RESUMEN
In Western Europe, river water quality can be assessed using sentinel species such as the amphipod Gammarus fossarum. In this work of environmental metabolomics, the objective was to develop suitable chemometrics methods, using a limited number of individuals, to assess the modification of the metabolism of G. fossarum exposed to two human pharmaceuticals. Males and females gammarids were exposed to a mixture of the anxiolytic oxazepam and the antiepileptic carbamazepine (1000â¯ngâ¯L-1) for 14 days under laboratory conditions according to a full factorial design 2² (repeated 5 times). They were analyzed at the single individual scale using a method including a µQuEChERS type extraction followed by a nanoliquid chromatography analysis coupled to high-resolution mass spectrometry. The molecular fingerprints obtained were investigated using XCMS. Several corrections of experimental drifts (by using lock mass and Quality Control samples) were tested prior to using APCA + method for the exploitation of the unbalanced designed data. Signal reproducibility was greatly improved by the lock mass normalisation. From the experimental design, a significant effect of both experimental factors "exposure to the mixture" and "gammarid gender" on the signals measured were highlighted by APCA+. Finally, the results obtained made it possible to identify variables responsible for each of the factor effects.
Asunto(s)
Anfípodos/efectos de los fármacos , Carbamazepina/farmacología , Nanotecnología , Oxazepam/farmacología , Anfípodos/metabolismo , Animales , Cromatografía Liquida , Femenino , Humanos , Masculino , Espectrometría de Masas , Análisis de Componente PrincipalRESUMEN
Among the release solutions for reducing the discharge of organic and persistent contaminants in the aquatic environment, the use of a tertiary treatment in addition to existing conventional wastewater treatment processes is considered. The use of micro-grain activated carbon in a fluidized bed is a promising technique investigated in this study. The effluents from a large-scale pilot system were analyzed by liquid chromatography coupled with high-resolution mass spectrometry (QToF). Several strategies were deployed, namely molecular fingerprint comparison, suspected and non-target analyses, identification of refractory compounds to treatment, and finally, quantification of identified compounds. The evaluation of the molecular fingerprints provided evidence of the overall effect of the tertiary treatment on the treated wastewater quality. The suspected approach highlighted the presence of 83 pharmaceuticals and pesticides as well as transformation products in the effluents. The non-target approaches also highlighted compounds refractory to tertiary treatment, such as illicit drugs or some pharmaceuticals. The identification and quantification of identified compounds underscored the suitability of micro-grain activated carbon in eliminating many classes of pharmaceuticals with various physicochemical properties, such as anti-hypertensive, analgesic, anti-viral, antidepressant and even various pesticides.
Asunto(s)
Carbón Orgánico/análisis , Espectrometría de Masas/métodos , Aguas Residuales/química , Purificación del Agua/métodos , Analgésicos , Antidepresivos , Antihipertensivos , Antivirales , Carbón Orgánico/química , Plaguicidas/análisis , Plaguicidas/aislamiento & purificación , Preparaciones Farmacéuticas/aislamiento & purificación , Contaminantes Químicos del Agua/análisisRESUMEN
The aim of this study was to develop an analytical method and contribute to the assessment of the Exposome. Thus, a targeted analysis of a wide range of contaminants in contact with humans on daily routines in urine was developed. The method focused on a list of 38 contaminants, including 12 pesticides, one metabolite of pesticide, seven veterinary drugs, five parabens, one UV filter, one plastic additive, two surfactants and nine substances found in different products present in the everyday human environment. These contaminants were analyzed by high performance liquid chromatography coupled to high resolution mass spectrometry (HPLC-HRMS) with a quadrupole-time-of-flight (QqToF) instrument from a raw urinary matrix. A validation according to the FDA guidelines was employed to evaluate the specificity, linear or quadratic curve fitting, inter- and intra-day precision, accuracy and limits of detection and quantification (LOQ). The developed analysis allows for the quantification of 23 contaminants in the urine samples, with the LOQs ranging between 4.3 ng.mL(-1) and 113.2 ng.mL(-1). This method was applied to 17 urine samples. Among the targeted contaminants, four compounds were detected in samples. One of the contaminants (tributyl phosphate) was detected below the LOQ. The three others (4-hydroxybenzoic acid, sodium dodecylbenzenesulfonate and O,O-diethyl thiophosphate potassium) were detected but did not fulfill the validation criteria for quantification. Among these four compounds, two of them were found in all samples: tributyl phosphate and the surfactant sodium dodecylbenzenesulfonate.
Asunto(s)
Cromatografía Liquida/métodos , Exposición a Riesgos Ambientales/análisis , Contaminantes Ambientales/orina , Espectrometría de Masas/métodos , Urinálisis/métodos , Adulto , Anciano , Contaminantes Ambientales/aislamiento & purificación , Femenino , Humanos , Masculino , Persona de Mediana Edad , Reproducibilidad de los Resultados , Adulto JovenRESUMEN
Among the solutions to reduce micropollutant discharges into the aquatic environment, activated carbon adsorption is a promising technique and a large scale pilot has been tested at the Seine Centre (240,000 m(3)/d - Paris, France) wastewater treatment plant (WWTP). While most of available works studied fixed bed or contact reactors with a separated separation step, this study assesses a new type of tertiary treatment based on a fluidized bed containing a high mass of activated carbon, continuously renewed. For the first time in the literature, micro-grain activated carbon (µGAC) was studied. The aims were (1) to determine the performances of fluidized bed operating with µCAG on both emerging micropollutants and conventional wastewater quality parameters, and (2) to compare its efficiency and applicability to wastewater to former results obtained with PAC. Thus, conventional wastewater quality parameters (n=11), pharmaceuticals and hormones (PPHs; n=62) and other emerging pollutants (n=57) have been monitored in µGAC configuration during 13 campaigns. A significant correlation has been established between dissolved organic carbon (DOC), PPHs and UV absorbance at 254 nm (UV-254) removals. This confirms that UV-254 could be used as a tertiary treatment performance indicator to monitor the process. This parameter allowed identifying that the removals of UV-254 and DOC reach a plateau from a µGAC retention time (SRT) of 90-100 days. The µGAC configuration substantially improves the overall quality of the WWTP discharges by reducing biological (38-45%) and chemical oxygen demands (21-48%), DOC (13-44%) and UV-254 (22-48%). In addition, total suspended solids (TSS) are retained by the µGAC bed and a biological activity (nitratation) leads to a total elimination of NO2(-). For micropollutants, PPHs have a good affinity for µGAC and high (>60%) or very high (>80%) removals are observed for most of the quantified compounds (n=22/32), i.e. atenolol (92-97%), carbamazepine (80-94%), ciprofloxacin (75-95%), diclofenac (71-97%), oxazepam (74-91%) or sulfamethoxazole (56-83%). In addition, alkylphenols, artificial sweeteners, benzotriazole, bisphenol A, personal care products (triclocarban and parabens) and pesticides have removals lying in the 50 ->90% range. Overall, the fluidized bed of µGAC allows obtaining performances comparable to PAC at the same activated carbon dose. Indeed, the average removal of the 13 PPHs found at a high occurrence (>75%) in WWTP discharges is similar at 20 g/m(3) of µGAC (78-89%) and PAC (85-93%). In addition, this recycled µGAC operation leads to several operational advantages (no FeCl3, reactivable, higher SRT, higher treated flow) and has a stronger impact on the overall wastewater quality compared to PAC.