Performance critical comparison of offline SPE, online SPE, and direct injection for the determination of CECs in complex liquid environmental matrices

Producción CientíficaSample preparation for the analysis of organic micropollutants in wastewater samples is commonly carried out by solid-phase extraction (SPE) procedures, which involve different manual laboratory operations. This conventional approach requires several hours of counter labour and entail the use of a lot of disposable material, and the subsequent contaminated non-recyclable plastic-residue production. In contrast, by coupling and automatizing the pre-treatment to the instrumental analysis most of that burden erases, sample size gets miniaturized and, thus, storage becomes freed-up. Even lab counters get cleared off from sample pre-treatment apparatus. However, method performance could get alter as a trade-off. This paper presents the results from a study in which methodology, including SPE online-coupled to UHPLC-MS/MS chromatography, was developed for multi-residue (58) determination of veterinary and pharmaceutical drugs in urban and piggery wastewater (influent and effluent to wastewater treatment plants (WWTPs)). Similarly, the direct injection (DI) of large volumes (hundreds of µL) of same matrix samples into the chromatographic system was optimized too. The performance of both automated methods was statistically compared with the classical off-line SPE. As dealing with trace analysis, suitable injection volumes for the alternative approaches were selected on the premise of low limits of quantification (MLQs). Under the selected conditions, validation parameters such as linearity range, method quantification limits, peak shape and carry over were determined. Usually more than 50 % of the analytes showed MLQs below 50 ng/L, for all matrices and methodologies, especially for DI. Real wastewater samples from a local urban WWTP and farm were analysed with all three tested methodologies. Determined concentrations and removal rates were statistically compared and turned out being quite similar. However, analysis under offline SPE and DI approaches provided a larger amount of information as they reached lower MLQs. Offline-SPE provided the worst precision among all.Junta de Castilla y León, y el programa EU-FEDER (CLU 2017-09),(CL-EI-2021-07),(UIC 071),(UIC 338),(INFRARED2018-UVA3).Ministerio de Ciencia, Innovación y Universidades (proyectos CTQ2017-84006-C3-1-R y PID2020-113544RB-I00

Analytical methodologies for the determination of pharmaceuticals and personal care products (PPCPs) in sewage sludge: A critical review

Producción CientíficaSeveral analytical approaches have been developed for the determination of emerging pollutants (EPs), including pharmaceuticals and personal care products (PPCPs) in environmental matrices. This paper reviews the sample preparation and instrumental methods proposed in the last few years (2012e2018) to assess PPCPs in sewage sludge. Three main steps are examined: extraction, clean-up and analysis. Sample preparation is critical as target compounds are normally found at low concentrations in complex matrices. Most procedures include sewage sludge pretreatment mostly through ultrasound-assisted extraction (UAE) although other novel techniques such as QuEChERS (Quick, Easy, Cheap, Effective, Rugged and Safe) or MSPD (matrix solid-phase dispersion) have been also employed. In one report, no differences in extraction efficiency were detected among the most commonly used extraction techniques such as ultrasound, microwave and pressurized liquid. Clean-up usually involves a conventional method such as solid phase extraction (SPE). This step is needed to appreciably reduce matrix suppression, and is followed by an instrumental analysis using techniques of preference such as gas chromatography (GC) or liquid chromatography (LC), mostly coupled to mass spectrometry (MS). A fully automated on-line system that includes extraction, chromatographic separation, and mass spectrometry in one-stage is here presented as a novel way of determining PPCPs in sewage sludge. This review also discusses the advantages and limitations of the different techniques used. Miniaturizing analytical techniques use of novel solid and liquid phase materials are emerging as efficient options that fulfill the principles of so-called "green chemistry".This study was supported by the Spanish Government (MINECO-CTM2015-70722-R) as well as by the Regional Government of Castilla y Le on and European Union through the FEDER Funding Program (CLU 2017e09, UIC 071 and Red Novedar). Nereida P erez-Lemus and Rebeca L opez-Serna acknowledge the Spanish Ministry of Science, Innovation and Universities for research grants (predoctoral CTM2015-70722-R and Juan de la Cierva Incorporaci on JCI-2015-23304, respectively)

Analysis of 60 pharmaceuticals and personal care products in sewage sludge by ultra-high performance liquid chromatography and tandem mass spectroscopy

Producción CientíficaThis paper presents a comparison of three different analytical proposals for the determination of 60 pharmaceuticals and personal care products (PPCPs) in solid urban sewage sludge. Two fast sample pretreatments, i.e., online solid-phase-extraction (online SPE) and direct injection (DI), were tested against the conventional offline solid phase extraction (offline SPE). In all cases, subsequently, extracts underwent ultra-high-performance-liquid chromatography coupled to tandem-mass-spectrometry (UHPLC-MS/MS), simultaneously operating in both positive and negative electrospray ionization (ESI) mode. In addition, as solid matrices, clean-up steps were necessarily preceded by ultra-sound-assisted extraction (UAE) in all cases. Matrix-matched quantification was combined with internal standard providing high reliability to all three approaches. Best performance was observed for the fully automatized and non-pretreated DI method, showing limits of detection below 30 ng g-1 for many of the target compounds, and recoveries between 80 and 120%. Finally, the best working method was validated and applied to the analysis of PPCPs in different dewatered digested sludge samples from the wastewater treatment plant (WWTP) in Valladolid (Spain). Acetaminophen was found at concentrations above 1,000 ng g-1.This work was supported by the University of Valladolid (UVa) through its General Foundation (063/136391), by the Spanish Government (MINECO-CTM2015-70722-R) and by the Regional Government of Castilla y León and the EU-FEDER (CLU 2017–09, UIC 071, INFRARED2018-UVA3, and VA080G18). It was partially carried out in the Laboratory of Instrumental Techniques from the UVa. The UVa is also recognized for the postdoctoral contract held by Rebeca López Serna (2018POSTDOC UVA12)

SETAC Europe 28th Annual Meeting

The demand of multicomponent methods for the analysis of compounds of emerging concern (CECs) in environmental matrices is a reality today. However, conventional techniques based on Solid Phase Extraction (SPE) coupled to Liquid Chromatography Mass Spectrometry (LC-MS) are very often only available in high-tech laboratorie

Ecological risk evaluation and removal of emerging pollutants in urban wastewater by a hollow fiber forward osmosis membrane

Producción CientíficaForward 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.Ministerio de Ciencia e Innovación/Agencia Estatal de Investigación (AEI)/10.13039/501100011033 - (project PID2019-109403RBC21

Multiresidue analytical method for pharmaceuticals and personal care products in sewage and sewage sludge by online direct immersion SPME on-fiber derivatization – GCMS

Producción CientíficaThe 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.Junta de Castilla y León (programa de apoyo a proyectos de investigación – Ref.VA067U16 and UIC71)Ministerio de Economía, Industria y Competitividad (Projects CTM2015-70722-R and Red NOVEDAR

Photolytic and photocatalytic removal of a mixture of four veterinary antibiotics

Producción CientíficaThe removal of a mixture of four veterinary antibiotics (VA) – tetracycline (TET), ciprofloxacin (CIP), sulfadiazine (SDZ) and sulfamethoxazole (SMX) – via photo-degradation (UVC) and photocatalysis with TiO2 (UVC/TiO2) was investigated in a batch reactor under different initial concentrations (20, 100, 500 and 1000 μg/L per antibiotic). Ultra-high performance liquid chromatography coupled to a mass spectrometry (UHPLC-MS/MS) was used to determine the removal of these veterinary antibiotics. The removal of all antibiotics via photolysis was around 98–99% after 100 h for TET, 122 h for CIP, 212 h for SDZ and 240 h for SMX. Nevertheless, the removal of all antibiotics via photocatalysis was around 99–100% after 4.2 h for TET, 3.5 h for CIP, 7.1 h for SDZ and 16.5 h for SMX. The photolysis for the four veterinary antibiotics followed a first-order irreversible kinetic model. The photocatalysis of TET, CIP and SDZ followed a Langmuir-Hinshelwood kinetic model, and adsorption was considered the limiting step. SMX followed a first-order irreversible kinetic model. The photolytic degradation rate constant (k1) was 0.00073 min−1 for TET, 0.00055 min−1 for CIP, 0.00031 min−1 for SDZ and 0.00027 min−1 for SMX. While for photocatalysis k1 was 0.0044 min−1 for SMX; kL-H was 0.0284 min−1 for TET, 0.0379 min−1 for CIP and 0.0141 min−1 for SDZ. The VA degradation was enhanced by the use of a catalyst. Additionally, electrical energy per order (EEO) was assessed to estimate the electrical energy efficiency of each process. EEO values for photolysis were 339.06 kWh/m3/order for TET, 449.84 kWh/m3/order for CIP, 795.31 kWh/m3/order for SDZ and 897.71 kWh/m3/order for SMX. On the other hand, EEO values for photocatalysis were 14.96 kWh/m3/order for TET, 12.07 kWh/m3/order for CIP, 20.39 kWh/m3/order for SDZ and 62.10 kWh/m3/order for SMX. The energy consumption for photocatalysis was considerably lower than for photolysis. This study determined an overall degradation rate constant for a wide range of TET, CIP, SDZ and SMX concentrations. Furthermore, when working with a pH of 8 (a typical pH from wastewater from livestock farms) and a VA mixture whose concentrations resemble the characteristics of real water samples, that photolysis and photocatalysis are potential processes for wastewater treatment with low energy consumption.Junta de Castilla y León (projects UIC 071, CLU 2017-09 and VA080G18)Ministerio de Ciencia, Innovación y Universidades (project PID2020-113544RB-I00)Unión Europea - Fondo Europeo de Desarrollo Regional (projects CLU 2017-09 and CTQ2017-84006-C3-1-R

Tumoral and normal brain tissue extraction protocol for wide-scope screening of organic pollutants

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 identify-ing 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)

Photobioreactors based on microalgae-bacteria and purple phototrophic bacteria consortia: A promising technology to reduce the load of veterinary drugs from piggery wastewater

Producción CientíficaTraditional 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 ± 3%) and oxytetracycline (93 ± 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.Gobierno regional de Castilla y León- FEDER (CLU 2017-09 and UIC71)EURICA program (Erasmus Mundus Action 2, Strand 1, Lot 15, grant 2013-2587)Ministerio de Ciencia, Innovación y Universidades (projects JCI-2015-23304, RED NOVEDAR and CTQ2017-84006-C3-1-R

Análisis y destino de residuos farmacéuticos en aguas subterráneas, superficiales y residuales

[spa] Los fármacos, compuestos químicos con actividad biológica, y sus productos de transformación, metabolitos y otros derivados en las plantas de tratamiento y en el medio ambiente, con actividad farmacológica remanente, son contaminantes antropogénicos que, en muchos casos, están llegando al medioambiente a través de las aguas residuales, y son las aguas superficiales el primer y principal compartimento ambiental destino. Este es un hecho que, en la actualidad, es ya ampliamente reconocido por la comunidad científica, tras el desarrollo de métodos de análisis capaces de la determinación de estos microcontaminantes en el medio ambiente, y su posterior aplicación en estudios de presencia en diferentes matrices ambientales. Los científicos, por lo tanto, están demandando medidas de control de los mismos por parte de las autoridades. Aunque tímidos, se están dando pasos adelante en materia legislativa en la lucha contra este tipo de contaminación, lo que muestra la toma de conciencia de la importancia en el control de las fuentes de entrada de estos contaminantes emergentes, así como de su eliminación del medioambiente. Esto conlleva un aumento importante en el número de estudios y, por lo tanto, en las muestras a procesar por parte de los laboratorios medioambientales. De ahí nace la necesidad de optimizar la eficiencia y competitividad de los métodos analíticos actuales, de manera que progresen en fiabilidad y sensibilidad, aumentando al mismo tiempo su versatilidad, así como su capacidad y rendimiento. El desarrollo tecnológico en el sector es muy rápido, y en general, es la comunidad científica la que evalúa en primer término la viabilidad y bonanza de las diferentes propuestas tecnológicas. Con la presente tesis se ha pretendido dar respuesta a estas necesidades. Así se ha llevado a cabo: - El desarrollo y validación de métodos analíticos para la determinación de fármacos y sus derivados en aguas medioambientales y residuales, mostrando las ventajas y puntos débiles de cada uno de ellos. En concreto, se han usado dos fuentes de fiabilidad, que no son excluyentes y pueden ser utilizadas simultáneamente. La primera ha consistido en la introducción de la automatización en el tratamiento de muestra, llevando al mínimo la manipulación de las muestras por parte del analista. La segunda ha consistido en la introducción de surrogados y patrones internos adecuados que han puesto de manifiesto las incidencias producidas durante el proceso analítico, para que hayan podido ser corregidas. Por otro lado, se han conseguido métodos que presentan una elevada sensibilidad para la determinación de los microcontaminantes objeto de estudio presentes a bajas concentraciones en matrices complejas. Para ello se ha utilizado espectrómetros de masas de triple cuadrupolo de última generación, que trabajando en modo SRM (Selected Reaction Monitoring), han proporcionado una muy buena sensibilidad, además de una elevada selectividad, que ha allananado el camino de la fiabilidad comentada anteriormente. Además, se apostó también, por el desarrollo de métodos con la suficiente versatilidad como para que hayan podido ser aplicados sobre cualquier tipo de agua ambiental dulce continental, tanto superficial como subterránea, así como a agua residual y potable, con el fin de propiciar la intercalación de muestras de diferente naturaleza analizadas consecutivamente en una misma tanda. Finalmente, se propusieron métodos dotados de una elevada capacidad, de manera que un solo método haya sido capaz de analizar el mayor número de residuos de interés posibles, incluyendo fármacos y sus derivados, metabolitos y otros productos de transformación. Pero a la vez, se ha conseguido un aumento en el rendimiento analítico de estos métodos, es decir, se ha logrado una disminución del tiempo de análisis por muestra y un aumento del número de muestras por día. Para esto se apostó claramente por la automatización, eliminando algunas etapas en el proceso analítico, lo que, además de redundar en fiabilidad como se ha comentado anteriormente, ha proporcionado métodos analíticos más cortos y autónomos y, por lo tanto, capaces de trabajar en ausencia del analista. Otra enfoque en esta dirección fue la utilización de cromatografía rápida. - Otra parte importante de la presente tesis, ha sido la aplicación posterior de los métodos desarrollados, en estudios medioambientales de elevado interés científico por su innovación. En concreto en los siguientes: A) Estudio del impacto medioambiental a escala real, en un escenario de reutilización de agua residual para el mantenimiento del caudal ecológico de un río mediterráneo. Además, se valoró el riesgo ecotoxicológico y de estrogenicidad en las muestras del río. B) Estudio de presencia de fármacos y sus productos de transformación en las aguas superficiales de la cuenca del río Ebro. C) Estudio de la distribución tridimensional y origen de residuos farmacéuticos (fármacos y sus productos de transformación) en las aguas subterráneas bajo la ciudad de Barcelona (España). D) Determinación enantiomérica de 13 residuos farmacéuticos quirales en las aguas superficiales de la cuenca del río Guadalquivir, así como en las aguas de entrada y salida a las principales EDARs asociadas a la cuenca. Además, se discutieron las implicaciones en la toxicidad de las relaciones racémicas y no racémicas.[eng] Pharmaceuticals are compounds with biological activity and their transformation products with remaining activity are arriving the environment through sewage waters, and superficial waters are the main receiving compartment. Some steps towards the fight this kind of contamination. This is creating an increase in the number of studies, and therefore, in the number of samples to be processed by the environmental laboratories. For this reason, the need to optimize the efficiency of current analytical methods, by improving the reliability, sensitivity, versatility, capacity and throughput, is a must. Technologic development is very fast in the sector, and the scientific community is generally the one that first assesses it. This thesis has tried to give answer to these requests. Thus, four multi-residue analytical methods for the analysis of pharmaceuticals and their transformation products in environmental and sewage waters, have been developed making use of cutting edge technology. The advantages and disadvantages of each of them have been discussed. Different online and offline pre-treatment technologies, fast and conventional liquid chromatographies and several kinds of triple quadrupoles for mass spectrometry, have been tested. Other important part of this thesis has been the application of the developed methods with high scientific studies, as follows: - Impact of the discharge of reclaimed sewage water in a Mediterranean river, and assessment of the eco-toxicological consequences. - Presence of pharmaceuticals and their transformation products in Ebro River basin, one of the main ones in the Iberian Peninsula. - Three-dimensional distribution of pharmaceuticals and their transformation products in the ground waters underlying Barcelona city (Spain). - Enantimeric determination of 13 chiral pharmaceutical residues in Guadalquivir River basin, one of the main ones in the Iberian Peninsula, and the assessment of the eco-toxicity issues related