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1.
J Vet Pharmacol Ther ; 2024 Sep 27.
Artículo en Inglés | MEDLINE | ID: mdl-39340123

RESUMEN

Water temperature is a critical environmental parameter that significantly influences fish metabolism. This study assessed the metabolism of florfenicol (FF) in tilapia (Oreochromis niloticus) at water temperatures typical of tropical and subtropical regions. Fish were treated with FF by oral administration of a dose of 10 mg kg-1 bw for 10 consecutive days. Fish fillet, liver, and kidney were sampled during the treatment phase (1, 5, and 10 days) and posttreatment (1, 2, 3, and 5 days after the last FF administration). FF, florfenicol amine (FFA), monochloro florfenicol (FFCl), and florfenicol alcohol (FFOH) were determined in the sampled tissues using a validated LC-LC-MS/MS method. The highest FF, FFA, and FFOH concentrations were determined on day 5 during the treatment phase. For FF, the concentration order is kidney > liver > fillet, while for the metabolites FFOH and FFA, the order is liver > kidney > fillet. In fillet and liver, the concentrations of FFOH were higher than the FFA concentrations, indicating that FFOH was the primary metabolite in these tissues. FFCl was only quantified at concentrations lower than 90 µg kg-1 in all tissues. The results indicated that FF can be readily absorbed and rapidly eliminated in tilapia cultivated in warm water environments. This study revealed FFOH as the primary and most persistent metabolite in tilapia farmed in warm water, followed by FFA.

2.
Environ Toxicol Pharmacol ; 106: 104382, 2024 Mar.
Artículo en Inglés | MEDLINE | ID: mdl-38325623

RESUMEN

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.


Asunto(s)
Cíclidos , Tilapia , Animales , Humanos , Aguas Residuales , Colorantes de Rosanilina
3.
Food Chem ; 438: 138010, 2024 Apr 16.
Artículo en Inglés | MEDLINE | ID: mdl-37983999

RESUMEN

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).


Asunto(s)
Alcaloides , Fagopyrum , Hiosciamina , Alcaloides/análisis , Espectrometría de Masas en Tándem , Cromatografía Líquida de Alta Presión/métodos , Harina/análisis , Brasil , Temperatura , Tropanos/química , Escopolamina/análisis
4.
Artículo en Inglés | MEDLINE | ID: mdl-37988113

RESUMEN

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.


Asunto(s)
Levamisol , Agua , Animales , Cromatografía Liquida , Gelatina , Espectrometría de Masas en Tándem , Peces , Alimentación Animal/análisis
5.
Environ Sci Pollut Res Int ; 29(28): 42185-42200, 2022 Jun.
Artículo en Inglés | MEDLINE | ID: mdl-34435291

RESUMEN

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.


Asunto(s)
Carbón Orgánico , Contaminantes Químicos del Agua , Adsorción , Cafeína/análisis , Carbón Orgánico/química , Concentración de Iones de Hidrógeno , Cinética , Termodinámica , Contaminantes Químicos del Agua/análisis
6.
J Pharm Biomed Anal ; 202: 114132, 2021 Aug 05.
Artículo en Inglés | MEDLINE | ID: mdl-34000519

RESUMEN

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-d8 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.


Asunto(s)
Dietilnitrosamina , Espectrometría de Masas en Tándem , Cromatografía Líquida de Alta Presión , Dietilnitrosamina/análogos & derivados , Extracción en Fase Sólida
7.
J Environ Manage ; 289: 112561, 2021 Jul 01.
Artículo en Inglés | MEDLINE | ID: mdl-33865021

RESUMEN

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.


Asunto(s)
Contaminantes Químicos del Agua , Purificación del Agua , Brasil , Aguas del Alcantarillado , Edulcorantes/análisis , Aguas Residuales/análisis , Agua , Contaminantes Químicos del Agua/análisis
8.
Toxicol Rep ; 8: 429-435, 2021.
Artículo en Inglés | MEDLINE | ID: mdl-33717995

RESUMEN

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.

9.
Environ Sci Pollut Res Int ; 28(19): 24034-24045, 2021 May.
Artículo en Inglés | MEDLINE | ID: mdl-33417129

RESUMEN

Photoperoxidation (UV/H2O2) 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/H2O2 process was able to degrade bupropion and fluoxetine in ultrapure water, using 0.042 mmol L-1 of H2O2 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/H2O2 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/H2O2 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.


Asunto(s)
Preparaciones Farmacéuticas , Contaminantes Químicos del Agua , Purificación del Agua , Antidepresivos , Peróxido de Hidrógeno , Oxidación-Reducción , Espectrometría de Masas en Tándem , Rayos Ultravioleta , Agua , Contaminantes Químicos del Agua/análisis
10.
Environ Sci Pollut Res Int ; 28(42): 59040-59049, 2021 Nov.
Artículo en Inglés | MEDLINE | ID: mdl-32207020

RESUMEN

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.


Asunto(s)
Contaminantes del Suelo , Suelo , Animales , Antiparasitarios , Bencimidazoles , Femenino , Ovinos , Espectrometría de Masas en Tándem
11.
Sci Total Environ ; 727: 138661, 2020 Jul 20.
Artículo en Inglés | MEDLINE | ID: mdl-32334225

RESUMEN

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.


Asunto(s)
Preparaciones Farmacéuticas , Contaminantes Químicos del Agua/análisis , Brasil , Monitoreo del Ambiente , Humanos , Psicotrópicos , Ríos , Extracción en Fase Sólida , Aguas Residuales/análisis
12.
Ecotoxicol Environ Saf ; 183: 109489, 2019 Nov 15.
Artículo en Inglés | MEDLINE | ID: mdl-31394379

RESUMEN

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 (DT50) 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 DT50 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.


Asunto(s)
Antiparasitarios/química , Ivermectina/análogos & derivados , Macrólidos/metabolismo , Plaguicidas/química , Contaminantes del Suelo/química , Suelo/química , Antiparasitarios/análisis , Brasil , Monitoreo del Ambiente , Semivida , Ivermectina/análisis , Ivermectina/química , Ivermectina/metabolismo , Macrólidos/análisis , Macrólidos/química , Plaguicidas/análisis , Contaminantes del Suelo/análisis
13.
Chemosphere ; 214: 111-122, 2019 Jan.
Artículo en Inglés | MEDLINE | ID: mdl-30261417

RESUMEN

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 µg1-1/n (cm3)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.


Asunto(s)
Contaminantes del Suelo/análisis , Suelo/química , Drogas Veterinarias/farmacología , Adsorción , Animales , Antibacterianos/química , Antibacterianos/farmacología , Antiparasitarios/farmacología , Brasil , Fluoroquinolonas , Ivermectina/análogos & derivados , Sulfonamidas , Tiabendazol
14.
J Environ Manage ; 232: 729-737, 2019 Feb 15.
Artículo en Inglés | MEDLINE | ID: mdl-30529415

RESUMEN

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 mgO3 L-1 to remove ABZ and RBZ. After ozonation, the COD and BOD5 of the effluents were reduced by 27%. Photolysis by UVA radiation was not effective to remove ABZ and FBZ from the effluent samples.


Asunto(s)
Ozono , Contaminantes Químicos del Agua , Bencimidazoles , Monitoreo del Ambiente , Humanos , Fotólisis , Espectrometría de Masas en Tándem , Eliminación de Residuos Líquidos , Aguas Residuales
15.
Environ Sci Pollut Res Int ; 24(19): 15995-16006, 2017 Jul.
Artículo en Inglés | MEDLINE | ID: mdl-28537016

RESUMEN

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 13C 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.


Asunto(s)
Fluoroquinolonas , Sustancias Húmicas , Suelo , Adsorción , Brasil , Enrofloxacina , Contaminantes del Suelo
16.
J Chromatogr A ; 1471: 118-125, 2016 Nov 04.
Artículo en Inglés | MEDLINE | ID: mdl-27745927

RESUMEN

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.


Asunto(s)
Cromatografía Líquida de Alta Presión , Monitoreo del Ambiente/métodos , Ivermectina/análogos & derivados , Macrólidos/análisis , Suelo/química , Extracción en Fase Sólida , Espectrometría de Masas en Tándem , Acetonitrilos/química , Ivermectina/análisis , Metanol/química , Plaguicidas/análisis , Drogas Veterinarias/análisis , Agua/química
17.
Chemosphere ; 163: 525-534, 2016 Nov.
Artículo en Inglés | MEDLINE | ID: mdl-27567152

RESUMEN

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.


Asunto(s)
Monitoreo del Ambiente/métodos , Contaminantes Ambientales/análisis , Plaguicidas/análisis , Polen/química , Aletrinas , Animales , Abejas , Brasil , Calibración , Cromatografía Líquida de Alta Presión , Cromatografía de Gases y Espectrometría de Masas , Iones , Límite de Detección , Residuos de Plaguicidas/análisis , Espectrometría de Masas en Tándem
18.
J Chromatogr A ; 1452: 89-97, 2016 Jun 24.
Artículo en Inglés | MEDLINE | ID: mdl-27234844

RESUMEN

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.


Asunto(s)
Residuos de Medicamentos/análisis , Suelo/química , Extracción en Fase Sólida/métodos , Sulfonamidas/análisis , Espectrometría de Masas en Tándem/métodos , Acetonitrilos , Cromatografía Líquida de Alta Presión , Drogas Veterinarias/química , Agua
19.
Talanta ; 152: 498-503, 2016 May 15.
Artículo en Inglés | MEDLINE | ID: mdl-26992547

RESUMEN

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.


Asunto(s)
Huevos/análisis , Electricidad , Fluoroquinolonas/aislamiento & purificación , Extracción en Fase Sólida/métodos , Cromatografía Líquida de Alta Presión , Fluoroquinolonas/análisis , Espectrometría de Masas en Tándem
20.
Chemosphere ; 151: 17-29, 2016 May.
Artículo en Inglés | MEDLINE | ID: mdl-26923238

RESUMEN

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.


Asunto(s)
Antiparasitarios/análisis , Ivermectina/análogos & derivados , Plaguicidas/análisis , Contaminantes del Suelo/análisis , Adsorción , Silicatos de Aluminio/química , Antiparasitarios/química , Brasil , Arcilla , Ivermectina/análisis , Ivermectina/química , Cinética , Modelos Teóricos , Plaguicidas/química , Suelo/química , Microbiología del Suelo , Contaminantes del Suelo/química , Drogas Veterinarias/análisis , Drogas Veterinarias/química
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