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1.
J Environ Manage ; 354: 120340, 2024 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-38368805

RESUMO

The performance of a pilot-scale thin-layer cascade photobioreactor, operated in semicontinuous mode, for the removal of veterinary drug residues and other contaminants of emerging concern (CECs) from pig manure has been assessed in six operation stages. Chlorella sp. (70-90%), Scenedesmus sp. (10-25%) and Diatomea (<5%) comprise the microalgae species present during the stages. The global performance to remove the total CEC content in the photobioreactor effluent varied from 62 to 86% on each stage, while an CEC mean amount close to 8% was accumulated in the photobioreactor biomass. A relation with weather conditions was not observed. Elimination ratio was not related to the concentration in the influent which reached up to 8000 ng L-1 for some CECs. As expected, the concentrations of veterinary drugs were higher than those of non-veterinary CECs. The concentrations accumulated in the grown biomass were relative low, lower than 10 ng per fresh g excepting for a few cases. However, statistical data suggested that the linkage of CECs to microalgae biomass boosted their removal from the influent. Furthermore, it was observed that the manure liquid phase contained higher amounts of CECs than the solid phase.


Assuntos
Chlorella , Microalgas , Scenedesmus , Suínos , Animais , Fotobiorreatores , Esterco , Biomassa
2.
Anal Bioanal Chem ; 415(29-30): 7297-7313, 2023 Dec.
Artigo em Inglês | MEDLINE | ID: mdl-37946034

RESUMO

Chemicals infiltrate our daily experiences through multiple exposure pathways. Human biomonitoring (HBM) is routinely used to comprehensively understand these chemical interactions. Historically, HBM depended on targeted screening methods limited to a relatively small set of chemicals with triple quadrupole instruments typically. However, recent advances in high-resolution mass spectrometry (HRMS) have facilitated the use of broad-scope target, suspect, and non-target strategies, enhancing chemical exposome characterization within acceptable detection limits. Despite these advancements, establishing robust and efficient sample treatment protocols is still essential for trustworthy broad-range chemical analysis. This study sought to validate a methodology leveraging HRMS-based strategies for accurate profiling of exogenous chemicals and related metabolites in urine samples. We evaluated five extraction protocols, each encompassing various chemical classes, such as pharmaceuticals, plastic additives, personal care products, and pesticides, in terms of their extraction recoveries, linearity, matrix effect, sensitivity, and reproducibility. The most effective protocol was extensively validated and subsequently applied to 10 real human urine samples using wide-scope target analysis encompassing over 2000 chemicals. We successfully identified and semi-quantified a total of 36 chemicals using an ionization efficiency-based model, affirming the methodology's robust performance. Notably, our results dismissed the need for a deconjugation step, a typically labor-intensive and time-consuming process.


Assuntos
Monitoramento Ambiental , Humanos , Monitoramento Ambiental/métodos , Cromatografia Líquida/métodos , Reprodutibilidade dos Testes , Cromatografia Gasosa-Espectrometria de Massas , Espectrometria de Massas/métodos
3.
MethodsX ; 10: 102069, 2023.
Artigo em Inglês | MEDLINE | ID: mdl-36879761

RESUMO

Little is known about the presence of organic pollutants in human brain (and even less in brain tumors). In this regard, it is necessary to develop new analytical protocols capable of identifying a wide range of exogenous chemicals in this type of samples (by combining target, suspect and non-target strategies). These methodologies should be robust and simple. This is particularly challenging for solid samples, as reliable extraction and clean-up techniques should be combined to obtain an optimal result. Hence, the present study focuses on the development of an analytical methodology that allows the screening of a wide range of organic chemicals in brain and brain tumor samples. This protocol was based on a solid-liquid extraction based on bead beating, solid-phase extraction clean-up with multi-layer mixed-mode cartridges, reconstitution and LC-HRMS analysis. To evaluate the performance of the extraction methodology, a set of 66 chemicals (e.g., pharmaceuticals, biocides, or plasticizers, among others) with a wide range of physicochemical properties was employed. Quality control parameters (i.e., linear range, sensitivity, matrix effect (ME%), and recoveries (R%)) were calculated and satisfactory results were obtained for them (e.g., R% within 60-120% for 32 chemicals, or ME% higher than 50% (signal suppression) for 79% of the chemicals).

4.
J Hazard Mater ; 448: 130876, 2023 Apr 15.
Artigo em Inglês | MEDLINE | ID: mdl-36736215

RESUMO

Submarine Groundwater Discharge (SGD) is recognized as a relevant source of pollutants to the sea, but little is known about its relevance as a source of chemicals of emerging concern (CECs). Here, both the presence and distribution of a wide range of CECs have been evaluated in the most comprehensive manner to date, in a well-characterized Mediterranean coastal aquifer near Barcelona (Spain). Samples from coastal groundwater and seawater allowed for the unique spatial characterization of the pollutants present in the land-ocean interface, an outstanding research gap that required attention. The main goals were (1) to determine CECs in the aquifer, so as to evaluate the SGD as a relevant source of marine pollution, and (2) to identify new tracers to improve our understanding of SGD dynamics. To this end, 92 CECs were located in the aquifer by using wide-scope analytical target methodologies (>2000 chemicals). Among them, the perfluoroalkyl and polyfluoroalkyl substances (PFAS), along with the pharmaceuticals carbamazepine and topiramate, were revealed to be good markers for tracing anthropogenic contamination in ground- and seawater, in concrete situations (e.g., highly contaminated sites). Additionally, non-target analysis expanded the number of potential tracers, making it a promising tool for identifying both the source and the fate of pollutants.

5.
Environ Sci Process Impacts ; 24(12): 2357-2367, 2022 Dec 14.
Artigo em Inglês | MEDLINE | ID: mdl-36285718

RESUMO

The content of veterinary drugs in manure is usually estimated by the amount of residues determined in its solid or liquid phase, individually, which previously required a separation step. As an alternative, a multiresidue method for the analysis of 48 veterinary drugs and other contaminants of emerging concern (CECs) in swine raw manure as a whole has been developed and in-house validated in this work. The impact of several experimental factors during ultrasound assisted extraction was assessed. Hence, the use of alumina seemed to especially decrease the matrix effect and improve the overall recovery of drugs, mainly those with a high octanol-water partition coefficient. CECs in the extracts were analyzed by ultra-high performance liquid chromatography coupled to mass spectrometry in tandem. A standard addition-matrix matched calibration was used for quantification. Application of the method to two related samples (raw manure and farm centrifuged raw manure) from a facility revealed that the concentrations of CECs determined in the raw manure by the comprehensive methodology were higher than those calculated by adding the concentrations measured in the solid and liquid phases, separately. This was attributed to the loss of CECs adsorbed on fine particles in the suspension during the sample preparation procedure of the liquid-phase. Furthermore, the decrease of residues in the raw manure when this is centrifuged in the farm to yield compost is shown.


Assuntos
Esterco , Drogas Veterinárias , Suínos , Animais , Esterco/análise , Drogas Veterinárias/análise , Espectrometria de Massas em Tandem/métodos , Cromatografia Líquida de Alta Pressão/métodos , Extração em Fase Sólida/métodos
6.
Sci Total Environ ; 827: 154262, 2022 Jun 25.
Artigo em Inglês | MEDLINE | ID: mdl-35271930

RESUMO

This work evaluated, for the first time, the performance of an integral microalgae-based domestic wastewater treatment system composed of an anoxic reactor and an aerobic photobioreactor, coupled with an anaerobic digester for converting the produced algal-bacterial biomass into biogas, with regards to the removal of 16 contaminants of emerging concern (CECs): penicillin G, tetracycline, enrofloxacin, ciprofloxacin, sulfamethoxazole, tylosin, trimethoprim, dexamethasone, ibuprofen, naproxen, acetaminophen, diclofenac, progesterone, carbamazepine, triclosan and propylparaben. The influence of the hydraulic retention time (HRT) in the anoxic-aerobic bioreactors (4 and 2.5 days) and in the anaerobic digester (30 and 10 days) on the fate of these CECs was investigated. The most biodegradable contaminants (removal efficiency >80% regardless of HRT) were tetracycline, ciprofloxacin, sulfamethoxazole, tylosin, trimethoprim, dexamethasone, ibuprofen, naproxen, acetaminophen and propylparaben (degraded predominantly in the anoxic-aerobic bioreactors), and tetracycline, sulfamethoxazole, tylosin, trimethoprim and naproxen (degraded predominantly in the anaerobic reactor). The anoxic-aerobic bioreactors provided removal of at least 48% for all CECs tested. The most recalcitrant contaminants in the anaerobic reactor, which were not removed at any of the HRT tested, were enrofloxacin, ciprofloxacin, progesterone and propylparaben.


Assuntos
Fotobiorreatores , Eliminação de Resíduos Líquidos , Acetaminofen , Anaerobiose , Bactérias Aeróbias , Reatores Biológicos , Ciprofloxacina , Dexametasona , Enrofloxacina , Ibuprofeno , Naproxeno , Progesterona , Esgotos , Sulfametoxazol , Tetraciclinas , Trimetoprima , Tilosina
7.
Membranes (Basel) ; 12(3)2022 Mar 04.
Artigo em Inglês | MEDLINE | ID: mdl-35323768

RESUMO

Forward osmosis (FO) is a promising technology for the treatment of urban wastewater. FO can produce high-quality effluents and preconcentrate urban wastewater for subsequent anaerobic treatment. This membrane technology makes it possible to eliminate the pollutants present in urban wastewater, which can cause adverse effects in the ecosystem even at low concentrations. In this study, a 0.6 m2 hollow fiber aquaporin forward osmosis membrane was used for the treatment of urban wastewater from the Valladolid wastewater treatment plant (WWTP). A total of 51 Contaminants of Emerging Concern (CECs) were investigated, of which 18 were found in the target urban wastewater. They were quantified, and their ecotoxicological risk impact was evaluated. Different salts with different concentrations were tested as draw solutions to evaluate the membrane performances when working with pretreated urban wastewater. NaCl was found to be the most appropriate salt since it leads to higher permeate fluxes and lower reverse saline fluxes. The membrane can eliminate or significantly reduce the pollutants present in the studied urban wastewater, producing water without ecotoxicological risk or essentially free of pollutants. In all cases, good recovery was achieved, which increased with molecular weight, although chemical and electrostatic interactions also played a role.

8.
Chemosphere ; 287(Pt 1): 132076, 2022 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-34478963

RESUMO

Concentration data of veterinary drugs in microalgae biomass collected from photobioreactors fed with piggery wastewaters are presented for the first time in this work. To this aim, a QuEChERS methodology and an ultrasound-assisted solid-liquid extraction have been assessed as sample preparation procedures with the purpose of determining 20 veterinary drugs, mainly antibiotics of different physico-chemical properties in addition to dexamethasone, fenbendazole and progesterone. Some critical operation parameters of the QuEChERS procedure were optimized by an experimental design but tetracycline, oxytetracycline, doxycycline, marbofloxacin and ciprofloxacin were not detected by the QuEChERS sample preparation. The use of a longer and thorough approach, a solid-liquid extraction with water/methanol in presence of primary secondary amine as a clean-up agent followed by solid-phase extraction on Oasis HLB cartridges, is recommended to monitor all intended analytes. The determination in extracts is carried out by ultra-high performance liquid chromatography-tandem mass spectrometry in selected reaction monitoring mode. Limits of detection about 0.2-42 ng per g of lyophilized microalgae sample, and repeatabilities about 6-46% (n = 5, RSDs) are reached. The solid-liquid extraction method was applied to microalgae biomass samples collected from a photobioreactor. Nine drugs were detected in the samples at relatively low concentration and a proportional relationship between the found concentrations and the octanol/water partition coefficients of the drugs has been outlined. Moreover, a linear ratio between the concentrations measured in biomass and effluent has been observed for most of the drugs.


Assuntos
Microalgas , Drogas Veterinárias , Biomassa , Cromatografia Líquida de Alta Pressão , Fotobiorreatores , Extração em Fase Sólida , Espectrometria de Massas em Tandem , Águas Residuárias/análise
9.
Bioresour Technol ; 340: 125552, 2021 Nov.
Artigo em Inglês | MEDLINE | ID: mdl-34352641

RESUMO

The domestic sewage treatment performance of an integrated anoxic-aerobic photobioreactor with biomass settling and recycling, coupled with anaerobic digestion of the produced bacterial-algal biomass and biogas upgrading in the photobioreactor was investigated. Hydraulic retention time in the photobioreactor initially was 4 days (stage I and II) and then reduced to 2.5 days (stage III). The integrated system supported high total organic carbon removals of 98.9 ± 1.1% regardless of the operational stage. A high total nitrogen removal of 90.8 ± 8.0% was recorded in the integrated system during the three operational stages, while total phosphorus removals accounted for 68.4 ± 20.1%, 68.3 ± 20.8% and 53.4 ± 25.0% in stages I, II and III, respectively. Biogas upgrading in the absorption column exhibited maximum removals of CO2 and H2S of 74.7 ± 3.0% and 99.0 ± 2.8%, respectively. Biomass settling and recycling resulted in overall improvement of biomass settleability.


Assuntos
Biocombustíveis , Esgotos , Anaerobiose , Biomassa , Reatores Biológicos , Nitrogênio , Fotobiorreatores , Eliminação de Resíduos Líquidos
10.
Chemosphere ; 275: 130039, 2021 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-33640746

RESUMO

The presence of residues of veterinary pharmaceuticals in farm wastewaters such as pig slurry represents a problem that needs to be tackled to avoid further contamination of environmental waters and the development of resistant bacteria. For their monitoring and control, it is necessary the existence of reliable analytical tools. The present paper describes for the first time the development and optimization by statistical experimental design of a specifically designed analytical method for the analysis of 21 veterinary drugs, including 18 antibiotics of several families (ß-lactams, tetracyclines, fluoroquinolones, sulfonamides, macrolides, among others), 1 antiparasitic, 1 analgesic and 1 hormone, in a complex environmental matrix such as the fresh solid phase of pig slurry. The resulting method, consisted of an ultrasound assisted extraction (UAE) combined with in-situ dispersive solid phase extraction (d-SPE) from a 0.3 g of freeze-dried sample aliquot followed by a preconcentration step by compact solid phase extraction (c-SPE) and subsequent instrumental analysis by ultra-high-performance-liquid-chromatography (UHPLC) coupled to mass spectrometry in tandem (MS/MS) by a triple quadrupole, was successfully validated as a very sensitive (method limit of quantification in the low ng g-1) and reliable method (relative recoveries around 100% and method repeatability featured by a general relative standard deviation below 20%). Provided raw data was intended to be processed by matrix-matched quantification approach. The resulting methodology was applied to the characterization of several pig manures from different Spanish farms sampled across breeding season between 2018 and 2019. Sample precedence showed to have a high impact in the positives, its frequency and concentration.


Assuntos
Drogas Veterinárias , Animais , Antibacterianos , Cromatografia Líquida de Alta Pressão , Esterco , Extração em Fase Sólida , Suínos , Espectrometria de Massas em Tandem
11.
Sci Total Environ ; 692: 259-266, 2019 Nov 20.
Artigo em Inglês | MEDLINE | ID: mdl-31349167

RESUMO

Traditional swine manure treatments are not fully effective in the removal of veterinary drugs. Moreover, they are costly and entail a significant carbon footprint in many cases. Innovative biological approaches based on phototrophic microorganisms have recently emerged as promising alternatives to overcome those limitations. This work evaluated the removal of 19 veterinary drugs (i.e., 16 antibiotics, 1 analgesic, 1 anti-parasitic and 1 hormone) from piggery wastewater (PWW) in two open photobioreactors (PBR) operated with a consortium of microalgae-bacteria (AB-PBR) and purple photosynthetic bacteria (PPB-PBR). Multiple hydraulic retention times (HRT), in particular 11, 8 and 4 days, were tested during stage I, II and III, respectively. Ten out of 19 target compounds were detected with inlet drug concentrations ranging from 'non-detected' (n.d.) to almost 23,000 ng L-1 for the antibiotic oxytetracycline. Moreover, three of the antibiotics (i.e., enrofloxacin, sulfadiazine and oxytetracycline) were found at concentrations above the analytical linearity range in some or all of the samples under study. AB-PBR supported higher removal efficiencies (REs) than PPB-PBR, except for danofloxacin. Overall, REs progressively decreased when decreasing the HRT. The highest REs (>90%) were observed for doxycycline (95 ±â€¯3%) and oxytetracycline (93 ±â€¯3%) in AB-PBR during stage I. The other drugs, except sulfadimidine that was the most recalcitrant, showed REs above 70% during stage I in the same photobioreactor. In contrast, no removal was observed for danofloxacin in AB-PBR during stage III, sulfadimidine in PPB-PBR during stage III or marbofloxacin in PPB-PBR during the entire experiment.


Assuntos
Bactérias/metabolismo , Microalgas/metabolismo , Consórcios Microbianos , Fotobiorreatores/microbiologia , Drogas Veterinárias/análise , Eliminação de Resíduos Líquidos/métodos , Criação de Animais Domésticos , Animais , Proteobactérias/metabolismo , Sus scrofa , Eliminação de Resíduos Líquidos/instrumentação , Águas Residuárias/análise
12.
Sci Total Environ ; 662: 32-40, 2019 Apr 20.
Artigo em Inglês | MEDLINE | ID: mdl-30684900

RESUMO

This work evaluates the removal of five pharmaceuticals and personal care products, i.e., ibuprofen, naproxen, salicylic acid, triclosan and propylparaben, from urban wastewater under two novel algal-bacterial photobioreactor settings. The first configuration (phase A) consisted of an anoxic-aerobic photobioreactor operating at a hydraulic retention time (HRT) of 2d at different concentrations of total organic carbon (TOC) (90mgL-1-200mgL-1). In the second configuration (phase B) an anaerobic step was introduced before the anoxic tank to set a photosynthetic A2O process. In this phase, the HRT varied between 3 and 4d and the TOC was kept constant at 200mgL-1. In addition, the impact of external aeration in the aerobic photobioreactor was assessed. The maximum removals for ibuprofen, naproxen, salicylic acid, triclosan and propylparaben (94±1%, 52±43%, 98±2%, 100±0%, 100±0%, respectively) were recorded during phase B. In phase A, low TOC concentrations triggered higher ibuprofen and naproxen removals likely due to the high contribution of biological oxidation on their removal. In phase B, total or very high removal efficiencies were observed for ibuprofen, propylparaben and triclosan independently on the operating conditions. In contrast, the removal efficiency of naproxen and salicylic acid decreased when the HRT dropped from 4 to 3d in the absence of external aeration, which suggests that biodegradation played a key role in their removal. In addition, sorption might have contributed to the elimination of triclosan and propylparaben from the wastewater.


Assuntos
Bactérias/metabolismo , Microalgas/metabolismo , Fotobiorreatores/microbiologia , Eliminação de Resíduos Líquidos/métodos , Águas Residuárias/análise , Poluentes Químicos da Água/análise , Aerobiose , Anaerobiose , Anti-Infecciosos/análise , Anti-Inflamatórios não Esteroides/análise , Cidades , Eliminação de Resíduos Líquidos/instrumentação
13.
Talanta ; 186: 506-512, 2018 Aug 15.
Artigo em Inglês | MEDLINE | ID: mdl-29784394

RESUMO

The work here presented aimed at developing an analytical method for the simultaneous determination of 22 pharmaceuticals and personal care products, including 3 transformation products, in sewage and sludge. A meticulous method optimization, involving an experimental design, was carried out. The developed method was fully automated and consisted of the online extraction of 17 mL of water sample by Direct Immersion Solid Phase MicroExtraction followed by On-fiber Derivatization coupled to Gas Chromatography - Mass Spectrometry (DI-SPME - On-fiber Derivatization - GC - MS). This methodology was validated for 12 of the initial compounds as a reliable (relative recoveries above 90% for sewage and 70% for sludge; repeatability as %RSD below 10% in all cases), sensitive (LODs below 20 ng L-1 in sewage and 10 ng g-1 in sludge), versatile (sewage and sewage-sludge samples up to 15,000 ng L-1 and 900 ng g-1, respectively) and green analytical alternative for many medium-tech routine laboratories around the world to keep up with both current and forecast environmental regulations requirements. The remaining 10 analytes initially considered showed insufficient suitability to be included in the final method. The methodology was successfully applied to real samples generated in a pilot scale sewage treatment reactor.


Assuntos
Preparações Farmacêuticas/análise , Esgotos/química , Microextração em Fase Sólida , Poluentes Químicos da Água/análise , Cromatografia Gasosa-Espectrometria de Massas , Humanos
14.
Chemosphere ; 115: 47-53, 2014 Nov.
Artigo em Inglês | MEDLINE | ID: mdl-24560776

RESUMO

This paper deals with urban groundwater contaminated with carbamazepine (CBZ) and five of its human metabolites in Barcelona. Groundwater samples were accordingly collected in the aquifers of Poble Sec and Besòs River Delta. Higher concentrations and more compounds were found in the Besòs River Delta aquifer, which is recharged by a river contaminated with treated effluent from numerous treatment plants. By contrast, the urban area of Poble Sec presented lower concentrations and fewer compounds. The results showed that CBZ could be attenuated in the Poble Sec aquifer since concentrations in groundwater were lower than those evaluated from mixing of the recharge sources. Conversely, CBZ and its human metabolites were not removed under the reducing conditions of the Besòs River Delta aquifer probably because of the short residence time in this aquifer.


Assuntos
Analgésicos não Narcóticos/análise , Carbamazepina/análise , Água Subterrânea/análise , Poluentes Químicos da Água/análise , Analgésicos não Narcóticos/metabolismo , Carbamazepina/metabolismo , Monitoramento Ambiental , Rios/química , Poluentes Químicos da Água/metabolismo
15.
Anal Bioanal Chem ; 405(18): 5859-73, 2013 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-23579471

RESUMO

This paper describes the development and application of a multi-residue chiral liquid chromatography coupled with tandem mass spectrometry method for simultaneous enantiomeric profiling of 18 chiral pharmaceuticals and their active metabolites (belonging to several therapeutic classes including analgesics, psychiatric drugs, antibiotics, cardiovascular drugs and ß-agonists) in surface water and wastewater. To the authors' knowledge, this is the first time an enantiomeric method including such a high number of pharmaceuticals and their metabolites has been reported. Some of the pharmaceuticals have never been studied before in environmental matrices. Among them are timolol, betaxolol, carazolol and clenbuterol. A monitoring programme of the Guadalquivir River basin (South Spain), including 24 sampling sites and five wastewater treatment plants along the basin, revealed that enantiomeric composition of studied pharmaceuticals is dependent on compound and sampling site. Several compounds such as ibuprofen, atenolol, sotalol and metoprolol were frequently found as racemic mixtures. On the other hand, fluoxetine, propranolol and albuterol were found to be enriched with one enantiomer. Such an outcome might be of significant environmental relevance as two enantiomers of the same chiral compound might reveal different ecotoxicity. For example, propranolol was enriched with S(-)-enantiomer, which is known to be more toxic to Pimephales promelas than R(+)-propranolol. Fluoxetine was found to be enriched with S(+)-enantiomer, which is more toxic to P. promelas than R(-)-fluoxetine.


Assuntos
Cromatografia Líquida/métodos , Preparações Farmacêuticas/análise , Preparações Farmacêuticas/metabolismo , Rios/química , Espectrometria de Massas em Tandem/métodos , Poluentes Químicos da Água/análise , Atenolol/análise , Monitoramento Ambiental/métodos , Fluoxetina/análise , Metoprolol/análise , Preparações Farmacêuticas/química , Propanolaminas/análise , Propranolol/análise , Reprodutibilidade dos Testes , Sensibilidade e Especificidade , Espanha , Estereoisomerismo , Poluentes Químicos da Água/química
16.
Environ Pollut ; 174: 305-15, 2013 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-23302545

RESUMO

The present paper presents the occurrence of 72 pharmaceuticals and 23 transformation products (TPs) in groundwaters (GWs) underlying the city of Barcelona, Spain. Thirty-one samples were collected under different districts, and at different depths. Aquifers with different geologic features and source of recharge were included, i.e., natural bank filtration, infiltration from wastewater and water supply pipes, rainfall recharge, etc. Antibiotics were the most frequently found compounds detected at levels reaching 1000 ng L(-1). Natural bank filtration from the river that receives large amounts of effluents from waste water treatment plants (WWTPs), turned out being the most influencing source of contamination, thus GW showed high range of compounds and concentrations as high as or even higher than in the river itself. In general, TPs were found at lower concentrations than the corresponding parent compounds, with some exceptions, such as 4OH propranolol and enalaprilat.


Assuntos
Monitoramento Ambiental , Água Subterrânea/química , Preparações Farmacêuticas/análise , Poluentes Químicos da Água/análise , Cidades , Espanha , Águas Residuárias/química , Águas Residuárias/estatística & dados numéricos , Abastecimento de Água/análise , Abastecimento de Água/estatística & dados numéricos
17.
Sci Total Environ ; 440: 280-9, 2012 Dec 01.
Artigo em Inglês | MEDLINE | ID: mdl-22809787

RESUMO

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.


Assuntos
Água Doce/análise , Preparações Farmacêuticas/análise , Rios/química , Poluentes Químicos da Água/análise , Cromatografia Líquida , Monitoramento Ambiental , Água Doce/química , Humanos , Preparações Farmacêuticas/química , Preparações Farmacêuticas/metabolismo , Espanha , Espectrometria de Massas em Tandem , Poluentes Químicos da Água/química , Poluentes Químicos da Água/metabolismo
18.
J Chromatogr A ; 1252: 115-29, 2012 Aug 24.
Artigo em Inglês | MEDLINE | ID: mdl-22794795

RESUMO

The work describes the development and validation of an analytical method for simultaneous determination of 58 pharmaceuticals and 19 metabolites and transformation products in environmental waters. The method is fully automated and consists of a direct injection of a small volume (several mL) of water sample to an on-line system composed of TurboFlow™ chromatography for the extraction and clean-up followed by liquid chromatography-electrospray-tandem mass spectrometry (TFC-LC-ESI-MS/MS). The feasibility and limitations of the technique in the analysis of environmental and wastewaters is discussed. The main advantages include high throughput, minimum sample manipulation, low error introduction, high selectivity, sensibility and reliability. The method provided a tool for the determination of a high number of active metabolites and transformation products and was successfully applied in the analysis of samples from the river Ebro basin.


Assuntos
Cromatografia Líquida/métodos , Preparações Farmacêuticas/análise , Espectrometria de Massas em Tandem/métodos , Poluentes Químicos da Água/análise , Análise dos Mínimos Quadrados , Preparações Farmacêuticas/química , Reprodutibilidade dos Testes , Rios/química , Sensibilidade e Especificidade , Poluentes Químicos da Água/química
19.
Environ Sci Pollut Res Int ; 19(4): 1000-12, 2012 May.
Artigo em Inglês | MEDLINE | ID: mdl-22544553

RESUMO

PURPOSE: The Llobregat River, which is characterized by important fluctuations of the flow rates, receives treated waters from WWTPs. During the years 2007 and 2008, the Llobregat River basin suffered from a severe drought which affected the supply of drinking water facilities (DWF) that rely on the exploitation of the river water. The Catalan Water Agency implemented a water reuse experiment with the objective of maintaining the river flow rate at sufficiently high level so as to ensure the supply of raw water to Barcelona's major DWF. METHOD: A total of 103 emerging contaminants belonging to the groups of pharmaceuticals (74), illicit drugs (17) and oestrogens (12) were determined using LC-MS/MS methods in river water samples during the water reuse campaign. The effect of the reclaimed water discharge on the river water quality, in terms of contamination loads and environmental risk (based on the concentration addition mode), is discussed. RESULTS: Fifty-eight pharmaceuticals out of 74 monitored were detected at least in one sample. In river water upstream (site R0) majority of compounds were detected at low nanograms per litre levels, while downstream of discharge of tertiary effluent only few compounds were detected at levels higher than 100 ng L(-1) (i.e. acetaminophen, diclofenac, erythromycin, sulfamethazine), but never exceeding 500 ng L(-1). The total concentration of illicit drugs was found to be very low at both sampling sites (<50 ng L(-1)). No relevant ecotoxicity risks were identified, except for pharmaceuticals vs. algae. CONCLUSIONS: In general, the discharge of reclaimed water in the river influenced perceptibly in terms of concentrations, mass loads and environmental risk, especially for pharmaceuticals and in less extent for illicit drugs. Nevertheless, it was not very significant in any case.


Assuntos
Medição de Risco , Rios/química , Eliminação de Resíduos Líquidos/métodos , Poluentes Químicos da Água/análise , Cromatografia Líquida , Água Potável/análise , Estrogênios/análise , Drogas Ilícitas/análise , Modelos Químicos , Preparações Farmacêuticas/análise , Extração em Fase Sólida , Espanha , Espectrometria de Massas em Tandem , Movimentos da Água , Qualidade da Água
20.
Chemosphere ; 85(8): 1390-9, 2011 Nov.
Artigo em Inglês | MEDLINE | ID: mdl-21981822

RESUMO

This work describes the development, optimization and validation of an analytical method for the simultaneous detection and identification of 74 pharmaceutically active compounds (PhACs), from various therapeutic groups, in both environmental (ground and surface water) and wastewaters (WW). The method is based on the simultaneous extraction of all target compounds by solid phase extraction (SPE), using a hydrophilic-lipophilic balanced polymer followed by ultra high performance liquid chromatography (UHPLC) tandem mass spectrometry (MS/MS). Two selected reaction monitoring (SRM) transitions have been monitored per compound in order to fulfil the EC guidelines, as well as to ensure an accurate identification of target compounds in the samples. Quantification is performed by internal standard approach, applying 24 specific isotopically labeled compounds. The main advantages of the developed method, besides the selectivity and reliability of the results, is its high throughput. All compounds are extracted in a single step and the instrumental analysis lasts 5 min (NI mode)+8 min (PI mode), allowing fast throughput of samples. The limits of detection range from 0.01 to 50 ng L(-1), depending on the matrix, for most of the compounds. Finally, the method developed has been applied to the analysis of pharmaceuticals in the Ebro river basin (NE Spain).


Assuntos
Cromatografia Líquida de Alta Pressão/métodos , Preparações Farmacêuticas/análise , Espectrometria de Massas em Tandem/métodos , Poluentes Químicos da Água/análise , Cromatografia Líquida de Alta Pressão/economia , Reprodutibilidade dos Testes , Rios/química , Sensibilidade e Especificidade , Extração em Fase Sólida/métodos , Espanha , Espectrometria de Massas em Tandem/economia , Água/análise
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