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Thomas Heberer - One of the best experts on this subject based on the ideXlab platform.
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Investigation of the behavior and metabolism of pharmaceutical residues during purification of contaminated ground water used for drinking water supply.
Chemosphere, 2007Co-Authors: Sebastian Zuehlke, Uwe Duennbier, Thomas HebererAbstract:Abstract Residues of phenazone-type pharmaceuticals originating from spills of a former pharmaceutical production plant have recently been detected in ground water in Berlin, Germany. The degradation pathways of phenazone, Propyphenazone, and dimethylaminophenazone (DMAA) during water purification were enlightened in batch experiments with groundwater and filter material obtained from operating waterworks. For phenazone and Propyphenazone a complete biological transformation into their respective metabolites 1,5-dimethyl-1,2-dehydro-3-pyrazolone (DP) and 4-(2-methylethyl)-1,5-dimethyl-1,2-dehydro-3-pyrazolone (PDP) was observed. Generally, removal of phenazone-type pharmaceutical residues during rapid sand filtration was almost exclusively caused by microorganisms only present in polluted raw water. DMAA applied to fresh filter materials was rapidly degraded into its metabolites 1-acetyl-1-methyl-2-phenylhydrazide (AMPH), acetoaminoantipyrine (AAA), formylaminoantipyrine (FAA), and 1-acetyl-1-methyl-2-dimethyloxamoyl-2-phenylhydrazide (AMDOPH). DMAA, AAA, and FAA were, however, only detected at low levels in a few samples of purified water from an operating water works. Whereas, the metabolites AMDOPH and DP were detected up to 1 μg l−1. Propyphenazone was rapidly removed and AMPH, phenazone, and PDP were only measured with concentrations in the low ng l−1 range. The concentrations of the metabolites DP and PDP are even higher in the purified water than in the raw water caused by their formation during degradation of phenazone and Propyphenazone. Reduction of filtration velocity on an experimental filter from 5 m h−1 down to 2 m h−1 resulted in improved removal of phenazone, Propyphenazone and their metabolites DP and PDP, respectively. AMDOPH, however, was highly persistent in all experiments independent from filtration velocities and contact times.
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mobility of pharmaceuticals carbamazepine diclofenac ibuprofen and Propyphenazone in miscible displacement experiments
Journal of Contaminant Hydrology, 2006Co-Authors: Traugott Scheytt, Petra Mersmann, Thomas HebererAbstract:Many pharmaceuticals pass the unsaturated zone before reaching an aquifer. Therefore, laboratory sand column transport experiments were conducted to study the transport behavior of carbamazepine, diclofenac, ibuprofen, and Propyphenazone under unsaturated conditions. The test water was artificial sewage effluent to simulate the infiltration of reused wastewater. The test water was spiked with the pharmaceutically active compounds and the tracer LiCl. Afterwards it was passed through laboratory sand columns, one experiment for each pharmaceutical. The physical and chemical parameters were recorded and general ions measured. Pharmaceuticals were measured using solid phase extraction, derivatization, and detection with GC-MS. The column experiments indicate a significant elimination of ibuprofen (54%), Propyphenazone (55%), and diclofenac (35%), whereas carbamazepine was not eliminated. Retardation factors varied between 1.84 for carbamazepine, 2.51 for Propyphenazone, 3.00 for ibuprofen, and 4.80 for diclofenac. These results show that mobility and elimination of diclofenac, ibuprofen, and Propyphenazone is about in the same range as for experiments under saturated conditions whereas carbamazepine had a significantly lower sorption and elimination under unsaturated conditions.
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1 octanol water partition coefficients of 5 pharmaceuticals from human medical care carbamazepine clofibric acid diclofenac ibuprofen and Propyphenazone
Water Air and Soil Pollution, 2005Co-Authors: Traugott Scheytt, Petra Mersmann, Ralph Lindstädt, Thomas HebererAbstract:Laboratory studies were conducted to characterize the 1-octanol/water partition coefficients of pharmaceutically active substances carbamazepine, clofibric acid, diclofenac, ibuprofen, and Propyphenazone. Partition coefficients determined by shake flask experiments (OECD guideline 107) varied between log KOW 1.51 for carbamazepine, 2.88 for clofibric acid, 1.90 for diclofenac, 2.48 for ibuprofen, and 2.02 for Propyphenazone. Comparison of these values with the literature values revealed rather significant differences for most of the compounds. The partitioning coefficients of the acidic compounds diclofenac and ibuprofen agreed much better with sorption and mobility data from previously conducted experiments, whereas KOW values for carbamazepine were lower and for clofibric acid higher than expected from experiments. Only KOW values for Propyphenazone were in the same range as reported in the literature and expected from column experiments.
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detection and identification of phenazone type drugs and their microbial metabolites in ground and drinking water applying solid phase extraction and gas chromatography with mass spectrometric detection
Journal of Chromatography A, 2004Co-Authors: Sebastian Zuhlke, Thomas Heberer, Uwe DunnbierAbstract:Abstract A new analytical method applying in situ derivatization was developed to enable the extraction of polar drug metabolites from water samples by solid-phase extraction (SPE). An additional derivatization by silylation was used to enhance the sensitivity of analyte detection by gas chromatography–mass spectrometry (GC–MS). Thus, the two metabolites 1,5-di-methyl-1,2-dehydro-3-pyrazolone (DP) and 4-(2-methylethyl)-1,5-dimethyl-1,2-dehydro-3-pyrazolone (PDP), postulated for the degradation of phenazone and Propyphenazone, were identified and detected up to the μg/L level in raw and drinking water samples from public water supply.
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identification and significance of phenazone drugs and their metabolites in ground and drinking water
Chemosphere, 2002Co-Authors: Kirsten Reddersen, Thomas Heberer, Uwe DunnbierAbstract:Abstract Residues of three phenazone-type pharmaceuticals have been identified in routine analyses of groundwater samples from selected areas in the north-western districts of Berlin, Germany. Phenazone, propiphenazone, and dimethylaminophenazone have been detected in some wells at concentrations up to the low μg/l-level. Additionally, three phenazone-type metabolites namely 1-acetyl-1-methyl-2-dimethyl-oxamoyl-2-phenylhydrazide (AMDOPH), 1-acetyl-1-methyl-2-phenylhydrazide, and dimethyloxalamide acid-(N′-methyl-N-phenyl)-hydrazide have also been identified in these groundwater samples. The residues are suspected to originate from former production spills of a pharmaceutical plant located in a city north of Berlin. It was observed that with the exception of AMDOPH all other residues were efficiently removed during conventional drinking water treatment. The drug metabolite AMDOPH deriving from dimethylaminophenazone residues was found at concentrations of 0.9 μg/l in finished drinking water. However, a following study on the toxicological relevance of the AMDOPH residues has shown that there is no toxicological harm for humans at the low concentrations of AMDOPH observed in Berlin drinking water.
Damia Barcelo - One of the best experts on this subject based on the ideXlab platform.
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pharmaceuticals and iodinated contrast media in a hospital wastewater a case study to analyse their presence and characterise their environmental risk and hazard
Environmental Research, 2015Co-Authors: A Mendoza, Damia Barcelo, Jaume Acena, Sandra Perez, Lopez M De Alda, A Gil, Y ValcarcelAbstract:This work analyses the presence of twenty-five pharmaceutical compounds belonging to seven different therapeutic groups and one iodinated contrast media (ICM) in a Spanish medium-size hospital located in the Valencia Region. Analysis of the target compounds in the hospital wastewater was performed by means of solid phase extraction (SPE) followed by liquid chromatography-tandem mass spectrometry analysis (HPLC-MS/MS). A screening level risk assessment combining the measured environmental concentrations (MECs) with dose-response data based on Predicted No Effect Concentration (PNEC) was also applied to estimate Hazard Quotients (HQs) for the compounds investigated. Additionally, the environmental hazard associated to the various compounds measured was assessed through the calculation of the Persistence, Bioaccumulation and Toxicity (PBT) Index, which categorizes compounds according to their environmentally damaging characteristics. The results of the study showed the presence of twenty-four out of the twenty-six compounds analysed at individual concentrations ranging from 5 ng L(-1) to 2 mg L(-1). The highest concentrations corresponded to the ICM iomeprol, found at levels between 424 and 2093 μg L(-1), the analgesic acetaminophen (15-44 μg L(-1)), the diuretic (DIU) furosemide (6-15 μg L(-1)), and the antibiotics (ABIs) ofloxacin and trimethoprim (2-5 μg L(-1)). The lowest levels corresponded to the anti-inflammatory Propyphenazone, found at concentrations between 5 and 44 ng L(-1). Differences in terms of concentrations of the analysed compounds have been observed in all the therapeutic groups when comparing the results obtained in this and other recent studies carried out in hospitals with different characteristics from different geographical areas and in different seasons. The screening level risk assessment performed in raw water from the hospital effluent showed that the analgesics and anti-inflammatories (AAFs) acetaminophen, diclofenac, ibuprofen and naproxen, the antibiotics (ABIs) clarithromycin, ofloxacin and trimethoprim, and the β-blocker (BBL) propranolol were present at concentrations leading to HQ values higher than 10, thus indicating high risk. When applying a factor to take into account potential dilution and degradation processes, only the compound ibuprofen showed a HQ higher than 1. Likewise, the cumulative HQ or Toxic Units (TUs) calculated in the raw water for each of the therapeutic groups studied showed that these three classes of drugs were at concentrations high enough to potentially generate high risk to aquatic organisms while taking into account possible dilution and degradation processes only one of them, the AAFs can be considered to represent high risk. Finally, the environmental hazard assessment performed showed that the AAFs diclofenac and ibuprofen and the ABI clarithromycin have the highest, maximum value of 9 of PBT Index due to their inherent environmentally damaging characteristics of persistence, bioaccumulation and toxicity. The methodology followed in the present case study can be taken as a novel approach to classify and categorize pharmaceuticals on the basis of their occurrence in hospital effluents, their derived environmental risks, and their associated environmental hazard. This classification becomes important because it can be used as a model or orientation for hospitals in the process of developing environmentally sustainable policies and as an argument to justify the adoption of advanced, specific treatments for hospital effluents before being discharged into the public sewage system.
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occurrence and distribution of multi class pharmaceuticals and their active metabolites and transformation products in the ebro river basin ne spain
Science of The Total Environment, 2012Co-Authors: Rebeca Lopezserna, Mira Petrovic, Damia BarceloAbstract:Abstract The present work reports the occurrence of pharmaceuticals and their metabolites and transformation products (TPs) in the Ebro river basin (NE Spain). Twenty-four samples of water collected along the basin were analysed using a fully automated method based on on-line turbulent chromatography–liquid chromatography–tandem mass spectrometry (TFC-LC-MS/MS). In total, 17 metabolites, 7 of them with remaining pharmacologic activity, and 2 transformation products, along with 58 parent pharmaceuticals are analysed. Metabolites and TPs were found at concentrations of the same order of magnitude as their corresponding parent pharmaceuticals, with the exception of 10,11-epoxi-carbamazepine which was found at approximately 10 times higher concentration than its corresponding parent pharmaceutical carbamazepine. In general, levels of all target compounds were below 100 ng L− 1, with the exception of 14 compounds; among them the aforementioned 10,11-epoxicarbamazepine with a maximum concentration of more than 1600 ng L− 1. The analgesic Propyphenazone, the psychiatric drug carbamazepine, the antibiotics clarithromycin and sulfadiazine, the cardiovascular drug propranolol, the antineoplastic tamoxifen and 1 pharmacologically active metabolite salicylic acid were found to be ubiquitous (detected in all samples). Smaller tributaries generally show higher concentrations than the main river Ebro, due to lower dilution of WWTP effluents discharged.
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fate and distribution of pharmaceuticals in wastewater and sewage sludge of the conventional activated sludge cas and advanced membrane bioreactor mbr treatment
Water Research, 2009Co-Authors: Jelena Radjenovic, Mira Petrovic, Damia BarceloAbstract:Abstract In this paper we report on the performances of full-scale conventional activated sludge (CAS) treatment and two pilot-scale membrane bioreactors (MBRs) in eliminating various pharmaceutically active compounds (PhACs) belonging to different therapeutic groups and with diverse physico-chemical properties. Both aqueous and solid phases were analysed for the presence of 31 pharmaceuticals included in the analytical method. The most ubiquitous contaminants in the sewage water were analgesics and anti-inflammatory drugs ibuprofen (14.6–31.3 μg/L) and acetaminophen (7.1–11.4 μg/L), antibiotic ofloxacin (0.89–31.7 μg/L), lipid regulators gemfibrozil (2.0–5.9 μg/L) and bezafibrate (1.9–29.8 μg/L), β-blocker atenolol (0.84–2.8 μg/L), hypoglycaemic agent glibenclamide (0.12–15.9 μg/L) and a diuretic hydrochlorothiazide (2.3–4.8 μg/L). Also, several pharmaceuticals such as ibuprofen, ketoprofen, diclofenac, ofloxacin and azithromycin were detected in sewage sludge at concentrations up to 741.1, 336.3, 380.7, 454.7 and 299.6 ng/g dry weight. Two pilot-scale MBRs exhibited enhanced elimination of several pharmaceutical residues poorly removed by the CAS treatment (e.g., mefenamic acid, indomethacin, diclofenac, Propyphenazone, pravastatin, gemfibrozil), whereas in some cases more stable operation of one of the MBR reactors at prolonged SRT proved to be detrimental for the elimination of some compounds (e.g., β-blockers, ranitidine, famotidine, erythromycin). Moreover, the anti-epileptic drug carbamazepine and diuretic hydrochlorothiazide by-passed all three treatments investigated. Furthermore, sorption to sewage sludge in the MBRs as well as in the entire treatment line of a full-scale WWTP is discussed for the encountered analytes. Among the pharmaceuticals encountered in sewage sludge, sorption to sludge could be a relevant removal pathway only for several compounds (i.e., mefenamic acid, propranolol, and loratidine). Especially in the case of loratidine the experimentally determined sorption coefficients ( K d s) were in the range 2214–3321 L/kg (mean). The results obtained for the solid phase indicated that MBR wastewater treatment yielding higher biodegradation rate could reduce the load of pollutants in the sludge. Also, the overall output load in the aqueous and solid phase of the investigated WWTP was calculated, indicating that none of the residual pharmaceuticals initially detected in the sewage sludge were degraded during the anaerobic digestion. Out of the 26 pharmaceutical residues passing through the WWTP, 20 were ultimately detected in the treated sludge that is further applied on farmland.
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rejection of pharmaceuticals in nanofiltration and reverse osmosis membrane drinking water treatment
Water Research, 2008Co-Authors: Jelena Radjenovic, Mira Petrovic, Francesc Ventura, Damia BarceloAbstract:Abstract This paper investigates the removal of a broad range of pharmaceuticals during nanofiltration (NF) and reverse osmosis (RO) applied in a full-scale drinking water treatment plant (DWTP) using groundwater. Pharmaceutical residues detected in groundwater used as feed water in all five sampling campaigns were analgesics and anti-inflammatory drugs such as ketoprofen, diclofenac, acetaminophen and Propyphenazone, β-blockers sotalol and metoprolol, an antiepileptic drug carbamazepine, the antibiotic sulfamethoxazole, a lipid regulator gemfibrozil and a diuretic hydrochlorothiazide. The highest concentrations in groundwater were recorded for hydrochlorothiazide (58.6–2548 ng L−1), ketoprofen ( 85%). Deteriorations in retentions on NF and RO membranes were observed for acetaminophen (44.8–73 %), gemfibrozil (50–70 %) and mefenamic acid (30–50%). Furthermore, since several pharmaceutical residues were detected in the brine stream of NF and RO processes at concentrations of several hundreds nanogram per litre, its disposal to a near-by river can represent a possible risk implication of this type of treatment.
Heinrich Huhnerfuss - One of the best experts on this subject based on the ideXlab platform.
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drugs and personal care products as ubiquitous pollutants occurrence and distribution of clofibric acid caffeine and deet in the north sea
Science of The Total Environment, 2002Co-Authors: Stefan Weigel, Jan Kuhlmann, Heinrich HuhnerfussAbstract:An analytical method is presented, which allows the simultaneous extraction of neutral and acidic compounds from 20-L seawater samples at ambient pH (approximately 8.3). It is based on a solid-phase extraction by means of a polystyrene-divinylbenzene sorbent and gas chromatographic-mass spectrometric detection, and provides detection limits in the lower pg/L range. The method was applied to the screening of samples from different North Sea areas for clofibric acid, diclofenac, ibuprofen, ketoprofen, Propyphenazone, caffeine and N,N-diethyl-3-toluamide (DEET). Whereas clofibric acid, caffeine and DEET showed to be present throughout the North Sea in concentrations of up to 1.3, 16 and 1.1 ng/L, respectively, Propyphenazone could only be detected after further clean-up. Diclofenac and ibuprofen were found in the estuary of the river Elbe (6.2 and 0.6 ng/L, respectively) but in none of the marine samples. Ketoprofen was below the detection limit in all samples.
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new method for rapid solid phase extraction of large volume water samples and its application to non target screening of north sea water for organic contaminants by gas chromatography mass spectrometry
Journal of Chromatography A, 2001Co-Authors: Stefan Weigel, Kai Bester, Heinrich HuhnerfussAbstract:A method has been developed that allows the solid-phase extraction of microorganic compounds from large volumes of water (10 l) for non-target analysis of filtered seawater. The filtration–extraction system is operated with glass fibre filter candles and the polymeric styrene–divinylbenzene sorbent SDB-1 at flow-rates as high as 500 ml/min. Recovery studies carried out for a couple of model substances covering a wide range of polarity and chemical classes revealed a good performance of the method. Especially for polar compounds (log KOW 3.3–0.7) quantitative recovery was achieved. Limits of detection were between 0.1 and 0.7 ng/l in the full scan mode of the MS. The suitability of the method for the analysis of marine water samples is demonstrated by the non-target screening of water from the German Bight for the presence of organic contaminants. In the course of this screening a large variety of substances was identified including pesticides, industrial chemicals and pharmaceuticals. For some of the identified compounds their occurrence in marine ecosystems has not been reported before, such as dichloropyridines, carbamazepine, Propyphenazone and caffeine.
Weberson Pereira Silva - One of the best experts on this subject based on the ideXlab platform.
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Determinação simultânea de propifenazona, paracetamol e cafeína utilizando eletrodo de diamante dopado com boro
Universidade Federal de Uberlândia, 2017Co-Authors: Weberson Pereira SilvaAbstract:No presente trabalho investigou-se o desenvolvimento de novos procedimentos analíticos para a determinação simultânea de paracetamol (PAR), propifenazona (PRO) e cafeína (CAF) em formulações farmacêuticas. Três métodos foram desenvolvidos usando as técnicas de voltametria de onda quadrada (SWV) e amperometria de múltiplos pulsos (MPA) e diamante dopado com boro (BDD) como eletrodo de trabalho. Empregando a SWV, duas estratégias de análise foram desenvolvidas: (I) uso de uma célula eletroquímica convencional (modo estacionário) e o método de adição de padrão; (II) uso de análise por injeção em batelada com detecção por voltametria de onda quadrada (BIA-SWV) e o método de calibração externa. Os métodos propostos foram desenvolvidos usando como eletrólito de suporte H2SO4 0,1 mol L-1 e os parâmetros otimizados da SWV foram: potencial de condicionamento: -1,5 V durante 20 s; frequência: 60 s-1; amplitude: 50 mV e incremento de potencial: 4 mV. No método proposto empregando BIA-SWV, o volume e a velocidade de injeção otimizados foram de 100 μL e 28 μL s-1, respectivamente. Um terceiro método proposto para determinação simultânea de PAR, PRO e CAF, o procedimento de análise por injeção em batelada com detecção por amperometria de múltiplos pulsos (BIA-MPA) foi empregado. Três pulsos de potenciais foram selecionados para realização da análise: +0,90 V /50 ms: apenas o PAR foi oxidado sem a interferência dos outros dois compostos; +1,20 V /50 ms: oxidação do PAR e da PRO livre da interferência da CAF; +1,60 V /50 ms: oxidação dos três compostos (PAR, PRO e CAF). A seletividade na detecção da PRO e CAF foi obtida mediante subtração de correntes entre os amperogramas adquiridos nos potenciais selecionados e o uso de fatores de correção (FCs). Todos os procedimentos de análise desenvolvidos mostraram-se estáveis (DPR < 4,1%) e lineares (r > 0,997). O método empregando uma célula eletroquímica convencional apresentou frequência analítica de 20 análises h-1 e limites de detecção de 0,005, 0,009 e 0,006 mg L-1 para PAR, PRO e CAF, respectivamente. Os métodos BIA-SWV e BIA-MPA apresentaram frequência analítica muito superior: 80 e 75 análises h-1, respectivamente. Os limites de detecção foram de 0,3, 0,2 e 0,3 mg L-1 (BIA-SWV) e 0,2, 0,3 e 0,1 mg L-1 (BIA-MPA) para PAR, PRO e CAF, respectivamente.In this work we investigated the development of new analytical procedures for simultaneous determination of paracetamol (PAR), Propyphenazone (PRO) and caffeine (CAF) in pharmaceutical formulations. Three methods was developed using of Square wave voltammetry (SWV), multiple pulse amperometry (MPA) and boron doped diamond (BDD) with work electrode. Employing SWV, two analysis strategies were developed (I) Use of a conventional electrochemical cell (stationary mode) and the standard addition method; (II) use of batch injection analysis with detection by square wave voltammetry (BIA-SWV) and external calibration method. The proposed methods were developed using H2SO4 0.1 mol L-1 as supporting electrolyte and optimized parameters of the SWV: Conditioning potential: -1.5 V during 20 s; frequency: 60 s-1; amplitude: 50 mV and step potential: 4 mV. In the proposed method using BIA-SWV, volume and speed of optimized injection were 100 μL e 28 μL s-1, respectively. On the third method proposed for simultaneous determination of the PAR, PRO and CAF, the batch injection analysis procedure with multiple pulse amperometry detection (BIA-MPA) was employed. Three potentials pulses were selected for the analysis: +0.90 V/50 ms: only PAR was oxidized without the interference of the other two compounds; +1.20 V/50 ms: oxidation PAR and PRO without the interference of the CAF; +1.60 V/50 ms: oxidation of the three compounds (PAR, PRO and CAF). The selectivity in the detection of PRO and CAF was obtained by subtracting currents between the amperograms acquired in the selected potentials and the use of correction factors (CFs). All developed analysis procedures remained stable (RSD < 4.1%) and linear (r > 0.997). The method using a conventional electrochemical cell showed an analytical frequency of 20 analysis h-1 and limits of detection of 0.005, 0.009, and 0.006 mg L-1 for PAR, PRO, and CAF, respectively. The BIA-SWV and BIA-MPA methods presented higher analytical frequency: 80 and 75 analysis h-1, respectively. The limits of detection were 0.3, 0.2, and 0.3 mg L-1 (BIA-SWV) and 0.2, 0.3, and 0.1 mg L-1 (BIA-MPA) for PAR, PRO and CAF, respectively
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FAST SIMULTANEOUS DETERMINATION OF PROPIFENAZONE, PARACETAMOL AND CAFFEINE USING BATCH INJECTION ANALYSIS WITH AMPEROMETRIC DETECTION
2017Co-Authors: Weberson Pereira Silva, Luiz André Juvêncio Silva, Rodrigo Alejandro Abarza Muñoz, Eduardo Mathias RichterAbstract:A fast and simple procedure for simultaneous determination of Propyphenazone (PRO), paracetamol (PAR) and caffeine (CAF) was performed using batch injection analysis with multiple pulse amperometric detection (BIA-MPA). Three potentials pulses were selected for the analysis: +0.90 V/50 ms: only PAR was oxidized; +1.20 V/50 ms: oxidation of PAR and PRO without the interference of CAF; +1.60 V/50 ms: oxidation of the three compounds (PAR, PRO and CAF). The sample aliquot (150 µL) was directly injected onto the boron-doped diamond (BDD) electrode immersed in a BIA cell. The analytical characteristics of the proposed method include high analytical frequency (75 injections per hour), good stability (RSD < 3.9%; n = 10), and low detection limits (0.3, 0.2 and 0.1 mg L−1 for PRO, PAR and CAF, respectively). The proposed method yielded similar results to those obtained by liquid chromatography at a 95% confidence level.
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Determinação simultânea de propifenazona, paracetamol e cafeína utilizando eletrodo de diamante dopado com boro
'EDUFU - Editora da Universidade Federal de Uberlandia', 2017Co-Authors: Weberson Pereira SilvaAbstract:In this work we investigated the development of new analytical procedures for simultaneous determination of paracetamol (PAR), Propyphenazone (PRO) and caffeine (CAF) in pharmaceutical formulations. Three methods was developed using of Square wave voltammetry (SWV), multiple pulse amperometry (MPA) and boron doped diamond (BDD) with work electrode. Employing SWV, two analysis strategies were developed (I) Use of a conventional electrochemical cell (stationary mode) and the standard addition method; (II) use of batch injection analysis with detection by square wave voltammetry (BIA-SWV) and external calibration method. The proposed methods were developed using H2SO4 0.1 mol L-1 as supporting electrolyte and optimized parameters of the SWV: Conditioning potential: -1.5 V during 20 s; frequency: 60 s-1; amplitude: 50 mV and step potential: 4 mV. In the proposed method using BIA-SWV, volume and speed of optimized injection were 100 μL e 28 μL s-1, respectively. On the third method proposed for simultaneous determination of the PAR, PRO and CAF, the batch injection analysis procedure with multiple pulse amperometry detection (BIA-MPA) was employed. Three potentials pulses were selected for the analysis: +0.90 V/50 ms: only PAR was oxidized without the interference of the other two compounds; +1.20 V/50 ms: oxidation PAR and PRO without the interference of the CAF; +1.60 V/50 ms: oxidation of the three compounds (PAR, PRO and CAF). The selectivity in the detection of PRO and CAF was obtained by subtracting currents between the amperograms acquired in the selected potentials and the use of correction factors (CFs). All developed analysis procedures remained stable (RSD 0.997). The method using a conventional electrochemical cell showed an analytical frequency of 20 analysis h-1 and limits of detection of 0.005, 0.009, and 0.006 mg L-1 for PAR, PRO, and CAF, respectively. The BIA-SWV and BIA-MPA methods presented higher analytical frequency: 80 and 75 analysis h-1, respectively. The limits of detection were 0.3, 0.2, and 0.3 mg L-1 (BIA-SWV) and 0.2, 0.3, and 0.1 mg L-1 (BIA-MPA) for PAR, PRO and CAF, respectively.Fundação de Amparo a Pesquisa do Estado de Minas GeraisDissertação (Mestrado)No presente trabalho investigou-se o desenvolvimento de novos procedimentos analíticos para a determinação simultânea de paracetamol (PAR), propifenazona (PRO) e cafeína (CAF) em formulações farmacêuticas. Três métodos foram desenvolvidos usando as técnicas de voltametria de onda quadrada (SWV) e amperometria de múltiplos pulsos (MPA) e diamante dopado com boro (BDD) como eletrodo de trabalho. Empregando a SWV, duas estratégias de análise foram desenvolvidas: (I) uso de uma célula eletroquímica convencional (modo estacionário) e o método de adição de padrão; (II) uso de análise por injeção em batelada com detecção por voltametria de onda quadrada (BIA-SWV) e o método de calibração externa. Os métodos propostos foram desenvolvidos usando como eletrólito de suporte H2SO4 0,1 mol L-1 e os parâmetros otimizados da SWV foram: potencial de condicionamento: -1,5 V durante 20 s; frequência: 60 s-1; amplitude: 50 mV e incremento de potencial: 4 mV. No método proposto empregando BIA-SWV, o volume e a velocidade de injeção otimizados foram de 100 μL e 28 μL s-1, respectivamente. Um terceiro método proposto para determinação simultânea de PAR, PRO e CAF, o procedimento de análise por injeção em batelada com detecção por amperometria de múltiplos pulsos (BIA-MPA) foi empregado. Três pulsos de potenciais foram selecionados para realização da análise: +0,90 V /50 ms: apenas o PAR foi oxidado sem a interferência dos outros dois compostos; +1,20 V /50 ms: oxidação do PAR e da PRO livre da interferência da CAF; +1,60 V /50 ms: oxidação dos três compostos (PAR, PRO e CAF). A seletividade na detecção da PRO e CAF foi obtida mediante subtração de correntes entre os amperogramas adquiridos nos potenciais selecionados e o uso de fatores de correção (FCs). Todos os procedimentos de análise desenvolvidos mostraram-se estáveis (DPR 0,997). O método empregando uma célula eletroquímica convencional apresentou frequência analítica de 20 análises h-1 e limites de detecção de 0,005, 0,009 e 0,006 mg L-1 para PAR, PRO e CAF, respectivamente. Os métodos BIA-SWV e BIA-MPA apresentaram frequência analítica muito superior: 80 e 75 análises h-1, respectivamente. Os limites de detecção foram de 0,3, 0,2 e 0,3 mg L-1 (BIA-SWV) e 0,2, 0,3 e 0,1 mg L-1 (BIA-MPA) para PAR, PRO e CAF, respectivamente
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DETERMINAÇÃO RÁPIDA E SIMULTÂNEA DE PROPIFENAZONA, PARACETAMOL E CAFEÍNA UTILIZANDO ANÁLISE POR INJEÇÃO EM BATELADA COM DETECÇÃO AMPEROMÉTRICA
Sociedade Brasileira de Química, 2024Co-Authors: Weberson Pereira Silva, Luiz André Juvêncio Silva, Rodrigo Alejandro Abarza Muñoz, Eduardo Mathias RichterAbstract:A fast and simple procedure for simultaneous determination of Propyphenazone (PRO), paracetamol (PAR) and caffeine (CAF) was performed using batch injection analysis with multiple pulse amperometric detection (BIA-MPA). Three potentials pulses were selected for the analysis: +0.90 V/50 ms: only PAR was oxidized; +1.20 V/50 ms: oxidation of PAR and PRO without the interference of CAF; +1.60 V/50 ms: oxidation of the three compounds (PAR, PRO and CAF). The sample aliquot (150 µL) was directly injected onto the boron-doped diamond (BDD) electrode immersed in a BIA cell. The analytical characteristics of the proposed method include high analytical frequency (75 injections per hour), good stability (RSD < 3.9%; n = 10), and low detection limits (0.3, 0.2 and 0.1 mg L−1 for PRO, PAR and CAF, respectively). The proposed method yielded similar results to those obtained by liquid chromatography at a 95% confidence level
Rosario Rodil - One of the best experts on this subject based on the ideXlab platform.
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reaction of phenazone type drugs and metabolites with chlorine and monochloramine
Science of The Total Environment, 2021Co-Authors: Benigno Jose Sieira, R Cela, Jose Benito Quintana, Rosario RodilAbstract:Abstract This work studies the chlorination and monochloramination reaction kinetics of two phenazone-type drugs (phenazone – Phe and Propyphenazone – PrPhe) and three metabolites of phenazone-type drugs (4-formylaminoantipyrine – FAA, 4-aminoantipyrine - AA and 4-acetoamidoantipyrine - AAA). Kinetics were faster with chlorine (apparent second-order constants between 100 and 66,500 times higher) than with monochloramine. For FAA and AAA, no significant reaction was observed during monochloramination. Further, apparent rate constants decreased as the pH increased from pH 5.7 to 8.3, except during chlorination of AA. The transformation products (TPs) formed were also elucidated by liquid chromatography-high resolution mass spectrometry. The main transformation pathway for Phe and PrPhe consisted of halogenations, hydroxylations and dealkylations, while AAA and FAA were firstly transformed to AA, then followed by pyrazole ring opening and hydroxylations. The extend of the reaction was also tested in real water samples, where, in general, slower reaction kinetics were obtained during monochloramination, while the chlorination reaction showed similar half-lives to ultrapure water. Finally, acute and chronic toxicity of the TPs were estimated using two quantitative structure-activity relationship (QSAR) software (ECOSAR and TEST), showing that some TPs could be more toxic than their precursor compounds.
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transformation of phenazone type drugs during chlorination
Water Research, 2012Co-Authors: Rosario Rodil, Jose Benito Quintana, R CelaAbstract:Abstract Chlorination is one of the most popular disinfection steps for water treatment in Europe. However, chlorine can react with pharmaceuticals and other micropollutants leading to either their elimination or by-products being formed. These by-products are frequently not identified and therefore the consequences of chlorination can be underestimated. In this work, the degradation of two analgesics and antipyretics, phenazone (antipyrine) and Propyphenazone, during chlorination was investigated by liquid chromatography-mass spectrometry (LC-MS). A quadrupole-time-of-flight (Q-TOF) system was used to follow the time course of the pharmaceuticals, and also used in the identification of the by-products. The degradation kinetics was investigated at different concentrations of chlorine (1–10 mg/L), bromide (0–100 μg/L) and sample pH (5.7–8.3) by means of a Box-Behnken experimental design. Depending on these factors, half-lives were in the ranges: 0.9–295 s for phenazone and 0.4–173 s for Propyphenazone. Also, it was observed that chlorine concentration was a significant factor for Propyphenazone, resulting in increased degradation rate as it is increased. The transformation path of these drugs consisted mainly of halogenations, hydroxylations and dealkylations. After several days of reaction two derivatives remained stable for phenazone: chloro-hydroxy-phenazone and N-demethyl-chloro-hydroxy-phenazone and two for Propyphenazone: N-demethyl-hydroxy-Propyphenazone and N-demethyl-chloro-hydroxy-Propyphenazone. Moreover, experiments conducted with real water matrices, tap and surface water, showed that reaction, and formation of by-products, can take place both at the emission source point (household) and during drinking water production.
