete TOC removal after 60 min of treatment. The effects of pH, bias potential, DBP concentration, and applied potential were investigated. The method was compared with photocatalysis and photolysis. An oxidation mechanism is proposed, based on intermediates detected by LC-MS/MS during 10 min of photoelectrocatalysis.

Sample preparation and antibiotic quantification in vinasse generated from sugarcane ethanol fuel production.

Vinasse - liquid organic residue derived from the production of sugarcane ethanol fuel, has been applied as soil amendment via fertigation for decades in Brazil. This organic residue is an important source of nutrients and water for sugarcane crops. Through fertigation, approximately 400 billion liters of vinasse are recycled annually. Despite the economic and agronomic importance of this practice, vinasse-based fertigation can be a source of antibiotic contamination in the environment. The present work reports the application of solid phase extraction (SPE), salting-out liquid-liquid extraction (SALLE), and on-line solid phase extraction (on-line SPE) as sample preparation techniques for the analysis of the following antibiotics (contaminants) in vinasse sample: monensin, penicillin G, virginiamycin M1, virginiamycin S1, tetracycline and erythromycin. The study also employed a totally automated quantitative method based on on-line SPE and liquid chromatography coupled to quadrupole linear ion trap tandem mass spectrometry (LC-QqLIT-MS/MS) for the analysis of these contaminants in vinasse. The application of the aforementioned sample preparation techniques led to the successful extraction of the analytes, and a comparative analysis of the techniques showed that the on-line SPE technique was the most advantageous among the techniques investigated. The quantitative analytical method applied yielded well-defined chromatographic peaks, working range of 1.0-370.0 ng·mL-1, apparent recovery ranging from 80 to 110% for most compounds, repeatability between 3 and 16%, and limits of detection ranging from1.0 to 10 ng·mL-1. The analysis of six vinasse samples from different ethanol producing plants led to the detection of monensin at the concentration of 14.3 ng·mL-1 in their compositions. The results obtained show that fertigation with vinasse is a source of antibiotic contamination in the environment.

Measuring concentrations of a dye in the hemolymph of a marine amphipod: Development of a protocol for exposure assessment.

The increasing pollution of aquatic environments due to old and emerging contaminants requires the development of integrative methods for exposure assessment. Internal concentrations are a reliable way to estimate total exposure of contaminants originated from different routes (water, sediment, and food). We developed a protocol to evaluate the concentration of a dye, C.I. Disperse Red 1, in the hemolymph of Parhyale hawaiensis, a marine amphipod. LOD and LOQ were satisfactory to detect the dye in all hemolymph samples. The concentration detected in the hemolymph varied related to exposure time and dye concentration (0.003 to 0.086 µg mL-1). Polynomial regression model was the best fit. The protocol was reliable to detect and quantify dye exposure in marine amphipods and can be considered for future assessments of estuarine and marine regions under the influence of dye processing plants. The method possibly can be easily adapted to other amphipods and other azo dyes.

Assessment of the compounds formed by oxidative reaction between p-toluenediamine and p-aminophenol in hair dyeing processes: Detection, mutagenic and toxicological properties.

Previous studies have demonstrated the presence of precursors and coupling agents in wastewater from hair dyeing processes. The complex reaction involved in the oxidation of these compounds can generate extremely hazardous sub-products, leading to an increase in the mutagenicity and toxicity of wastewater. Without proper treatment, this highly toxic wastewater may find its way into the drinking water treatment plant. The present work aimed to investigate the main products generated after the oxidation reaction involving p-toluenediamine (PTD) and p-aminophenol (PAP) - precursors that widely used in the composition of commercial permanent hair dyes, under experimental conditions close to the routine hair dyeing process (in the presence and absence of hydrogen peroxide in ammoniacal medium), using spectroscopic techniques. The study also investigated the mutagenicity and toxicity of the products formed in the hairdressing wash water and conducted detection analysis to determine the presence of the precursors and Bandrowski's Base Derivative (BBD) in samples of wastewater, surface and drinking water using HPLC-DAD and linear voltammetry techniques. Based on this investigation, we identified several PTD and PAP self-oxidation products and eleven sub-products derived from the reaction between PTD and PAP. Assays conducted using Salmonella typhimurium YG1041, with and without activation-induced rat liver metabolism (S9), indicated mutagenicity of the reaction products in concentrations above 10.0 µg µL-1. The concentrations of PTD, PAP, and several reactions and oxidation products of these precursors were detected in wastewater and water samples.

Self-doping of Nb2O5NC by cathodic polarization for enhanced conductivity properties and photoelectrocatalytic performance.

A simple novel electrochemical reduction approach was developed for the self-doping of Nb4+ in niobium oxide nanochannels (Nb2O5NC), changing the conductivity, optical properties, and photocatalytic properties of the material. Nb2O5NC was synthesized using different electrolytes: 0.4 wt% HF in 1 M H2SO4 (EI), 0.4 M NH4F in glycerol (EII), and 0.25 g NH4F with 4 vol% water in glycol at 50 °C (EIII). Field emission scanning electron microscopy (FEG-SEM) analysis showed well-organized arrays of Nb2O5 nanochannels produced on Nb foil, with varying tube diameters in the order EII < EI < EIII and film thickness in the order EI < EII < EIII, which drastically affected the photocurrent vs. potential curves. In order to self-dope the Nb2O5, the samples were electrochemically reduced in 0.1 M KH2PO4 buffer solution (pH 10) for 5 min, at -2.5 V vs. Ag/AgCl, resulting in the doped samples denoted P-EI, P-EII, and P-EIII. The results showed that reduction of Nb5+ to Nb4+ occurred for all the Nb2O5NC samples, leading to decreased surface charge transfer resistance between the Nb2O5NC and the electrolyte, as well as increases of the charge carrier density and photocurrent for all the self-doped samples, compared to undoped samples. Sample P-EI was also tested for the degradation of reactive red 120 (RR120) dye, achieving efficient photoelectrocatalytic degradation of a 10 mg L-1 dye solution. These results reveal that the self-doping approach can enhance the photoelectrocatalytic properties of Nb2O5 photoanode, offering an alternative way for the removal of reactive dyes.

Assessment of p-aminophenol oxidation by simulating the process of hair dyeing and occurrence in hair salon wastewater and drinking water from treatment plant.

This work reports the study of oxidation reaction of p-aminophenol (PAP) in ammoniacal medium in dissolved atmospheric oxygen and hydrogen peroxide, simulating the process of hair dyeing with permanent dyes. The products formed, which included semi-quinoneimine radical, quinoneimine, dimers, trimers and tetramers, were identified by mass spectrometry, infrared spectroscopy, UV-vis spectrophotometry, and nuclear magnetic resonance of hydrogen. The process was found to involve an autoxidation mechanism. The mutagenicity of the products was carried out by Salmonella Typhimurium YG1041 assay, and the results indicated no mutagenic properties. The presence of PAP and its oxidative products in samples of wastewater collected from hairdressing salon effluent (WW), raw river water (RRW), and water inlet and outlet of drinking water treatment plant (DWTP) was analyzed by HPLC-DAD. PAP was detected in the collected samples of WW, water samples from DWTP (before and after treatment), at concentrations of 2.1 ± 0.5 mg L-1, 1.9 ± 0.3 × 10-3 mg L-1 and 1.3 ± 0.2 × 10-3 mg L-1, respectively. The reaction products, including dimers, trimers and tetramers were identified only in the WW sample; this shows that both the precursor in the sample and its derivatives were released into the wastewater.

Simple, fast and environmentally friendly method to determine ciprofloxacin in wastewater samples based on an impedimetric immunosensor.

In this study an impedimetric immunosensor was developed in order to determine ciprofloxacin (CIP) in wastewater samples, an emergent contaminant widely found in wastewater. To achieve this, an anti-ciprofloxacin antibody was immobilized on the surface of a printed carbon electrode. Then, the developed immunosensor was applied in wastewater samples from Université Laval residences (Québec, Canada) through the load transfer resistance (R ct) using [Fe(CN)6]3-/4- as a redox probe, and the average CIP concentration was found to be 2.90 × 10-4 µg mL-1. The observed R ct changes presented a linear relationship from CIP concentrations of 10-5 to 1.0 µg mL-1, with detection and quantification limits of 2.50 × 10-6 and 7.90 × 10-6 µg mL-1, respectively. The immunosensor presented high selectivity and repeatability, as well as a good recovery rate in wastewater samples (97%). Significant interference with other compounds was not observed. The proposed method requires only 30 µL of sample without the use of organic solvents or preceding sample preparation and/or extraction techniques. Moreover, the method is fast: only 20 min of incubation followed by 2 min of analysis time was sufficient to obtain the CIP concentration. The method's estimated cost is U$ 2.00 per sample.

Electrochemical sensors based on biomimetic magnetic molecularly imprinted polymer for selective quantification of methyl green in environmental samples.

A new biomimetic sensor was prepared on carbon paste with magnetic molecularly imprinted polymer (mag-MIP) for sensitive and selective detection of methyl green dye. The mag-MIP was synthesized using a functional monomer that was selected before by computational simulation. A mag-NIP (magnetic non-imprinted polymer) control material was also prepared for comparative purposes. Modeling adsorption studied revealed that the dye-polymer interface followed pseudo-first order kinetics and that maximum adsorption (Qm) of the dye on mag-MIP was 3.13 mg g-1, while the value for mag-NIP was 1.58 mg g-1. The selective material was used as a sensing spot in fabrication of an electrochemical sensor based on modified carbon paste. For electrochemical analysis, the best achievement of the sensor was acquire by tack together a paste with 6.7% (w/w) of mag-MIP and using square-wave adsorptive anodic stripping voltammetry (SWAdASV) in 0.1 mol L-1 phosphate buffer (pH 7.0), with an applied potential (Eappl) of 0.3 V vs. Ag|AgClsat during an adsorption time (Tads) of 120 s. The results were obtained under optimized conditions in which sensor provided a linear concentration range of methyl green from 9.9 × 10-8 to 1.8 × 10-6 mol L-1, with a limit of detection (LOD) of 1.0 × 10-8 mol L-1 and a satisfactory relative standard deviation (RSD) of 4.3% (n = 15). The proposed sensor was applying using two spiked river water samples, obtaining recoveries ranging from 93% to 103%. The proposed method exhibits excellent precision also high reliability and proved to be an alternative method for the quantification of methyl green in real samples.

Assessment of the autoxidation mechanism of p-toluenediamine by air and hydrogen peroxide and determination of mutagenic environmental contaminant in beauty salon effluent.

The present work investigated the autoxidation reaction of p-toluenediamine (PTD) - a precursor - widely used in permanent hair dyeing formulation, under experimental conditions close to the hair dyeing process (oxygen and/or peroxide in ammoniacal medium), by chromatographic and spectroscopic techniques. In additional, evaluated the mutagenicity of the PTD oxidation products and the presence of PTD and this products in wastewater from beauty salon, as well as in surface water and drinking water using HPLC coupled to a diode array detector and linear scan voltammetry. Through this study, it was possible the identification of semi-quinonediimine, quinonediimine, dimers (derived from toluenediamine), and trimer radical identified as Bandrowski's Base derivative (BBD) formed during autoxidation of PTD. Salmonella Typhimurium YG1041 assay with and without metabolic activation induced rat-liver (S9) indicated mutagenic activity for BBD. Levels of PTD were determined by the standard addition method in samples collected from the wastewater of a beauty salon, as well as from the water before and after treatment in a drinking water treatment plant (DWTP) reached concentrations of 2.08 ±â€¯0.21, 2.36 ±â€¯0.10 × 10-3, and 1.77 ±â€¯0.13 × 10-3 mg L-1, respectively. In addition, linear sweep voltammetry was used to monitor the BBD found at the concentration of 1.59 ±â€¯0.35 mg L-1 in wastewater collected from the beauty salon.

Biotransformation of disperse dyes using nitroreductase immobilized on magnetic particles modified with tosyl group: Identification of products by LC-MS-MS and theoretical studies conducted with DNA.

The present work evaluates the action of nitroreductase enzyme immobilized on Tosylactivated magnetic particles (MP-Tosyl) on three disperse dyes which contain nitro and azo groups. The dyes included Disperse Red 73 (DR 73), Disperse Red 78 (DR 78), and Disperse Red 167 (DR 167). The use of a magnet enabled the rapid and easy removal of the immobilized enzyme after biotransformation; this facilitated the identification of the products generated using high-performance liquid chromatography with diode array detector (HPLC-DAD) and mass spectrometry (LC-MS/MS). The main products formed by the in vitro biotransformation were identified as the product of nitro group reduction to the correspondent amine groups, which were denoted as follows: 50% of 2-(2-(4-((2-cyanoethyl)(ethyl)amino)phenyl)hydrazinyl)-5-nitrobenzonitrile, 98% of 3-((4-((4-amino-2-chlorophenyl) diazenyl)phenyl) (ethyl)amino)propanenitrile and 99% of (3-acetamido-4 - ((4-amino-2-chlorophenyl) diazenyl) phenyl) azanediyl) bis (ethane-2,1-diyl) for DR 73, DR 78 and DR 167, respectively. Based on the docking studies, the dyes investigated were found to be biotransformed by nitroreductase enzyme due to their favorable interaction with the active site of the enzyme. Theoretical results show that DR73 dye exhibits a relatively lower rate of degradation; this is attributed to the cyanide substituent which affects the electron density of the azo group. The docking studies also indicate that all the dyes presented significant reactivity towards DNA. However, Disperse Red 73 was found to exhibit a substantially higher reactivity compared to the other dyes; this implies that the dye possesses a relatively higher mutagenic power. The docking results also show that DR 73, DR 78 and DR 167 may be harmful to both humans and the environment, since the mutagenicity of nitro compounds is associated with the products formed during the reduction of nitro groups. These products can interact with biomolecules, including DNA, causing toxic and mutagenic effects.

Influence of auxochrome group in disperse dyes bearing azo groups as chromophore center in the biotransformation and molecular docking prediction by reductase enzyme: Implications and assessment for environmental toxicity of xenobiotics.

Synthetic azo dyes have increasingly become a matter of great concern as a result of the genotoxic and mutagenic potential of the products derived from azo dye biotransformation. This work evaluates the manner in which reducing enzymes produced by Escherichia coli (E. coli) act on three disperse dyes bearing azo groups, namely Disperse Red 73 (DR 73), Disperse Red 78 (DR 78), and Disperse Red 167 (DR 167). UV-Vis spectrophotometry, high-performance liquid chromatography with diode array detector (HPLC-DAD), and liquid chromatography mass spectrometry (LC-MS/MS) were applied towards the identification of the main products. Seven days of incubation of the azo dyes with the tested enzymes yielded a completely bleached solution. 3-4-Aminophenyl-ethyl-amino-propanitrile was detected following the biotransformation of both DR 73 and DR 78. 4-Nitroaniline and 2-chloro-4-nitroaniline were detected upon the biotransformation of DR 73 and DR 78, respectively. The main products derived from the biotransformation of DR 167 were dimethyl 3,3'-3-acetamido-4-aminophenyl-azanedyl-dipropanoate and 2-chloro-4-nitroaniline. The results imply that DR 73 lost the CN- substituent during the biotransformation. Furthermore, theoretical calculations were also carried out aiming at evaluating the interaction and reactivity of these compounds with DNA. Taken together, the results indicate that DR 73, DR 78, and DR 167 pose health risks and serious threats to both human beings and the environment at large as their biotransformation produces harmful compounds such as amines, which have been widely condemned by the International Agency for Research on Cancer.

A simple electrochemical method to monitor an azo dye reaction with a liver protein.

Disperse Orange 37 (DO37) is an efficient azo dye for dyeing synthetic textile materials owing to its resistance to degradation that may also be harmful to humans as DO37 is not entirely eliminated in wastewater treatment. In this paper, we demonstrate that DO37 is bleached by reduced glutathione (GSH) in a reaction catalyzed by glutathione-s-transferase (GST), a phase II detoxification enzyme. The reaction included a nucleophilic attack involving sulfhydryl groups, confirmed using density functional theory (DFT) calculations. DO37 also induced quenching in the fluorescence of GST through static suppression. The reaction was determined using differential pulse voltammetry (DPV) by monitoring the oxidation peak at 0.65 V of GSH sulfhydryl group. Quantitative estimation of the product reaction could be made by measuring an additional oxidation peak at 0.91 V which increased linearly with DO37 concentration. These electrochemical determinations were made possible by preconcentrating the reaction product on a graphite-epoxy electrode with immobilization of GST onto magnetite nanoparticles. Straightforward biological implications from the results are associated with the known toxicity of azo dyes such as DO37, which has been proven here to interact strongly with both GSH and the liver enzyme GST, and may induce hepatocarcinogenesis or other types of cancer.

Adsorptive stripping voltammetry for simultaneous determination of hydrochlorothiazide and triamterene in hemodialysis samples using a multi-walled carbon nanotube-modified glassy carbon electrode.

Hemodialysis is the most commonly used method for the treatment of chronic kidney disease. In this procedure, some patients use diuretics to control weight gain and blood pressure. In this work, a voltammetric sensor based on a glassy carbon electrode modified with carbon nanotubes (GCE/MWCNT) is described for the simultaneous determination of the diuretics hydrochlorothiazide (HCT) and triamterene (TRT). The oxidation of the diuretics on the GCE/MWCNT surface was observed at 1.01 and 1.17V for HCT and TRT, respectively, allowing simultaneous determination, which was not possible with the unmodified glassy carbon electrode. The GCE/MWCNT electrode provided 6-fold and 10-fold gains in anode peak intensity for HCT and TRT, respectively, compared to the unmodified electrode. After optimization of the conditions (pH, accumulation time, and accumulation potential), analytical curves were constructed for the analytes in the range from 1.0 × 10-7 to 2.0 × 10-5molL-1. The detection limits for HCT and TRT were 2.8 × 10-8 and 2.9 × 10-8molL-1, respectively. A high performance liquid chromatography method with diode array detection was also developed for the determination of HCT and TRT in hemodialysis samples, for comparison with the electroanalytical method.

Quantifying the contribution of dyes to the mutagenicity of waters under the influence of textile activities.

The combination of chemical analyses and bioassays allows the identification of potentially mutagenic compounds in different types of samples. Dyes can be considered as emergent contaminants and were detected in waters, under the influence of textile activities. The objective of this study was to evaluate the contribution of 9 azo dyes to the mutagenicity of representative environmental samples. Samples were collected along one year in the largest conglomerate of textile industries of Brazil. We analyzed water samples from an important water body, Piracicaba River, upstream and downstream two main discharges, the effluent of a wastewater treatment plant (WWTP) and the tributary Quilombo River, which receives untreated effluent from local industries. Samples were analyzed using a LC-MS/MS and tested for mutagenicity in the Salmonella/microsome microsuspension assay with TA98 and YG1041. Six dyes were detected in the collected samples, Disperse Blue 291, Disperse Blue 373, Disperse Orange 30, Disperse Red 1, Disperse Violet 93, and Disperse Yellow 3. The most sensitive condition for the detection of the mutagenicity was the strain YG1041 with S9. The concentration of dyes and mutagenicity levels varied along time and the dry season represented the worst condition. Disperse Blue 373 and Disperse Violet 93 were the major contributors to the mutagenicity. We conclude that dyes are contributing for the mutagenicity of Piracicaba River water; and both discharges, WWTP effluent and Quilombo River, increase the mutagenicity of Piracicaba River waters in about 10-fold. The combination of chemical analysis and bioassays were key in the identification the main drivers of the water mutagenicity and allows the selection of priority compounds to be included in monitoring programs as well for the enforcing actions required to protect the water quality for multiple uses.

Synthesis and evaluation of a molecularly imprinted polymer for selective adsorption and quantification of Acid Green 16 textile dye in water samples.

An alternative for determining environmental pollutants, like textile dyes, is the use of molecularly imprinted polymers (MIPs) as solid phase extraction (SPE) or as sensor recognition systems. MIPs are tailor-made artificial receptor sites in a polymer, which present good affinity and selectivity. This work shows the synthesis of MIPs for the Acid Green 16 (AG16) textile dye and the results of rebinding, selectivity and application of this MIP in water samples. MIP synthesis was performed using AG16 dye (template), 1-vinylimidazole (functional monomer), ethylene-glycol-dimethacrylate (cross-link), 2,2'-azobis(2-methylpropionitrile) (initiator) and methanol (solvent) by bulk synthesis. The imprinted polymer presented excellent rebinding of 83%, an imprinted factor of 6.91 and great selectivity in comparison with other textile dyes. Additionally, the MIP showed high efficiency in the extraction of this dye in water samples, presenting a recovery rate close to 100% and a better performance when compared to commercial SPE cartridges. Due to this excellent performance for AG16, the application of this MIP to determine dyes in different matrices of environmental importance is promising.

Ecotoxicological risk assessment of the "Acid Black 210" dye.

The "Acid Black 210" dye is one of the most used black dyes by the leather industry. This compound contains three azo groups in its chemical structure, and has been quoted as a non-regulated dye with toxicological concern, since it could generate carcinogenic aromatic amines. The objective of this study was to perform the ecotoxicological risk assessment of this dye through testing its toxicity in vitro and in vivo with the Ames test, the Comet assay, the Daphnia similis test, and the zebrafish embryo acute toxicity test. Moreover, we evaluated the presence of this dye in environmental samples related with a tannery industry. All the tests performed were negative, with the exception of the Ames test with the Salmonella typhimurium TA98 strain, which resulted in a low mutagenic potency. Due to the low concentrations of the "Acid Black 210" dye found in tannery effluents, and the high concentrations where any toxic activity is occasionally described, we concluded that this dye is safe from the ecotoxicological point of view in the areas evaluated and in the light of the current knowledge.

Assessment of molecularly imprinted polymers (MIPs) in the preconcentration of disperse red 73 dye prior to photoelectrocatalytic treatment.

Magnetic molecularly imprinted polymers (MMIPs) have become a research hotspot due to their two important characteristics: target recognition and magnetic separation. This paper presents the preparation, characterization, and optimization of an MMIP for the preconcentration of disperse red 73 dye (DR73) and its subsequent efficient degradation by photoelectrocatalytic treatment. The MMIPs were characterized by scanning electron microscopy (SEM), which revealed homogeneous distribution of the particles. Excellent encapsulation of magnetite was confirmed by transmission electron microscopy (TEM). A study of dye binding showed that the dye was retained more selectively in the MIP, compared to the NIP. The release of DR73 from the imprinted polymers into methanol and acetic acid was analyzed by UV-Vis spectrophotometry. The extracts showed higher absorbance values for MMIP, compared to MNIP, confirming greater adsorption of dye in the MMIP material. The extracts were then subjected to photoelectrocatalytic treatment. LC-MS/MS analysis following this treatment showed that the dye was almost completely degraded. Hence, the combination of MMIP extraction and photoelectrocatalysis offers an alternative way of selectively removing an organic contaminant, prior to proceeding with its complete degradation.