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This study concerns the synthesis of the florfenicol (FF) metabolites florfenicol amine (FFA), florfenicol alcohol (FFOH), and monochloroflorfenicol (FFCl), for their subsequent use as reference standards in On-line solid-phase extraction-ultra high-performance liquid chromatography-tandem mass spectrometry (SPE-UHPLC-MS/MS) analysis. The metabolites were characterized using 1 H and 13 C NMR, as well as HRMS, and their purities were confirmed by quantitative NMR to ensure analytical reliability. Validation of the developed analytical method showed that it presented acceptable performance, with linearity >0.99 for all the target analytes, accuracies within ±10 % of nominal concentrations, and intra- and inter-day precisions within 15 %. Application of this method to fillets from fish that had been treated with florfenicol (dose of 10 mg/kg bw daily) demonstrated its effectiveness in consistently detecting FF and its metabolites throughout the treatment. The results emphasized the utility of the method for enhancing pharmacokinetic and residue depletion research. The ability to precisely monitor the drug and its metabolites in treated fish provides important insights into florfenicol metabolism, laying the groundwork for further comprehensive profiling studies of metabolites in fish tissue., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

In recent years, the monitoring of tropane alkaloids, specifically hyoscyamine and scopolamine, in food has become a pressing concern. This is due to increasing reports of food contamination with these compounds worldwide, raising awareness about the potential risks associated with their consumption. A novel method is proposed here for the determination of the sum of (+)-hyoscyamine, (-)-hyoscyamine, and (-)-scopolamine in buckwheat-based matrices, using solid-liquid extraction at low temperature and quantification by bidimensional chromatography coupled to tandem mass spectrometry. The validated method presented a linear response in the concentration range of 2.5-15 μg kg -1 (r > 0.99). The precision and accuracy were in the ranges from 0.8 to 11.0 % and from 96 to 103 %, respectively. The limit of quantification (LOQ) was 2.5 μg kg -1 . No contamination was found at levels above the LOQ in any of the 18 samples analyzed (buckwheat flour, grains, and gluten-free mix)., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Ltd. All rights reserved.)

Sulfur polymers produced through 'inverse vulcanization' exhibit various attributes, such as photocatalytic activity and a high capacity to adsorb heavy metals. Nevertheless, there is a lack of research investigating the use of sulfur polymers as materials for the removal of organic contaminants. In this work, porous sulfur polymers (PSPs) were synthesized from elemental sulfur and 1,3-diisopropenylbenzene, with porosity introduced via salt templating. The result is a material that can strongly adsorb and chemically neutralize a model organic contaminant (caffeine). PSPs show adsorption up to 5 times higher than a leading adsorption material (activated carbon). Furthermore, either the adsorption or degradation processes can govern the removal efficiency depending on the synthesis parameters of PSPs. This is the first-ever report demonstrating sulfur polymers as effective materials for removing emerging contaminants from water. The versatile synthesis of sulfur polymers offers variation, which means that there is much more to explore in this exciting research area., (© 2024. The Author(s).)

Although banned in food-producing animals, residues of malachite green (MG) and its primary metabolite, leucomalachite green (LMG), have been found in fish due to illegal use in aquaculture and the release of industrial wastewater, which represent a serious risk to food and environmental securities. This study aimed to investigate the residue depletion profile of MG and LMG in edible tissues of Nile tilapia (Oreochromis niloticus) and pacu (Piaractus mesopotamicus) cultured simultaneously under the same environmental conditions to support control measures in case of abuse. An analytical method involving QuEChERS sample preparation and liquid chromatography coupled to tandem mass spectrometry was developed, validated, and applied to quantify MG and LMG residues in fish fillets from two depletion experiments after treatment by immersion bath (MG at 0.10 mg L -1 for 60 min). During the experiment, the average water temperature was 30 ºC, while the pH was 6.9. The method is selective, precise (CV = 0.4 - 22%) and accurate (recovery 92 - 114%). The limits of detection and quantification are 0.15 and 0.5 ng g -1 , respectively. In both species, the sum of MG and LMG residues were quantified up to the 32nd day post-exposure, and the concentrations were significantly higher in the pacu fillets (up to 3284 ng g -1 ) than in Nile tilapia (up to 432 ng g -1 ). The sums of MG and LMG residues were below 2 ng g -1 at 44 days and 342 days for Nile tilapia and pacu, respectively - the Minimum Required Performance Limit (MRPL) for analytical methods intended to monitor forbidden substances in food according to old European Commission guidelines. The persistence of MG residues in pacu may be attributed to its higher lipid content, which favors the accumulation of the non-polar metabolite LMG. These results provide insights into the concern about human, animal, and environmental health risks resulting from unauthorized use or aquatic contamination by industrial wastewater containing MG residues., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Levamisole, an anthelmintic and immunostimulant drug, has been studied as a promising alternative for aquaculture use. While oral administration through feeding is the main route of administration in fish farming, no studies evaluating methods of levamisole incorporation into the feed have been reported so far. Therefore, this study aimed to evaluate potential procedures for levamisole incorporation in extruded fish feed using ethyl cellulose, gelatin, or vegetable oil, to avoid drug leaching to the water during the animal's medication. A suitable LC-MS/MS method was optimized (full factorial design), validated, and applied to evaluate the efficiency of the process, the homogeneity of the drug concentration, and the leaching rate. The method has been demonstrated to be selective, precise (RSD < 4.9%), accurate (recovery > 98.4%), and linear ( r  > 0.99, 125-750 mg kg -1 ). The incorporation procedures using the three coating agents showed high incorporation efficiency (70%) and a homogeneous drug concentration among the extruded feed pellets. A low levamisole leaching rate was verified in the feed prepared using the ethyl cellulose coating procedure (4.3% after 15 min of immersion in the water). On the other hand, fish feed coated with gelatin and oil resulted in a high leaching rate (30-35% after 15 min). Thus, this study shows that coating ethyl cellulose may be a promising procedure for levamisole incorporation in fish feed and with the potential to enhance its use in animal production while reducing environmental contamination.

In the last five years, the presence of N-nitrosamines in commonly used medicines has become a significant concern for patients, physicians, and the pharmaceutical industry, due to their carcinogenic properties, even at low concentrations. Analytical methods that enable the unequivocal monitoring of these compounds, with low detection limits and covering a range of drugs, are indispensable. The present work proposes a bidimensional liquid chromatography-tandem mass spectrometry method capable of quantifying eleven N-nitrosamines in lipophilic active pharmaceutical ingredients (APIs). The API is retained in the first chromatographic dimension, while the fraction containing the N-nitrosamines is transferred to the second chromatographic dimension and, after separation, to the mass spectrometer. The logP values for the APIs and N-nitrosamines enabled prediction of the APIs that could be separated from the target analytes. The method was validated and successfully applied for the quantification of 1-methyl-4-nitroso piperazine (MNP) and N-nitrosodimethylamine (NDMA) in rifampicin, a drug used to treat tuberculosis. Although NDMA was not detected in two pharmaceutical analyzed, MNP was found at concentrations of 0.44 ± 0.05 and 2.1 ± 0.3 µg g -1 . Given the ability to apply the method to various APIs, together with its reliance solely on logP values for determining suitability, the proposed technique could be extended to the determination of N-nitrosamines in other drugs besides rifampicin., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023. Published by Elsevier B.V.)

Wastewater treatment is becoming ever more challenging due to the increasing levels of molecular pollutants that are challenging for existing approaches. Innovative materials are required to help produce potable water from heavily contaminated water sources. One such material is titanium dioxide-activated carbon (TiO 2 /AC) heterostructures, which combine the photocatalytic properties of TiO 2 with the adsorption properties of the ACs. To date, studies on TiO 2 /AC heterostructures for real-world water purification have yet to be performed. This study aimed to address this gap by comparing the effectiveness of titanium isopropoxide (Ti(OiPr) 4 ) and titanium butoxide (Ti(OBu) 4 ) for synthesizing TiO 2 /AC heterostructures using four different methods (sol-gel, solvothermal, and microwave-assisted hydrothermal methods [x2]). The elaborated heterostructures were compared with commercial TiO 2 materials for their ability to degrade five emerging contaminants (caffeine, hydrochlorothiazide, saccharin, sulfamethoxazole, and sucralose). Hydrochlorothiazide and sulfamethoxazole were demonstrated to be rapidly degraded by UV-C irradiation within 15 min. Caffeine, saccharin, and sucralose were less susceptible to UV degradation. All the elaborated TiO 2 /AC heterostructures consisted of pure anatase phase, with Ti(OBu) 4 syntheses generating larger average crystal sizes and lower surface areas. Sol-gel preparations produced the most effective TiO 2 /AC heterostructures due to their high surface area. Compared with the commercial TiO 2 , the heterostructures enhanced the photocatalytic activity of TiO 2 by up to 10.0 times. Also, the heterostructures remained effective at environmentally relevant conditions (i.e., concentration of the contaminant and water matrices). The reuse of the materials was tested and showed no reduction in efficiency after four removal/regeneration cycles. Overall, this study presents novel TiO 2 /AC heterostructures with increased photocatalytic efficiency that can serve as an efficient material for removing contaminants at large scales (e.g., water treatment plants)., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Ltd. All rights reserved.)

This work investigated the adsorption of five model contaminants of emerging concern (CECs) that are released daily in domestic effluents (caffeine, hydrochlorothiazide, saccharin, sulfamethoxazole and sucralose) onto two activated carbons (ACs), in fixed-bed column experiments with different aqueous matrices (ultrapure water, wastewater treatment plant (WWTP) effluent and WWTP effluent pretreated by reverse osmosis and photoperoxidation (reuse water)). The ACs were chemically similar, but AC1 had smaller particles (0.7-1.7 mm) and lower surface area (551 m 2 g -1 ) than AC2 (1.2-2.4 mm and 716 m 2 g -1 ). AC1 had a higher adsorption capacity (q ads ) for the CECs in the downflow mode. Overall, the q ads values of the CECs followed the order: caffeine > sulfamethoxazole > hydrochlorothiazide = saccharin > sucralose. In the downflow mode, preferential pathways reduced the hydraulic retention time (HRT) of the fixed-bed column loaded with AC, which reduced the useful lifetime of column and the adsorption capacity. Nevertheless, the adsorption capacity and useful lifetime of the fixed-bed columns remained similar in the upflow mode (no preferential pathways were observed) regardless of the AC used. Since the HRTs were also found to be similar, it was evident that the crucial factor influencing the adsorption of the CECs was the HRT, which played a pivotal role in the overall process becoming evident. Compared to ultrapure water, use of the WWTP effluent reduced q ads for all the CECs by up to 4.1 times, while reuse water reduced q ads by up to 1.2 times. The AC1 could be in-situ regenerated using ethanol, with a global efficiency of 97.2 %. The results showed the importance of pretreatment techniques and optimization of the operational parameters, such as HRT, for enhancing the useful lifetime and q ads of fixed-bed columns., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier B.V. All rights reserved.)

According to the World Health Organization (WHO), the definition of water quality indicators, including contaminants of emerging concern (CECs), associated with the development of multi-barrier approaches for wastewater treatment, are crucial steps towards direct potable reuse of water. The aims of this study were 1) quantifying twelve CECs (including pharmaceutical, stimulant, and artificial sweetener compounds) in both untreated and treated wastewater samples in a Brazilian wastewater treatment plant (WWTP) using bidimensional liquid chromatography coupled with tandem mass spectrometry, allowing the selection of five marker (i.e., priority) CECs; 2) evaluating the adsorption potential of such selected CECs [caffeine, hydrochlorothiazide, saccharin, sucralose (SUC), and sulfamethoxazole (SMX)] onto coconut-shell granular activated carbon (GAC); and 3) investigating the removal of the same CECs by a multi-barrier system (pilot-scale, 350 L h -1 ) treating the effluent of the WWTP and composed of reverse osmosis (RO), photoperoxidation (UV/H 2 O 2 ), and filtration with GAC. Such technologies were tested separately and in binary or ternary combinations. Eleven and eight CECs were detected and quantified on the untreated and treated wastewater samples of the Brazilian WWTP, respectively. For the treated wastewater, the concentrations ranged from 499 ng L -1 (SMX) to 87,831 ng L -1 (SUC). The adsorption onto AC data fitted the Sips isotherm model, indicating monolayer chemisorption, which was also suggested by the mean adsorption energy values (>16 kJ mol -1 ). SMX and SUC were the most and the least adsorbed CECs (4.33 and 1.21 mg g -1 , respectively). Concerning the pilot-scale treatment plant, the ternary combination (RO + UV/H 2 O 2 +GAC) removed >99% of the five marker CECs and promoted reductions on water color, turbidity, as well as on nitrogen and phosphorus concentrations. Further studies on water reuse could prioritize the selected marker CECs as quality indicators. While the removal of marker CECs is one of the WHO performance requirements, the RO + UV/H 2 O 2 +GAC system showed promising results as a first approach to direct potable reuse of water., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier Ltd. All rights reserved.)

Activated carbon (AC) can be used for the removal of emerging contaminants (e.g., drugs) in water and wastewater treatment plants. In the present study, we investigated the performance of two ACs (from coconut shell and Pinnus sp.) in the adsorption of caffeine, carbamazepine, and ricobendazole considering the compounds separately and in combination in batch-scale experiments. The concentrations of the drugs were determined by a validated method using solid-phase extraction with on-line ultra-high performance liquid chromatography-tandem mass spectrometry. The most mesoporous AC provided higher drug removal. The kinetic data were described by the pseudo-second-order, Elovich, and Weber-Morris models, while the adsorption isotherms showed a better fit to the Freundlich model, indicative of multilayer adsorption. The Dubinin-Radushkevich model was used as a first approach to estimate the mean adsorption energy (E) and the results indicate that chemisorption governed the adsorption process, with E higher than 8 kJ mol -1 . In the multicomponent assays, the adsorption of caffeine showed the greatest hindrance caused by the presence of other drugs. Multicomponent assays are fundamental to evaluate the potential adsorption capacity in real water treatment plants. Our study suggests that drugs with different structures and physicochemical properties may interact differently with ACs, especially in multicomponent solutions, with important implications for the design (e.g., volumes and areas of treatment plants) and operation (e.g., water residence time) of the treatment plants., (© 2021. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

Benzimidazoles are anthelmintics frequently used in sheep farming due to the high susceptibility of these animals to parasitic diseases. Sheep excreta are often disposed onto soils as a fertilizer, and they may contain benzimidazole residues that can contaminate soil and water. This work aimed to assess the leaching behavior of benzimidazole drugs (albendazole, fenbendazole, and thiabendazole) and their metabolites in two Brazilian soils of different textural classifications (sandy and clay), as well as sheep excreta-amended soils, following the OECD 312 Guidelines. Ewes received a single oral dose of 10 mg kg -1 b.w. of either albendazole or fenbendazole. The feces were collected at 24, 48, 72, 96, and 120 h post-dose, and the parent drugs and their metabolites extracted using the QuEChERS approach and quantified by UHPLC-MS/MS. For the leaching assays, a benzimidazole solution was directly applied onto the soil columns, or an amount of 5 g of the medicated sheep feces was distributed over the top of the soil columns. In soil samples, benzimidazoles were extracted by solid-liquid extraction and quantified by UHPLC-MS/MS. For the leaching studies, atrazine was used as a reference substance to determine the relative mobility factor of the analytes of interest. Benzimidazoles were considered slightly to moderately mobile in both soils tested, with a leaching distance of up to 25 cm in a 30-cm soil column. Approximately 3 to 6% of the benzimidazoles present in ewe feces were able to leach into the soil columns. This finding is of concern since benzimidazoles are persistent in soil and may pose a risk to soil biota and induce the development of resistant strains of parasites., (© 2020. Springer-Verlag GmbH Germany, part of Springer Nature.)

N-nitrosodiethanolamine (NDELA) is a carcinogenic contaminant of concern in the cosmetics industry. Contaminated raw material, degradation, reactions of ingredients of the formulation, or migration of packaging material can be responsible for the presence of NDELA in the final product. Liquid chromatography coupled to tandem mass spectrometry is the most widely accepted technique for the quantitation of NDELA in cosmetic products. Still, there is no consensus regarding the sample preparation procedure. The aim of this work was to evaluate the performance of two-dimensional liquid chromatography coupled with tandem mass spectrometry for the determination of NDELA in shampoo. In the first dimension an Oasis HLB SPE-column was used and in the second dimension a CSH C18 column. NDELA-d 8 was used as an internal standard. The 2D-LC parameters were optimized by a central composite multivariate design. However, before quantitation, a sample preparation step using solid-phase extraction was necessary to eliminate compounds present in the formulation, especially surfactants that were not compatible with the chromatographic columns. Moreover, the complex matrices and singular compositions of shampoo from different manufacturers required adjustments of the sample preparation procedure for each sample. The limit of quantitation of the method for the determination of NDELA in shampoo was in the range of 5-10 ng g -1 . The accuracy of the method at the LOQ (10 ng g -1 ) was 114 % and the inter-day precision of 15.3 % (n = 9). One sample out of 12 presented an NDELA concentration of 54 ng g -1 ., Competing Interests: Declaration of Competing Interest The authors report no declarations of interest., (Copyright © 2021 Elsevier B.V. All rights reserved.)

The consumption of low-calorie sweeteners (LCSs) such as acesulfame (ACE), sucralose (SUC), saccharin (SAC), cyclamate (CYC), aspartame (ASP), neotame (NEO), and stevioside (STV) is increasing worldwide to meet the demand for reduced-calorie foods and beverages. However, there are no consumption data available in Brazil, as well as their concentration in sewage and removal on wastewater treatment plants (WWTPs). In the present study, ACE, SUC, SAC, CYC, ASP, NEO, and STV were assessed at five WWTPs located in the metropolitan region of Campinas (São Paulo State, Brazil), in operation with different treatment processes. Surface water was also analyzed. Analyses were carried out by on-line solid-phase extraction ultra-high performance liquid chromatography-tandem mass spectrometry. The major points are the following: LCS concentrations in the influents ranged from 0.25 to 189 μg L -1 and followed the order CYC > ACE > SAC > SUC. NEO, ASP, and STV were not detected at any sampling site. Sweetener concentrations in the WWTP outputs differed mainly due to the different treatment setups employed. CYC and SAC were completely removed by biodegradation-based processes, while ACE removal was favored by the anaerobic-anoxic-aerobic process. SUC presented the highest concentration in the treated sewage, even at the WWTP operating with ultrafiltration membranes and therefore could be a marker compound for evaluation of the efficiency of removal of contaminants in WWTPs. Risk quotient estimation, using the PNEC and MEC values, indicated that the levels of the LCS reported here were harmless to the biota. The consumption of ACE, CYC, SAC, and SUC was estimated to be 2634 t year -1 ., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

Photoperoxidation (UV/H 2 O 2 ) was used to degrade three of the worldwide most consumed antidepressant pharmaceuticals-bupropion, escitalopram, and fluoxetine-in ultrapure water, drinking tap water, surface water, and reclaimed water. The study was performed with antidepressants in concentration levels in which these compounds usually occur in the water matrices. Online solid-phase extraction coupled to UHPLC-MS/MS was used to quantify the analytes during degradation studies. The UV/H 2 O 2 process was able to degrade bupropion and fluoxetine in ultrapure water, using 0.042 mmol L -1 of H 2 O 2 and 1.9 kJ of UV-C irradiation. Nevertheless, escitalopram, which had the most recalcitrant character among the studied antidepressants, needed a tenfold more oxidant and UV-C irradiation. The primary metabolites of the antidepressants were identified as the major by-products generated by the UV/H 2 O 2 process, and they persisted in the solution even when the parent compound was degraded. The residual toxicity of the solution was evaluated for two different trophic levels. The UV/H 2 O 2 process reduced the toxicity of the solution to Raphidocelis. subcapitata microalgae after 30 min of reaction. On the other hand, the toxicity of the residual solution increased over the reaction time to the marine bacteria Vibrio fischeri (reaching up to 48.3% of bioluminescence inhibition after 60 min of reaction). Thus, our results evidenced that the toxicity against different trophic levels and the monitoring of the by-products formed are important aspects to be considered regarding the safety of the treated solution and the optimization of the treatment process.

Ciprofloxacin (CIP) is an antimicrobial "pseudo-persistent" in aquatic ecosystems. Once dispersed in the water compartments, it can also affect the microalgae. Thus, the evaluation of its long-term ecotoxicological effects is necessary. CIP interactions with other pharmaceuticals are not well known. In this study, we investigated the toxic effects of CIP alone and combined with caffeine (CAF), using the modified Gompertz model parameters and the chlorophyll-a production of the microalga Raphidocelis subcapitata as endpoints, throughout a 16-day exposure assay. The exposure to CIP alone led to significant reductions of the growth rate and the cell density of the microalgae compared to control groups. The combination with CAF lowered the adverse effects of CIP to R. subcapitata . However, as the toxicity is dynamic, our results indicated that the toxic effects in respect to the studied endpoints changed throughout the exposure period, reinforcing the need for longer-term ecotoxicity assessments., Competing Interests: The authors report no declarations of interest., (© 2021 The Authors.)

According to the World Health Organization, >360 million people worldwide suffer from mental diseases such as depression, anxiety, or bipolar disorder, for which psychotropic drugs are frequently prescribed. Despite being highly metabolized in the human organism, non-metabolized portions of these drugs are excreted, subsequently reaching wastewater treatment plants (WWTPs), where they may be incompletely removed during treatment, leading to the contamination of surface waters. In this work, ten psychotropic drugs widely consumed in Brazil (alprazolam, amitriptyline, bupropion, carbamazepine, clonazepam, escitalopram, fluoxetine, nortriptyline, sertraline, and trazadone) were monitored at five WWTPs located in the metropolitan region of Campinas (São Paulo State, Brazil). The drugs were determined in the influents, at different stages of the treatments, and in the effluents. Surface waters from the Atibaia River and the Anhumas Creek were also monitored. Quantitation of the pharmaceuticals was carried out by online solid-phase extraction coupled with ultra-high performance liquid chromatography and tandem mass spectrometry. The method was validated and presented a limit of quantitation of 50 ng L -1 for all the drugs assessed. Six of the substances monitored were quantified in the samples collected from the different treatment processes employed at the WWTPs. These technologies were unable to act as barriers for these psychotropics drugs. The concentrations ranged from 50 to 3000 ng L -1 in the WWTP effluents, while the main contaminants were found in surface waters at concentrations from 25 to 3530 ng L -1 . The levels of the psychotropic detected in this work did not appear to present risks to the aquatic biota., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier B.V. All rights reserved.)

The screening of compounds is the initial step in research for the development of new drugs. For this reason, the availability of fast and reliable tools for the screening of a large number of compounds becomes essential. Among the therapeutic targets, the enzyme xanthine oxidase (XO) is of great interest for its importance as a biological source of superoxide radicals, which contribute to the oxidative stress on organisms and are involved in many pathological processes. In the present study, we validated a new method using an immobilized capillary enzyme reactor in an LC system directly coupled to triple quadrupole mass spectrometry to screen for XO ligands. The use of mass spectrometry provided selectivity and speed to the system, eliminating the analytical separation step. The Michaelis-Menten constant (K M ) value determined for the immobilized enzyme was 14.5 ± 0.4 μmol L -1 , which is consistent with the value previously reported for the XO-ICER with UV detection in a 2D LC method. The on-line approach was successfully applied to assay the XO inhibitory activities of thirty isolated compounds from different classes of natural products and provided greater productivity (288 analysis/day) than 2D LC method (84 analysis/day) of screened samples., (Copyright © 2020 Elsevier B.V. All rights reserved.)

Avermectins and moxidectin are antiparasitics widely used as active pharmaceutical ingredients in veterinary medicine, as well as in pesticide formulations for pest control in agriculture. Although the use of these compounds provides benefits to agribusiness, they can impact the environment, since a large part of these substances may reach the soil and water from the excreta of treated animals and following direct applications to crops. The present work had the objective of evaluating the dissipation behaviors of abamectin, doramectin, eprinomectin, ivermectin, and moxidectin in four native Brazilian soils of different textural classes (clay, sandy-clay, sandy, and sandy-clay-loam), following OECD Guideline 307. The studies were conducted in a climate chamber at 22 °C, 71% relative humidity, and protected from light. The dissipation studies were carried out with all drugs together, since no difference was verified when studies were done with each drug separately. The concentrations of the drugs in the soils were determined using an ultra-high performance liquid chromatograph coupled to a fluorescence detector or a tandem mass spectrometer. The dissipation half-life (DT 50 ) values ranged from 9 to 16 days and the calculated GUS index values were in the range from -1.10 to 0.08, indicating low mobility of the drugs in the soils evaluated and low tendency for leaching. In addition, a field study was carried out to evaluate the dissipation of abamectin after application of a foliar pesticide in an orange crop. A DT 50 of 9 days was determined, which was similar to that obtained under controlled conditions in the climate chamber (12 days), indicating that biotransformation was the primary process influencing the overall dissipation., (Copyright © 2019 Elsevier Inc. All rights reserved.)

Background: Aquaculture is on the rise worldwide, and the use of antibiotics is fostering higher production intensity. However, recent findings suggest that the use of antibiotics comes at the price of increased antibiotic resistance. Yet, the effect of the oral administration of antibiotics on the mobility of microbial resistance genes in the fish gut is not well understood. In the present study, Piaractus mesopotamicus was used as a model to evaluate the effect of the antimicrobial florfenicol on the diversity of the gut microbiome as well as antibiotic resistance genes (ARGs) and mobile genetic elements (MGEs) using a metagenomic approach., Results: The total relative abundance of ARGs and MGEs significantly increased during the antibiotic exposure. Additionally, phage integrases, transposases, and transposons flanking ARGs accumulated in the gut microbiome of P. mesopotamicus because of the antibiotic exposure. MGEs co-occurring with ARGs showed a significant positive correlation with the total ARGs found. Furthermore, shifts in the gut microbiome towards well-known putative pathogens such as Salmonella, Plesiomonas, and Citrobacter were observed following florfenicol treatment. Mainly Plesiomonas and Citrobacter harbored genes that code for multidrug and phenicol efflux pumps. Moreover, several genes related to RNA processing and modification, cell motility, SOS response, and extracellular structure were enriched due to the antibiotic application. The observed effects were visible during the complete application phase and disappeared at the post-exposure phase., Conclusions: Our findings suggest that the oral administration of antibiotics increases the potential for MGE-mediated exchange of ARGs in the gut of fish and could contribute to the enrichment and dispersion of ARGs in aquaculture systems. Importantly, this increase in the potential for ARGs exchange could be an effect of changes in community structure and/or ARG mobilization.

Pharmaceutical residues are constantly released into natural waters, mainly from wastewater treatment plants (WWTPs) whose processes are unable to completely eliminate them. Among these drugs, the occurrence of benzimidazoles, a class of antiparasitics for human and veterinary use, has been reported in WWTP effluents and surface waters. In this study, an SPE-UHPLC-MS/MS method was developed and optimized for extraction and quantitation of benzimidazoles in influents and effluents of a local WWTP and in hospital wastewater. The extraction procedure was optimized using response surface methodology (Box-Behnken design) and the optimal parameters were as follows: 2.0 mL of loading solvent consisting of a mixture of water:methanol (95:5, v/v) and temperature at 43 °C. In hospital wastewater, albendazole (ABZ) and its principal metabolite ricobendazole (RBZ) were the main benzimidazole-related contaminants and were found at concentrations of up to 3810 and 3894 ng L -1 , respectively. The WWTP system was able to remove from 46% to 95% of the ABZ quantified in the influent, discharging an effluent with 16-441 ng L -1 of ABZ. The concentrations of other benzimidazoles and metabolites in the WWTP effluents remained below 350 ng L -1 . WWTP effluents fortified with 50 μg L -1 of ABZ required 26.7 mg O3 L -1 to remove ABZ and RBZ. After ozonation, the COD and BOD 5 of the effluents were reduced by 27%. Photolysis by UVA radiation was not effective to remove ABZ and FBZ from the effluent samples., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

Brazil is one of the world's largest producers of animal protein, requiring the large-scale use of veterinary drugs. The administration of antimicrobials and antiparasitics is a common practice. However, there is a lack of information on how these drugs impact the environment. Antimicrobials are capable of altering the soil microbial population and are responsible for the development of multidrug-resistant microbial strains. Therefore, it is important to evaluate the fate and transport of these compounds in the environment, and one parameter used for this purpose is the soil-water partition coefficient. In this work, an assessment was made of the soil sorption behaviors of 18 drugs from seven different families, including antimicrobials (sulfonamides, fluoroquinolones, amphenicols, and macrolides) and antiparasitic drugs (milbemycin, avermectins, and benzimidazoles). Seven subtropical soils of different textural classes were tested. The Freundlich sorption coefficients, expressed as μg 1-1/n (cm 3 ) 1/n g -1 , were in the following ranges: 0.45 to 19 (sulfonamides), 72 to 2410 (fluoroquinolones), 9 to 58 (thiabendazole), 0.03 to 0.48 (florfenicol), 105 to 424 (moxidectin), 14 to 184 (avermectins), and 1.5 to 74 (macrolides). The results showed that the drugs belonging to the same family, with chemical structures in common, presented similar behaviors regarding sorption and desorption, for the different soils tested and are generally in agreement with soils from temperate regions. The data set obtained in this work give an overview of the fate of the veterinary drugs in Brazilian subtropical soils with different textures and composition and can be very helpful for exposure risk assessments., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

Veterinary antimicrobials are emerging environmental contaminants of concern. In this study, the sorption of enrofloxacin (ENR) onto humic acids (HAs) extracted from three Brazilian soils was evaluated. HAs were characterized by elemental analysis and solid 13 C nuclear magnetic resonance spectroscopy. The sorption of ENR onto HAs was at least 20-fold higher than onto the soils from which they were separated. Ionic and cation bridging are the primary interactions involved. The interactions driven by cation exchange are predominant on HAs, which appear to have abundant carboxylic groups and a relatively high proportion of H-bond donor moieties with carbohydrate-like structures. Interactions explained by cation bridging and/or surface complexation on HAs are facilitated by moieties containing conjugated ligands, significant content of oxygen-containing functional groups, such as phenolic-OH or lignin-like structures. HAs containing electron-donating phenolic moieties and carboxylic acid ligand groups exhibit a sorption mechanism that is primarily driven by strong metal binding, favoring the formation of ternary complexes between functional groups of the organic matter and drugs.

Avermectins and milbemycin are widely used as veterinary drugs and as agricultural pesticides, and their residues have been detected in soil. This study reports a simple and high-throughput method for determining ivermectin (IVER), abamectin (ABA), doramectin (DORA), eprinomectin (EPRI), and moxidectin (MOXI) residues in soils, employing an on-line solid-phase extraction technique coupled with ultra-high performance liquid chromatography and tandem mass spectrometry (SPE-UHPLC-MS/MS). The method was validated and applied for the determination of ABA in soils from an orange plantation treated with this pesticide. The sample preparation procedure consisted of extraction of the compounds from soil using methanol (with recoveries of 73-85%), and subsequent on-line SPE cleanup and concentration using a C8 sorbent coupled to the UHPLC-MS/MS system. The optimal conditions were: water:methanol (40:60, v/v) sample solvent; water:methanol (96:4, v/v) loading solvent; 2×250μL sample volume; and elution of the analytes retained on the SPE column in back flush with 5mmolL -1 ammonium acetate:acetonitrile (10:90, v/v) chromatographic mobile phase. The method produced linear results in the ranges 0.1-10ngg -1 (IVER, ABA, DORA, and MOXI) and 0.5-10ngg -1 (EPRI), with linearity greater than 0.99. The precision of the method was better than 19% and accuracy was in the range 74-89%. The limits of quantitation were 0.2ngg -1 for EPRI and 0.1ngg -1 for the other compounds. The SPE column could be reused in more than 2000 analyses without loss of efficiency. The ABA concentration in the soil varied between 1.7 and 18ngg -1 , and no dissipation was observed during five consecutive days after application of the pesticide to the orange plantation., (Copyright © 2016 Elsevier B.V. All rights reserved.)

Honeybees and bee products are potential bioindicators of the presence of contaminants in the environment, enabling monitoring of large areas due to the long distances travelled by bees. This work evaluates the use of bee pollen as a bioindicator of environmental contamination by pesticides. A GC-MS/MS analytical method for multiresidue determination of 26 different pesticides in pollen was developed and validated in accordance with the recommendations of the European Union SANCO guide. Environmental monitoring was conducted using the analysis of 145 pollen samples collected from ten beehives in the experimental apiary of Embrapa in Jaguariúna (São Paulo State, Brazil). Bioallethrin and pendimethalin were identified in four and eighteen samples, respectively, at concentrations below the LOQ of the method (25 ng g(-1)). Passive sampling with polyurethane foam discs was used as a control, and no pesticides were found. The detection of pesticide residues in seven samples (33%) from commercial apiaries in Ribeirão Preto (São Paulo State) confirmed the efficiency of the analytical method and the need for environmental monitoring for the presence of pesticide residues. The results demonstrated the potential of bee pollen as a bioindicator of environmental contamination by pesticides., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

Sulfonamides are antimicrobials used widely as veterinary drugs, and their residues have been detected in environmental matrices. An analytical method for determining sulfadiazine, sulfathiazole, sulfamethazine, sulfamethoxazole, sulfadimethoxine and sulfaquinoxaline residues in soils employing a solid phase extraction on-line technique coupled with ultra-high performance liquid chromatography and tandem mass spectrometry (SPE-UHPLC-MS/MS) was developed and validated in this study. SPE and chromatographic separation were performed using an Oasis HLB column and an Acquity UPLC BEH C18 analytical column, respectively, at 40°C. Samples were prepared by extracting sulfonamides from soil using a solid-liquid extraction method with water:acetonitrile, 1:1v/v (recovery of 70.2-99.9%). The following parameters were evaluated to optimize the on-line SPE process: sorbent type (Oasis and C8), sample volume (100-400μL), loading solvent (water and different proportions of water:methanol) and washing volume (0.19-0.66mL). The method produced linear results for all sulfonamides from 0.5 to 12.5ngg(-1) with a linearity greater than 0.99. The precision of the method was less than 15%, and the matrix effect was -27% to -87%. The accuracy was in the range of 77-112% for all sulfonamides. The limit of quantitation in the two soils (clay and sand) was 0.5ngg(-1). The SPE column allowed for the analysis of many (more than 2000) samples without decreasing the efficiency., (Copyright © 2016 Elsevier B.V. All rights reserved.)

The use of electric fields as additional driving forces in sample preparation techniques is an innovative approach that is environmentally friendly, straightforward, and able to overcome several limitations of conventional sample preparation procedures. In this work, the advantages of electric field-assisted solid phase extraction (E-SPE) using syringe-type cartridges were demonstrated for the extraction of four fluoroquinolones (FQs) in their anionic forms. The FQs were extracted from eggs and subsequently determined by UHPLC-MS/MS. The use of electric fields during the washing and final elution steps resulted in a significant improvement of the extraction efficiencies for almost all FQs when compared to conventional SPE. Intra- and inter-day assays showed coefficients of variation below 10%. The better cleanup also resulted in the appearance of less precipitated matter in the final eluate, as well as reduced matrix effects. The results showed that the electrophoretic forces derived from electric fields are a promising way of significantly increasing the extraction efficiency of ionic analytes, while minimizing matrix effects associated with complex samples., (Copyright © 2016 Elsevier B.V. All rights reserved.)

Abamectin is a broad-spectrum antiparasitic agent that has been widely employed in veterinary medicine and has also been used as a pesticide in agriculture. Veterinary drugs may reach the soil and may be transported to surface and ground waters, posing risks to terrestrial and aquatic organisms. Sorption, transformation and transport processes are primarily responsible for the fate of these substances in the environment. In this study, the sorption and the aerobic dissipation of abamectin in Brazilian soils (sand, clay and sandy-clay) were evaluated. For sorption studies, batch equilibrium experiments were performed. Sorption and desorption isotherms were fitted to the Freundlich model. Abamectin showed a high affinity to soil particles, with Freundlich sorption and desorption coefficients ranging from 44 to 138 μg(1-1/n) (cm(3))(1/n) g(-1) and from 89 to 236 μg(1-1/n) (cm(3))(1/n) g(-1), respectively. Dissipation of abamectin was evaluated in sterile and non-sterile soils in an aerobic and dark environment under controlled temperature and humidity. The time required for a 50% reduction of the amount of abamectin present in non-sterile soils was up to 4 days, and the time period for 90% dissipation was up to 12 days. In sterilized soils, there was no reduction in the concentration of abamectin over 37 days of exposure, suggesting that aerobic microbial degradation must have been the primary mechanism responsible for the dissipation of abamectin in soils., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

Ivermectin (IVM) is a broad-spectrum antiparasitic drug that is regularly employed in veterinary medicine. In this work, the sorption and desorption of IVM in two Brazilian soils (N1-sand and S2-clay) as well as its leaching capacity, dissipation under aerobic conditions, and degradation in aqueous solution by photocatalysis with TiO2 in suspension were evaluated. The kinetic sorption curves of IVM were adjusted to a pseudo-second-order model. The sorption and desorption data were well fitted with the Freundlich isotherms in the log form (r > 0.96). The Freundlich sorption coefficient (K F (ads) ) and the Freundlich desorption coefficient (K F (des) ) were 77.7 and 120 μg(1-1/n) (cm(3))(1/n) g(-1) and 74.5 and 138 μg(1-1/n) (cm(3))(1/n) g(-1), for soils N1 and S2, respectively. A greater leaching capacity of IVM was observed for the sandy soil N1 than for the clay soil S2. Under aerobic conditions, the dissipation (DT50) at 19.3 °C was 15.5 days (soil N1) and 11.5 days (soil S2). Photocatalysis with UVC and TiO2 in suspension resulted in the degradation of 98 % of IVM (500 μg L(-1)) in water in 600 s. The toxicity (Daphnia similis) of the solutions submitted to the photocatalytic process was completely eliminated after 10 min.

An HPLC-PAD method using a gold working electrode and a triple-potential waveform was developed for the simultaneous determination of streptomycin and dihydrostreptomycin in veterinary drugs. Glucose was used as the internal standard, and the triple-potential waveform was optimized using a factorial and a central composite design. The optimum potentials were as follows: amperometric detection, E1=-0.15V; cleaning potential, E2=+0.85V; and reactivation of the electrode surface, E3=-0.65V. For the separation of the aminoglycosides and the internal standard of glucose, a CarboPac™ PA1 anion exchange column was used together with a mobile phase consisting of a 0.070 mol L(-1) sodium hydroxide solution in the isocratic elution mode with a flow rate of 0.8 mL min(-1). The method was validated and applied to the determination of streptomycin and dihydrostreptomycin in veterinary formulations (injection, suspension and ointment) without any previous sample pretreatment, except for the ointments, for which a liquid-liquid extraction was required before HPLC-PAD analysis. The method showed adequate selectivity, with an accuracy of 98-107% and a precision of less than 3.9%., (Copyright © 2014 Elsevier B.V. All rights reserved.)

Fluoroquinolones are potent antibacterial agents that are active against a wide range of pathogenic organisms and are widely used in veterinary medicine. Fluoroquinolones and their metabolites may reach the soil through animal excreta or manure and may contaminate water and soils. The degree of sorption of these antimicrobials to soils varies widely, as does the mobility of these drugs. In the present study, sorption of norfloxacin in four soils of the state of São Paulo was investigated with batch equilibrium experiments. A strong matrix effect on the chromatographic determination of norfloxacin was verified. Sorption kinetics were best fit by a pseudo second-order model (r>0.99), and sorption/desorption isotherms were well fit by the Freundlich model in log form (r>0.97). Norfloxacin showed high affinity for soil particles, with KF sorption values ranging from 643 to 2410 μg(1-1/n)(cm(3))(1/n)g(-1) and KF desorption values ranging from 686 to 2468 μg(1-1/n)(cm(3))(1/n)g(-1). The high desorption KF values indicate that norfloxacin is highly immobile in the evaluated soils., (Copyright © 2014 Elsevier Ltd. All rights reserved.)

Adsorption and desorption are important processes that influence the transport, transformation and bioavailability of antimicrobials in soils. The adsorption-desorption characteristics of sulfadimethoxine, sulfaquinoxaline and sulfamethazine in Brazilian soils (sandy, sandy-clay and clay) were evaluated using the batch equilibrium method. The sulfonamides were quantified in the soil solutions by a previously in house validated HPLC-PAD method. The adsorption/desorption data for the sulfonamides in soils fit the Freundlich isotherms well in the logarithmic form. The Freundlich adsorption coefficients ranged from 1.4 to 19.0 μg(1-1/n)(cm(3))(1/n)g(-1), suggesting that all of the sulfonamides weakly adsorbed on the evaluated soils. The Freundlich desorption coefficients ranged from 0.85 to 24.8 μg(1-1/n)(cm(3))(1/n)g(-1), indicating that the sulfonamides tend to be leached from soils with high sand and low organic carbon contents, suggesting that there is high potential for surface and groundwater contamination., (Copyright © 2014 Elsevier B.V. All rights reserved.)

Hebanthe eriantha (Poir.) Pedersen (Amaranthaceae), which is known as Brazilian ginseng is widely used in folk medicine as an aphrodisiac and antidiabetic tonic. The anti-tumor activity, attributed to the pfaffic acid present in roots of H. eriantha, is responsible for the great interest in the commercialization of this species. In Brazil, the species H. eriantha is mainly used in commercial preparations, although other plants of the genus Pfaffia and Hebanthe have been marketed as Pfaffia paniculata or Brazilian ginseng. The pfaffic acid present in the roots is mainly conjugated with sugars (pfaffosides) and can be used as an active marker of H. eriantha, which helps to differentiate this species from others marketed as Brazilian ginseng. The main objective of this study was to develop and validate a liquid chromatographic method to quantify pfaffic acid in the roots of H. eriantha. The extraction and hydrolysis conditions were optimized using an univariate and experimental design, respectively, and the quantification of pfaffic acid by high performance liquid chromatography with diode-array detection (HPLC-DAD) was validated. This method was used to evaluate the pfaffic acid content in 30 different genotypes of the species from a germplasm collection. The content of pfaffic acid ranged from 0.97 to 4.29% (w/w) on a dry weight basis., (Copyright © 2013 Elsevier B.V. All rights reserved.)

Flumequine is a broad-spectrum antimicrobial agent of the quinolone class, and it is widely used as a veterinary drug in food-producing animals. The presence of flumequine in the environment may contribute to the development of drug resistant bacterial strains. In this study, water samples fortified with flumequine (500 μg L(-1)) were degraded using the Fenton and photo-Fenton processes. The maximum degradation efficiency for flumequine by the Fenton process was approximately 40% (0.5 mmol L(-1) Fe(II), 2.0 mmol L(-1) H(2)O(2) and 15 min). By applying UV radiation (photo-Fenton process), the efficiency reached more than 94% in 60 min when 0.25 mmol L(-1) Fe(II) and 10.0 mmol L(-1) H(2)O(2) were used. Under these conditions, the Fenton process was able to reduce the biological activity, whereas the photo-Fenton process eliminated almost all of the antimicrobial activity because it was not detected. Four byproducts with an m/z of 244, 238, 220 and 202 were identified by mass spectrometry, and a degradation pathway for flumequine was proposed. The byproducts were derived from decarboxylation and defluorination reactions and from modifications in the alkylamino chain of the fluoroquinolone., (Copyright © 2013 Elsevier B.V. All rights reserved.)

Antimicrobials, among them sulfonamides are widely used in veterinary medicine and can contaminate the environment. The degree to which antimicrobials adsorb onto soil particles varies widely, as does the mobility of these drugs. Sulfadiazine (SDZ) was used to study the adsorption-desorption in Brazilian soil-water systems, using batch equilibrium experiments. Sorption of SDZ was carried out using four types of soils. Adsorption and desorption data were well fitted with Freundlich isotherms in log form (r>0.999) and (0.984

Methylparaben (MePa), ethylparaben (EtPa) and propylparaben (PrPa) have been widely used, among others, as chemical preservatives in cosmetics, drugs and foods. As these compounds are linked with allergies, dermatitis and estrogenic properties, it is necessary to control the concentration of these substances in different matrices. The aim of this paper are: to evaluate the electrochemical behavior of parabens on the boron-doped diamond (BDD) electrode and the development of a chromatographic method, with electrochemical detection (HPLC-ED), for determination of parabens in shampoo. A BDD (8000 ppm) electrode was adapted in a thin layer mode analytical cell consisting of a stainless steel and a platinum wire as reference and auxiliary electrodes, respectively. Chromatographic separations were obtained with a reversed phase C8 analytical column and a mobile phase of 0.025 molL(-1) disodium phosphate, pH 7.0, and acetonitrile (40:60, v/v), delivered at a flow rate of 1.0 mL min(-1). Sample preparation was performed by solid phase extraction using C18 cartridges and acetonitrile for elution. Benzylparaben was employed as internal standard. The HPLC-ED method developed, using the BDD electrode, was validated for the determination of parabens in shampoos and presented adequate linearity (>0.999), in the range of 0.0125-0.500% (w/w), detectability 0.01% (w/w), precision (RSD of 2.3-9.8%) and accuracy (93.1-104.4%) and could be applied for routine quality control of shampoos containing MePa, EtPa and PrPa., (Copyright © 2011 Elsevier B.V. All rights reserved.)

A new and selective sorbent for molecularly imprinted solid-phase extraction (MISPE) was developed and applied for the determination of residues of fenitrothion (FNT) in tomatoes, using HPLC coupled to photodiode array detection (HPLC-DAD). Using FNT as the template molecule, methacrylic acid as the functional monomer, ethylene glycol dimethacrylate as the cross-linker, toluene as the porogenic solvent, and bulk polymerization as the synthetic method, a molecularly imprinted polymer (MIP) was synthesized. In order to choose the medium which promotes the best molecular recognition of FNT by the MIP, the adsorption of FNT by the MIP was studied in different media containing acetonitrile and toluene. Besides FNT, three structurally related compounds were used to evaluate the selectivity of the FNT-molecularly imprinted polymer. The MIP exhibited the highest selective rebinding to FNT. The method developed was validated, using fortified blank tomato samples. The extraction efficiency was 96%. The limits of detection and quantitation were 0.050 and 0.130 microg g(-1), respectively. The intra-day precision was 5.9% and the inter-day precision 8.1%. The accuracy was higher than 89% for a concentration level around the maximum residue limit of 0.5 microg g(-1).

A method for simultaneous determination of flumequine (FLM), oxolinic acid (OXO), sarafloxacin (SAR), danofloxacin (DAN), enrofloxacin (ENR), and ciprofloxacin (CIP) in tilapia (Orechromis niloticus) fillets, using liquid chromatography-tandem mass spectrometry (LC-ESI-MS-MS QToF) is presented. The quinolones were extracted from the food matrix with a solution of 10% trichloroacetic acid-methanol (80:20 v/v) with ultrasonic assistance. Clean-up of the extract solution was performed by using polymeric solid-phase extraction cartridges. The LC separation was carried out on an octadecyl hybrid silica column (C18, 150 mm x 3 mm, 5 microm). The column temperature was set at 30 degrees C, and gradient elution (0.2 mL min(-1)) was performed using water and acetonitrile, both containing 0.1% of acetic acid, as mobile phase components. The analytes were ionized using electrospray in the positive polarity mode. The following analytical results were obtained: linearity was about 0.99 for all the quinolones; intra and inter-assay precision (RSD%) were lower than 12.7 and 20%, respectively; and recoveries were from 89 to 112%. The quantitation limits were below the maximum residue limits established for the analytes. The method is suitable for the determination of quinolone residues in fish fillets and the QToF technique made it possible to obtain m/z ratios with less than 10 ppm of error for each analyte.

Organophosphorus insecticides are widely employed in agriculture, and residues of them can remain after harvesting or storage. Pesticide residue control is an important task for ensuring food safety. Common chromatographic methods used in the determination of pesticide residues in food require clean-up and concentration steps prior to quantitation. While solid-phase extraction has been widely employed for this purpose, there is a need to improve selectivity. Due to their inherent biomimetic recognition systems, molecularly imprinted polymers (MIP) allow selectivity to be enhanced while keeping the costs of analysis low. In this work, a MIP that was designed to enable the selective extraction of fenitrothion (FNT) from tomatoes was synthesized using a noncovalent imprinting approach. The polymer was prepared using methacrylic acid as functional monomer and ethyleneglycol dimethacrylate as crosslinking monomer in dichloromethane (a porogenic solvent). The polymer was characterized by Fourier transform infrared spectroscopy, solid-state nuclear magnetic resonance (NMR), scanning electron microscopy (SEM), and nitrogen sorption porosimetry. The pore structure and the surface area were evaluated using the BET adsorption method. To characterize the batch rebinding behavior of the MIP, the adsorption isotherm was measured, allowing the total number of binding sites, the average binding affinity and the heterogeneity index to be established. A voltammetric method of quantifying FNT during the molecularly imprinted solid-phase extraction (MISPE) studies was developed. The polymer was placed in extraction cartridges which were then used to clean up and concentrate FNT in tomato samples prior to high-performance liquid chromatographic quantitation. The material presented a medium extraction efficiency of 59% (for analyses performed with three different cartridges on three days and a fortification level of 5.0 microg g(-1)) and selectivity when used in the preparation of tomato samples, and presented the advantage that the polymer could be reused several times after regeneration.

A capillary zone electrophoresis (CZE) method for the determination of chloramphenicol (CLP), danofloxacin (DANO), ciprofloxacin (CIPRO), enrofloxacin (ENRO), sulfamethazine (SMZ), sulfaquinoxaline (SQX) and sulfamethoxazole (SMX) is described. For the development, the effective mobilities were estimated and a central composite design was performed. The method was in-house validated for CLP, CIPRO, ENRO and SMX determination in pharmaceuticals. In comparison with the HPLC method recommended by the United States Pharmacopoeia, this CZE method exhibited the same performance, with the advantage that seven different antimicrobials in pharmaceutical formulations could be simultaneously determined.

An analytical method for the determination of oxytetracycline (OTC) in tomatoes was developed and validated. Liquid-liquid extraction (LLE) and a solid-phase extraction (SPE) were used for sample preparation. Reversed-phase high performance liquid chromatography (RP-HPLC) using a C18 column and a mobile phase containing MeOH: calcium chloride, disodium ethylenediaminetetraacetate (EDTA) and sodium acetate, pH 7.3 (30:70, v/v), with fluorescence detection at 390nm excitation and 512nm emission, was used for separation and quantitation of OTC. The method was validated through the following performance criteria: linearity and linear range, sensitivity, selectivity, intra-day and inter-day precision, detection and quantitation limits and accuracy. Limit of quantitation show that the method developed is suitable for the determination of OTC at a level below the maximum residue limits established by the Brazilian legislations (250μgkg(-1)). Of 40 samples analyzed, none contained OTC above the limit of quantitation., (Copyright © 2007 Elsevier Ltd. All rights reserved.)

Arsenic oxidation (As(III) to As(V)) and As(V) removal from water were assessed by using TiO2 immobilized in PET (polyethylene terephthalate) bottles in the presence of natural sunlight and iron salts. The effect of many parameters was sequentially studied: TiO2 concentration of the coating solution, Fe(II) concentration, pH, solar irradiation time; dissolved organic carbon concentration. The final conditions (TiO2 concentration of the coating solution: 10%; Fe(II): 7.0 mg l(-1); solar exposure time: 120 min) were applied to natural water samples spiked with 500 microg l(-1) As(III) in order to verify the influence of natural water matrix. After treatment, As(III) and total As concentrations were lower than the limit of quantitation (2 microg l(-1)) of the voltammetric method used, showing a removal over 99%, and giving evidence that As(III) was effectively oxidized to As(V). The results obtained demonstrated that TiO2 can be easily immobilized on a PET surface in order to perform As(III) oxidation in water and that this TiO2 immobilization, combined with coprecipitation of arsenic on Fe(III) hydroxides(oxides) could be an efficient way for inorganic arsenic removal from groundwaters.