Suchergebnisse

[EN] This study focused on the effect of salinity on the performance of a pilot-scale nanofiltration (NF) for preconcentration of microcontaminants (MCs) in combination with solar photo-Fenton or photo-Fenton-like treatment for their elimination from NF permeate and concentrate streams. Photo-Fenton was carried out in a solar simulator at pH of 3 and at natural pH using Ethylenediamine-N, N'-disuccinic acid (EDDS) as an iron complexing agent Degradation efficacy was tested with MCs commonly found in urban wastewater treatment plant effluents (caffeine, imidacloprid, thiacloprid, carbamazepine and diclofenac). Hydrogen peroxide and persulfate were compared in solar processes. Increase in salinity and pressure had a negligible influence on MC permeability order and NF selectivity. Solar photo-Fenton was able to degrade MCs present in the concentrated stream, and rapidly eliminate any residual MCs that might finally be present in permeate streams. Persulfate used instead of hydrogen peroxide was shown to be inefficient for the selected MCs. Fe(Ill):EDDS at circumneutral pH was able to remove MCs as quickly as classical photo-Fenton at acid pH, or even faster. This effect supports use of Fe(III):EDDS at natural pH for treating NF concentrates or polishing NF permeates when NF membranes are operated under extreme conditions of salinity. ; This paper is part of a project that received funding from the European Union's Horizon 2020 Research and Innovation Programme under Marie Sklodowska-Curie Grant Agreement No 765860. Dennis Deemter would like to thank the staff at the Plataforma Solar de Almeria. The authors wish to thank the Spanish Ministry of Science, Innovation and Universities (MCIU), AEI and FEDER for funding under the CalypSol Project (Reference: RTI2018-097997-B-C32 and RTI2018097997-B-C31). ; Deemter, D.; Oller, I.; Amat Payá, AM.; Malato, S. (2021). Effect of salinity on preconcentration of contaminants of emerging concern by nanofiltration: Application of solar photo-Fenton as a tertiary treatment. ...

Environmental monitoring of hazardous chemicals in wildlife conventionally uses target screening for selected contaminants, but relatively few contaminants are moni-tored and knowledge of potentially hazardous contaminants of emerging concern (CECs) in wildlife is lacking. In this thesis, a non-target screening (NTS) method com-bined with temporal trend analysis was developed and applied as a prioritisation tool for identification of CECs in top predators, using high-resolution mass spectrometry (HRMS). A multi-residue sample extraction and HRMS screening method was devel-oped and validated for various biota tissue types and species, to capture chemicals with a broad range of physiochemical properties (Paper I). Minimised sample pre-treatment and clean-up resulted in a non-specific extraction method for NTS in biota. A tool for creating suspect lists for screening of CECs in biota was developed based on an exten-sive database of chemicals (Paper II). Systematic ranking of chemicals based on rele-vant physicochemical properties was used to prioritize CECs relevant for biota and water. Finally, a NTS workflow was developed for prioritizing CECs in time series of archived biological tissue of top predators. The samples included time series of muscle tissue from white-tailed sea eagle (Haliaeetus albicilla) (1965-2017) and Eurasian lynx (Lynx lynx) (1969-2017) obtained from the environmental specimen bank (ESB) at the Swedish Museum of Natural History (SMNH). The prioritisation method was validated with an artificial time series using spiked matrix samples of increasing concentrations (Paper III). A total of 14 compounds (six of anthropogenic origin) with increasing time trends were tentatively identified in white-tailed sea eagle samples, while two com-pounds with increasing time trends and one compound with a decreasing time trend were tentatively identified in lynx samples (Paper IV). The tentatively identified com-pounds originated from different chemical categories (pharmaceuticals, personal care products, industrial chemicals, herbicides). These results showed that, despite the high matrix effect and low expected concentrations in terrestrial species (lynx), it was possi-ble to tentatively identify new CECs in wildlife. The novel prioritisation strategy and NTS workflow developed in this thesis can provide a useful tool for future identifica-tion of CECs in biota. The overall findings can help government agencies expand their monitoring programmes for identification of CECs in biota.

Water scarcity is an issue of global concern due to the increase of the population and the climate change, which both increase the water demand. Many arid and semiarid countries are facing high water stress and the use of reclaimed water becomes a valuable resource. Many countries' economy is based on the agro-food sector, with amounts ca. the 70% of water demand. For this reason, reclaimed water represents an important component of wise water management. Wastewater treatment plants (WWTP) are designed to remove efficiently some biodegradable compounds, however, they are not able to remove a number of recalcitrant organic coñtamina0nts known as chemical oxygen demand (COD). There are many sources of water pollution, and contaminants of emerging concern (CECs) including many compounds that they are not legislated and recently some effects to the environment have been observed. For example, pharmaceuticals, personal care products, flame retardants, microplastics, etc. Consequently, plants are exposed to a huge number of chemical contaminants that are present not only in water, but also in air or soil. For this reason, it is important to understand the dynamics involved in the plant uptake of these CECs and more specifically in crops. In this Thesis, the uptake of some CECs, chosen by their occurrence in the environment and their physical-chemical properties, has been assessed. To elucidate the factors that are involved in the uptake of these contaminants, three different experiments were performed in a greenhouse. Therefore, this Thesis is divided in the three experiments. In the first one, the plant uptake of some CECs with a perlite:sand mixture and its modelling were assessed. Moreover, a mass balance was performed to evaluate the persistence of the CECs in the substrate. Then, by inverse modelling, the half-lives of CECs in the soil-plant system were estimated. In the second experiment, most of the CECs that were added in the irrigation water were taken up by lettuce. Hence, in this experiment, biochar, which ...

Contaminants of emerging concern (CECs) are one of the main barriers in the water cycle as they limit the water reuse due to their adverse effects on humans and the ecosystem. Natural and/or engineered ecosystems, such as conventional wastewater treatment processes, are not designed to remove CECs and contribute to the bioaccumulation in organisms considering high volumes of treated water discharges. The adoption of innovative solutions to upgrade urban water cycle facilities has gained relevance for the removal of these substances from final effluents. Molecularly imprinted polymers (MIPs) show promising selective removal toward a wide range of CECs. However, this process is still limited to lab/bench scale and needs to be critically analyzed and assessed for possible scale-up in real environment. Therefore, in this review, an overview of the fate and occurrence of CECs in wastewater is initially reported together with the state-of-the-art adsorption mechanisms to remove these compounds. In the central part of the paper, an evaluation of MIPs synthesis and their status in removing CECs from water matrix are presented. An upscaling pathway of MIPs column from lab- to pilot-scale is given to be applied for enhanced CECs removal and safe water reuse in irrigation/fertigation. Finally, possible integration of MIP columns to real wastewater treatment facilities is discussed and advantages and disadvantages of the potential solutions are addressed to enhance their sustainability. ; Funding The authors acknowledge the Partnership on Research and Innovation in the Mediterranean Area (PRIMA) Programme for funding "FIT4REUSE" innovation action under grant agreement number: [1823][FIT4REUSE][Call 2018 Section 1 Water]. The PRIMA Programme is supported under the Horizon2020, the European Union's Framework Programme for Research and Innovation.

Water scarcity is an issue of global concern due to the increase of the population and the climate change, which both increase the water demand. Many arid and semiarid countries are facing high water stress and the use of reclaimed water becomes a valuable resource. Many countries' economy is based on the agro-food sector, with amounts ca. the 70% of water demand. For this reason, reclaimed water represents an important component of wise water management. Wastewater treatment plants (WWTP) are designed to remove efficiently some biodegradable compounds, however, they are not able to remove a number of recalcitrant organic coñtamina0nts known as chemical oxygen demand (COD). There are many sources of water pollution, and contaminants of emerging concern (CECs) including many compounds that they are not legislated and recently some effects to the environment have been observed. For example, pharmaceuticals, personal care products, flame retardants, microplastics, etc. Consequently, plants are exposed to a huge number of chemical contaminants that are present not only in water, but also in air or soil. For this reason, it is important to understand the dynamics involved in the plant uptake of these CECs and more specifically in crops. In this Thesis, the uptake of some CECs, chosen by their occurrence in the environment and their physical-chemical properties, has been assessed. To elucidate the factors that are involved in the uptake of these contaminants, three different experiments were performed in a greenhouse. Therefore, this Thesis is divided in the three experiments. In the first one, the plant uptake of some CECs with a perlite:sand mixture and its modelling were assessed. Moreover, a mass balance was performed to evaluate the persistence of the CECs in the substrate. Then, by inverse modelling, the half-lives of CECs in the soil-plant system were estimated. In the second experiment, most of the CECs that were added in the irrigation water were taken up by lettuce. Hence, in this experiment, biochar, which is a soil improver, was assessed as a soil amendment to mitigate the uptake of these CECs in lettuce. To confirm this hypothesis, different biochar amendments were performed (O, 2.5 and 5% w/w biochar) to an agricultural soil from the Llobregat's Delta. Finally, it could be observed that the addition of biochar, reduced the concentration of CECs in lettuces. Since these two experiments demonstrated that CECs can be uptaken by crops and translocated to edible parts, and it well known that plants can metabolize xenobiotics through transformation, conjugation and sequestration steps, in the third experiment, an enzymatic digestion was performed to determine the conjugated CECs fraction. Interestingly, the conjugated fraction accounted up to more than 80%, which should be taken into account in risk assessment studies. Finally, in the same experiment, some effects of CECs to lettuce were elucidated. Visual differences between non-exposed and exposed lettuce were observed. For this reason, a metabolomic approach was applied to correlate the presence of CECs with the changes in the metabolome and the changes in chlorophyll content and plant morphology. ; L'escassetat d'aigua és un tema de gran preocupació degut a l'augment de la població i el canvi climàtic, que tan que s'elevi la demanda d'aigua. Molts països amb un clima àrid o semiàrid s'enfronten a un elevat estrès hídric. En aquest context, l'ús d'aigua regenerada es converteix en una practica clau. L'economia de molts passos es basa en el sector agroalimentari, que requereix grans quantitats d'aigua pel seu desenvolupament. Per aquesta raó, l'aigua regenerada representa un component important en la gestió intel·ligent de l'aigua. Les estacions depuradores d'aigües residuals (EDAR) estan dissenyades per eliminar de manera eficient alguns compostos biodegradables. Tot i així, no són capaces d'eliminar una sèrie de contaminants orgànics. Hi ha molts tipus de contaminació en l'aigua i els contaminants emergent (CECs) inclouen molts compostos que no estan legislats i recentment s'han observat alguns efectes en el medi ambient. Alguns exemples de CECs són fàrmacs, productes de cura personal, retardants de flama, microplàstics, etc. En conseqüència, les plantes estan exposades a un gran nombre de contaminants que es troben presents no només en aigua, sinó també en l'aire o el sol. Per aquest motiu, és important entendre la dinàmica implicada en l'absorció d'aquests contaminants en plantes i cercar estratègies per mitigar aquesta possible absorció. Aquest treball de recerca té com a objectiu estudiar l'absorció de diversos CECs en enciams, que han estat seleccionats perla seva presencia en el medi ambient i les seves propietats fisicoquímiques. Per dilucidar els paràmetres que estan implicats en l'absorció d'aquests contaminants en enciams, tres experiments diferents s'han dut a terme en l'estació experimental Agròpolis pertanyent a la UPC. Per tant, aquesta Tesi es pot separar en els 3 experiments duts a terme. En el primer experiment, es va avaluar l'absorció d'alguns CECs en enciams emprant un substrat format per una mescla de sorra i perlita. L'experiment va dilucidar que la majoria deis CECs van ser absorbits pels enciams i translocats a les parts aèries deis enciams. D'altra banda, un balanç;: de masses es va realitzar per avaluar la persistència deis CECs en el substrat. Després, mitjançant models d'incorporació de contaminants en plantes, es van estimar les vides mitjanes deis CEC en el sistema sol-planta. En un següent experiment, l'ús de biocarbó (biochar) es va proposar com una esmena del sol per reduir l'absorció d'aquests CECs als enciams. Per dur confirmar aquesta hipòtesi, es van afegir diferents percentatges de biochar (O, 2,5 i 5% de biochar) en un sol agrícola de la zona agrícola del Delta del Llobregat. Finalment, es va poder observar que l'addició de biochar reduí la concentració deis CECs en els enciams. Aquests dos primers experiments van ser útils per evidenciar que aquests compostos es poden absorbir fàcilment perles plantes i arribar a les parts que comestibles. No obstant, en altres estudis s'ha demostrat que les plantes són capaços de metabolitzar xenobiòtics a través de tres passos: transformació, conjugació i segrest deis CECs. Per aquest motiu, es va realitzar una digestió enzimàtica per determinar la fracció de CECs que podrien ser conjugats. Curiosament i segons el contaminant, la fracció conjugada va representar més del 80% del compost parental, evidenciant que la fracció conjugada s'ha de tenir en compte en els estudis d'avaluació de risc humà. Finalment, en aquest mateix experiment, es varen observar diferencies morfològiques entre els enciams exposats a un còctel de CECs i els no exposats als contaminants. A més, la determinació de clorofil·les també va evidenciar diferencies entre tractaments. Per aquesta raó, es van extreure els metabòlits secundaris deis enciams emprant un enfocament metabolòmic juntament amb tècniques quimiomètriques per correlacionar la presencia d'aquests contaminants amb els canvis morfològics i en el contingut de clorofil·la i dels metabòlits secundaris ; Postprint (published version)

Water scarcity is an issue of global concern due to the increase of the population and the climate change, which both increase the water demand. Many arid and semiarid countries are facing high water stress and the use of reclaimed water becomes a valuable resource. Many countries' economy is based on the agro-food sector, with amounts ca. the 70% of water demand. For this reason, reclaimed water represents an important component of wise water management. Wastewater treatment plants (WWTP) are designed to remove efficiently some biodegradable compounds, however, they are not able to remove a number of recalcitrant organic coñtamina0nts known as chemical oxygen demand (COD). There are many sources of water pollution, and contaminants of emerging concern (CECs) including many compounds that they are not legislated and recently some effects to the environment have been observed. For example, pharmaceuticals, personal care products, flame retardants, microplastics, etc. Consequently, plants are exposed to a huge number of chemical contaminants that are present not only in water, but also in air or soil. For this reason, it is important to understand the dynamics involved in the plant uptake of these CECs and more specifically in crops. In this Thesis, the uptake of some CECs, chosen by their occurrence in the environment and their physical-chemical properties, has been assessed. To elucidate the factors that are involved in the uptake of these contaminants, three different experiments were performed in a greenhouse. Therefore, this Thesis is divided in the three experiments. In the first one, the plant uptake of some CECs with a perlite:sand mixture and its modelling were assessed. Moreover, a mass balance was performed to evaluate the persistence of the CECs in the substrate. Then, by inverse modelling, the half-lives of CECs in the soil-plant system were estimated. In the second experiment, most of the CECs that were added in the irrigation water were taken up by lettuce. Hence, in this experiment, biochar, which is a soil improver, was assessed as a soil amendment to mitigate the uptake of these CECs in lettuce. To confirm this hypothesis, different biochar amendments were performed (O, 2.5 and 5% w/w biochar) to an agricultural soil from the Llobregat's Delta. Finally, it could be observed that the addition of biochar, reduced the concentration of CECs in lettuces. Since these two experiments demonstrated that CECs can be uptaken by crops and translocated to edible parts, and it well known that plants can metabolize xenobiotics through transformation, conjugation and sequestration steps, in the third experiment, an enzymatic digestion was performed to determine the conjugated CECs fraction. Interestingly, the conjugated fraction accounted up to more than 80%, which should be taken into account in risk assessment studies. Finally, in the same experiment, some effects of CECs to lettuce were elucidated. Visual differences between non-exposed and exposed lettuce were observed. For this reason, a metabolomic approach was applied to correlate the presence of CECs with the changes in the metabolome and the changes in chlorophyll content and plant morphology. ; L'escassetat d'aigua és un tema de gran preocupació degut a l'augment de la població i el canvi climàtic, que tan que s'elevi la demanda d'aigua. Molts països amb un clima àrid o semiàrid s'enfronten a un elevat estrès hídric. En aquest context, l'ús d'aigua regenerada es converteix en una practica clau. L'economia de molts passos es basa en el sector agroalimentari, que requereix grans quantitats d'aigua pel seu desenvolupament. Per aquesta raó, l'aigua regenerada representa un component important en la gestió intel·ligent de l'aigua. Les estacions depuradores d'aigües residuals (EDAR) estan dissenyades per eliminar de manera eficient alguns compostos biodegradables. Tot i així, no són capaces d'eliminar una sèrie de contaminants orgànics. Hi ha molts tipus de contaminació en l'aigua i els contaminants emergent (CECs) inclouen molts compostos que no estan legislats i recentment s'han observat alguns efectes en el medi ambient. Alguns exemples de CECs són fàrmacs, productes de cura personal, retardants de flama, microplàstics, etc. En conseqüència, les plantes estan exposades a un gran nombre de contaminants que es troben presents no només en aigua, sinó també en l'aire o el sol. Per aquest motiu, és important entendre la dinàmica implicada en l'absorció d'aquests contaminants en plantes i cercar estratègies per mitigar aquesta possible absorció. Aquest treball de recerca té com a objectiu estudiar l'absorció de diversos CECs en enciams, que han estat seleccionats perla seva presencia en el medi ambient i les seves propietats fisicoquímiques. Per dilucidar els paràmetres que estan implicats en l'absorció d'aquests contaminants en enciams, tres experiments diferents s'han dut a terme en l'estació experimental Agròpolis pertanyent a la UPC. Per tant, aquesta Tesi es pot separar en els 3 experiments duts a terme. En el primer experiment, es va avaluar l'absorció d'alguns CECs en enciams emprant un substrat format per una mescla de sorra i perlita. L'experiment va dilucidar que la majoria deis CECs van ser absorbits pels enciams i translocats a les parts aèries deis enciams. D'altra banda, un balanç;: de masses es va realitzar per avaluar la persistència deis CECs en el substrat. Després, mitjançant models d'incorporació de contaminants en plantes, es van estimar les vides mitjanes deis CEC en el sistema sol-planta. En un següent experiment, l'ús de biocarbó (biochar) es va proposar com una esmena del sol per reduir l'absorció d'aquests CECs als enciams. Per dur confirmar aquesta hipòtesi, es van afegir diferents percentatges de biochar (O, 2,5 i 5% de biochar) en un sol agrícola de la zona agrícola del Delta del Llobregat. Finalment, es va poder observar que l'addició de biochar reduí la concentració deis CECs en els enciams. Aquests dos primers experiments van ser útils per evidenciar que aquests compostos es poden absorbir fàcilment perles plantes i arribar a les parts que comestibles. No obstant, en altres estudis s'ha demostrat que les plantes són capaços de metabolitzar xenobiòtics a través de tres passos: transformació, conjugació i segrest deis CECs. Per aquest motiu, es va realitzar una digestió enzimàtica per determinar la fracció de CECs que podrien ser conjugats. Curiosament i segons el contaminant, la fracció conjugada va representar més del 80% del compost parental, evidenciant que la fracció conjugada s'ha de tenir en compte en els estudis d'avaluació de risc humà. Finalment, en aquest mateix experiment, es varen observar diferencies morfològiques entre els enciams exposats a un còctel de CECs i els no exposats als contaminants. A més, la determinació de clorofil·les també va evidenciar diferencies entre tractaments. Per aquesta raó, es van extreure els metabòlits secundaris deis enciams emprant un enfocament metabolòmic juntament amb tècniques quimiomètriques per correlacionar la presencia d'aquests contaminants amb els canvis morfològics i en el contingut de clorofil·la i dels metabòlits secundaris ; Postprint (published version)

AbstractHuman biomonitoring (HBM) frameworks assess human exposure to hazardous chemicals. In this review, we discuss and summarize sample preparation procedures and analytical methodology for six groups of chemicals of emerging concern (CECs), namely diisocyanates, benzotriazoles, benzothiazoles, 4-methylbenzylidene camphor, isothiazolinones, fragrances, and non-phthalate plasticizers, which are increasingly detected in urine, however, are not yet widely included in HBM schemes, despite posing a risk to human health. The sample preparation procedures depend largely on the chemical group; however, solid-phase extraction (SPE) is most often used due to the minimized sample handling, lower sample volume, and generally achieving lower limits of quantification (LOQs) compared to other extraction techniques. In terms of sample analysis, LC-based methods generally achieve lower limits of quantification (LOQs) compared to GC-based methods for the selected six groups of chemicals owing to their broader chemical coverage. In conclusion, since these chemicals are expected to be more frequently included in future HBM studies, it becomes evident that there is a pressing need for rigorous quality assurance programs to ensure better comparability of data. These programs should include the reporting of measurement uncertainty and facilitate inter-laboratory comparisons among the reporting laboratories. In addition, high-resolution mass spectrometry should be more commonly employed to enhance the specificity and selectivity of the applied analytical methodology since it is underrepresented in HBM. Furthermore, due to the scarcity of data on the levels of these CECs in urine, large population HBM studies are necessary to gain a deeper understanding of the associated risks.

AbstractThe enhancement of the ultrasound system by adding diverse oxidants to remove a model contaminant (acetaminophen, ACE) in water was investigated. Different parameters were evaluated to study their effect on both the degradation kinetics and the synergy of the combination. The variables studied were the ultrasonic frequency (575, 858, and 1135 kHz), type of oxidant (hydrogen peroxide, sodium peroxydisulfate (or persulfate, PDS), and potassium peroxymonosulfate (PMS)), ACE concentration (4, 8, and 40 µM), and oxidant concentration (0.01, 0.1, 1, and 5 mM). Particular interest was placed on synergistic effects, implying that one process (or both) is activated by the other to lead to greater efficiency. Interestingly, the parameters that led to the higher synergistic effects did not always lead to the most favorable degradation kinetics. An increase in ACE removal of 20% was obtained using the highest frequency studied (1135 kHz), PMS 0.1 mM, and the highest concentration of ACE (40 µM). The intensification of degradation was mainly due to the ability of ultrasound to activate oxidants and produce extra hydroxyl radicals (HO•) or sulfate radicals (SO4•–). Under these conditions, treatment of ACE spiked into seawater, hospital wastewater, and urine was performed. The hospital wastewater matrix inhibited ACE degradation slightly, while the urine components inhibited the pollutant degradation completely. The inhibition was mainly attributed to the competing organic matter in the effluents for the sono-generated radical species. On the contrary, the removal of ACE in seawater was significantly intensified due to "salting out" effects and the production of the strong oxidant HOCl from the reaction of chloride ions with PMS.