RESUMEN
The study of the presence of antibiotics in the aquatic environment is a preliminary step to analyse their possible harmful effects on aquatic ecosystems. In order to monitor their occurrence in the aquatic environment, the European Commission established in 2015, 2018, and 2020 three Watch Lists of substances for Union-wide monitoring (Decisions (EU) 2015/495, 2018/840, and 2020/1161), where some antibiotics within the classes of macrolides, fluoroquinolones and penicillins were included. In the Basque coast, northern Spain, three macrolide antibiotics (erythromycin, clarithromycin, azithromycin) and ciprofloxacin were monitored quarterly from 2017 to 2020 (covering a period before and after the COVID19 outbreak), in water samples collected from two Waste Water Treatment Plants (WWTPs), and three control points associated with receiving waters (transitional and coastal water bodies). This work was undertaken for the Basque Water Agency (URA). The three macrolide antibiotics in water showed a frequency of quantification >65 % in the Basque coast, with higher concentrations in the WWTP emission stations than in receiving waters. Their frequency of quantification decreased from 2017 to 2020, as did the consumption of antibiotics in Spanish primary care since 2015. Ciprofloxacin showed higher frequencies of quantification in receiving waters than in wastewaters, but the highest concentrations were observed in the WWTP emission stations. Although consumption of fluoroquinolones (among which is ciprofloxacin) in primary care in the Basque Country has decreased in recent years, this trend was not observed in the waters sampled in the present study. On the other hand, concentrations of clarithromycin, azithromycin, and ciprofloxacin in receiving waters exceeded their respective Predicted No-Effect Concentrations, so they could pose an environmental risk. These substances are widely used in human and animal medicine, so, although only ciprofloxacin is included in the third Watch List, it would be advisable to continue monitoring macrolides in the Basque coast as well.
Asunto(s)
COVID-19 , Contaminantes Químicos del Agua , Antibacterianos/análisis , Azitromicina , Ciprofloxacina/análisis , Claritromicina , Ecosistema , Monitoreo del Ambiente , Fluoroquinolonas/análisis , Humanos , Penicilinas , Medición de Riesgo , España , Eliminación de Residuos Líquidos , Aguas Residuales/análisis , Contaminantes Químicos del Agua/análisisRESUMEN
The influence of the type of smoking process (natural/liquid; hot/cold) and salt (NaCl or KCl) on the levels of polybrominated diphenyl ethers (PBDEs) and polycyclic aromatic hydrocarbons (PAHs) in smoked salmon was evaluated. One parent compound - BDE 47 - and two methoxylated forms - 2'-MeO-BDE-68 and 6-MeO-BDE-47 - were detected in all the samples. Among the 14 PAHs analysed, naphthalene was the most abundant followed by phenanthrene and fluorene. Only smoked salmon treated with NaCl presented quantifiable levels of chrysene and benzo[b]fluoranthene. Among the four smoking processes evaluated, natural smoke led to higher levels of PAHs. Risk characterization tools, such as hazard index (HI) and incremental lifetime cancer risk (ILCR), showed that the risk of both PBDEs and PAHs to human health through the consumption of smoked salmon was very low.
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Contaminación de Alimentos/análisis , Éteres Difenilos Halogenados/análisis , Hidrocarburos Policíclicos Aromáticos/análisis , Animales , Manipulación de Alimentos/métodos , Conservación de Alimentos/métodos , Inocuidad de los Alimentos , Éteres Difenilos Halogenados/toxicidad , Hidrocarburos Policíclicos Aromáticos/toxicidad , Cloruro de Potasio/química , Medición de Riesgo , Salmón , Alimentos MarinosRESUMEN
Despite an improvement of water quality across Europe there are many pollution hotspots for both nitrates and PPPs, mainly due to agricultural activities. The BMPs and MMs to reduce pollution from agriculture are well known, and there are policy instruments in place to ensure drinking water standards, but the current approach has not been efficient enough. Within the H2020 Water Protect project the premise was that there is a need for a multi-actor, participatory approach to tackle the issue from a new angle, and to assess why the uptake of known BMPs and MMs was not better among farmers. Seven "Action Labs" were selected that represent major physical, socio-economical, cultural and farming settings across Europe. A methodology of multi-actor engagement was chosen but with different approaches due to the local context. Initially the level of farmers' awareness about water quality issues was matched to the observed uptake rates of BMPs and MMs. In a second survey barriers hindering the uptake of measures were identified. The first survey revealed a low general awareness on the potential pollution to drinking water sources. Despite this, between 24% to 88% of the surveyed farmers per Action Lab were already voluntarily adopting one quarter of the selected BMPs and MMs. The second survey demonstrated the need to address organisational, legislative, sociological and technical barriers. The lack of coordination between different institutional bodies promoting measures and the financial incentives needed to invest and operate these often-costly measures need to be considered. The multi-actor, participatory approach with its improved awareness and collaboration made it possible to identify the crucial factors for improvement - to build a social acceptance among all actors and communicate the issues and solutions from the start.
RESUMEN
Wastewater-based epidemiology (WBE) has become a very useful tool to monitor a population's drug consumption or exposure to environmental and food contaminants. In this work, WBE has been applied to estimate tobacco consumption in seven Spanish regions. To this end, 24 h composite wastewater samples were taken daily for one week in 17 wastewater treatment plants, covering altogether a population of ca. 6 million inhabitants. The samples were treated by enzymatic deconjugation and the wastewater content of two human-specific nicotine metabolites (namely, cotinine and trans-3'-hydroxycotinine) was measured to estimate the daily consumption of nicotine. The population-weighted average nicotine consumption in the seven analyzed regions was 2.2 g/(dayâ1000 inh.), without any daily pattern. This average estimated nicotine consumption value agreed with the value derived from official tobacco sales data. Differences in consumption among the seven studied regions were found, being Galicia, the region with the lowest rate, and the Basque Country and Catalonia those with the highest rates. However, no conclusive correlation was found between those values and the prevalence data taken from two different national surveys, nor sociodemographic and health data. This study demonstrates that this tool can complement other indicators in order to accurately assess tobacco consumption rates at regional and national levels and provides the most extensive application of the approach in the Spanish territory.
Asunto(s)
Uso de Tabaco , Monitoreo Epidemiológico Basado en Aguas Residuales , Humanos , Nicotina/análisis , España , Aguas Residuales/análisisRESUMEN
The occurrence of the extensively used herbicide diuron in the environment poses a severe threat to the ecosystem and human health. Four different ligninolytic fungi were studied as biodegradation candidates for the removal of diuron. Among them, T. versicolor was the most effective species, degrading rapidly not only diuron (83%) but also the major metabolite 3,4-dichloroaniline (100%), after 7-day incubation. During diuron degradation, five transformation products (TPs) were found to be formed and the structures for three of them are tentatively proposed. According to the identified TPs, a hydroxylated intermediate 3-(3,4-dichlorophenyl)-1-hydroxymethyl-1-methylurea (DCPHMU) was further metabolized into the N-dealkylated compounds 3-(3,4-dichlorophenyl)-1-methylurea (DCPMU) and 3,4-dichlorophenylurea (DCPU). The discovery of DCPHMU suggests a relevant role of hydroxylation for subsequent N-demethylation, helping to better understand the main reaction mechanisms of diuron detoxification. Experiments also evidenced that degradation reactions may occur intracellularly and be catalyzed by the cytochrome P450 system. A response surface method, established by central composite design, assisted in evaluating the effect of operational variables in a trickle-bed bioreactor immobilized with T. versicolor on diuron removal. The best performance was obtained at low recycling ratios and influent flow rates. Furthermore, results indicate that the contact time between the contaminant and immobilized fungi plays a crucial role in diuron removal. This study represents a pioneering step forward amid techniques for bioremediation of pesticides-contaminated waters using fungal reactors at a real scale.
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Diurona/análisis , Herbicidas/análisis , Biodegradación Ambiental , Ecosistema , Hongos , HumanosRESUMEN
Occurrence of pharmaceuticals in the aquatic environment is nowadays a well-established issue that has become a matter of both scientific and public concern. Tons of different classes of pharmaceuticals find their way to the environment at variable degrees, after their use and excretion through wastewater and sewage treatment systems. The main goal of this study was to correlate the dynamics and the environmental risk of pharmaceuticals with different temporal and hydrological patterns, at the Guadiana Basin (South of Portugal). Water samples were collected bimonthly during 2017 (classified as a drought year) and 2018 (post-drought year) in: Zebro, Álamos and Amieira (intermittent hydrological streams), and Lucefécit (perennial hydrological stream). The pharmaceuticals quantified in higher concentrations, out of 27 investigated, were diclofenac (up to 4806 ng L-1), ibuprofen (3161 ng L-1), hydrochlorothiazide (2726 ng L-1) and carbamazepine (3223 ng L-1). Zebro and Álamos presented the highest contamination by this group of environmental hazardous substances, which may be correlated with the presence of wastewater treatment plants upstream the sampling point of each stream. Furthermore, the highest concentrations occurred mainly during the dry period (2017), when the flow was nearly inexistent in Zebro, and in Álamos after the first heavy rainfalls. In specific periods, the high concentrations of pharmaceuticals detected may induce risk for the organisms of lowest trophic levels, damaging the balance of the ecosystems at these streams. The risk quotient optimised approach (RQf) integrating exposure, toxicity and persistence factors, ranks the pharmaceuticals investigated in terms of risk for the aquatic ecosystems as follows: diclofenac, ibuprofen and carbamazepine (high risk), clarithromycin (moderate risk), acetaminophen, ofloxacin and bezafibrate (endurable risk), and hydrochlorothiazide (negligible risk).
Asunto(s)
Medición de Riesgo , Ecosistema , Monitoreo del Ambiente , Preparaciones Farmacéuticas , Portugal , Ríos , Contaminantes Químicos del AguaRESUMEN
Anticancer drugs are continuously released into hospital and urban wastewaters, where they, most commonly, undergo conventional treatment in wastewater treatment plants (WWTPs). Wastewaters contain complex mixtures of substances including parent compounds, their metabolites and transformation products (TPs). In this study, samples of hospital effluents and WWTP influents and effluents from Slovenia and Spain were analyzed for twenty-two selected anticancer drugs, their metabolites and transformation products. Acute and chronic toxicity tests were performed on the crustacean Ceriodaphnia dubia, genotoxicity was determined with Tradescantia and Allium cepa micronucleus (MN) assays and in vitro comet assay in zebrafish (Danio rerio) liver cell line (ZFL cells). Sixty of the two hundred-twenty determinations revealed detectable levels of anticancer drug residues. Among the targeted compounds, platinum based were most frequently detected (90%). Furthermore, erlotinib was detected in 80%, cyclophosphamide and tamoxifen in 70% and methotrexate in 60% of the samples. Seven of ten samples were toxic to C. dubia after acute exposure, whereas after chronic exposure all samples reduced reproduction of C. dubia at high sample dilutions. Allium cepa proved insensitive to the potential genotoxicity of the tested samples, while in Tradescantia increased MN frequencies were induced by a hospital effluent and WWTP influents. In ZFL comet assay all but one sample induced a significant increase of DNA strand breaks. Correlations of chemotherapeutics or their TPs were detected for all bioassays except for Allium cepa genotoxicity test, however for each test the highest correlations were found for different substances indicating differential sensitivities of the test organisms.
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Antineoplásicos/análisis , Antineoplásicos/toxicidad , Aguas Residuales/análisis , Aguas Residuales/toxicidad , Contaminantes Químicos del Agua/análisis , Contaminantes Químicos del Agua/toxicidad , Animales , Bioensayo , Ciudades , Ensayo Cometa , Crustáceos/efectos de los fármacos , Ciclofosfamida/análisis , Ciclofosfamida/toxicidad , Hospitales , Residuos Sanitarios/análisis , Pruebas de Micronúcleos , Pruebas de Mutagenicidad , Cebollas/efectos de los fármacos , Eslovenia , España , Tradescantia/efectos de los fármacos , Pez CebraRESUMEN
Retention indices for 70 polycyclic aromatic sulfur heterocycles (PASHs) were determined using reversed-phase liquid chromatography (LC) on a monomeric and a polymeric C18 stationary phase. Molecular shape parameters [length, breadth, thickness (T), and length-to-breadth ratio (L/B)] were calculated for all the compounds studied. Correlations between the retention on the polymeric C18 phase and PASH geometry (L/B and T) were investigated for six specific PASH isomer groups with molecular mass (MM) 184Da, 234Da, 258Da, 284Da, 334Da, and 384Da. Similar to previous studies for polycyclic aromatic hydrocarbons (PAHs), PASH elution order on the polymeric C18 phase was generally found to follow increasing L/B values. Correlation coefficients for retention vs L/B ranged from r=0.45 (MM 184Da) to r=0.89 (MM 284Da). In the case of smaller PASHs (MM≤258Da), the location of the sulfur atom in the bay-region of the structure resulted in later than expected elution of these isomers based on L/B. In the case of the larger PASHs (MM≥284Da), nonplanarity had a significant influence on earlier than predicted elution based on L/B values.
Asunto(s)
Cromatografía de Fase Inversa/métodos , Hidrocarburos Policíclicos Aromáticos/química , Hidrocarburos Policíclicos Aromáticos/aislamiento & purificación , Azufre/química , Isomerismo , Peso Molecular , Azufre/aislamiento & purificaciónRESUMEN
Retention indices for 79 alkyl-substituted polycyclic aromatic sulfur heterocycles (PASHs) were determined by using reversed-phase liquid chromatography (LC) on a monomeric and polymeric octadecylsilane (C18) stationary phase. Molecular shape parameters [length, breadth, thickness (T), and length-to-breadth ratio (L/B)] were calculated for all the compounds studied. Based on separations of isomeric methylated polycyclic aromatic hydrocarbons on polymeric C18 phases, alkyl-substituted PASHs are expected to elute based on increasing L/B ratios. However, the correlation coefficients had a wide range of values from r=0.43 to r=0.93. Several structural features besides L/B ratios were identified to play an important role in the separation mechanism of PASHs on polymeric C18 phases. First, the location of the sulfur atom in a bay-like-region results in alkylated-PASHs being more retentive than non-bay-like-region alkylated-PASHs, and they elute later than expected based on L/B value. Second, the placement of the alkyl group in the k region of the structure resulted in a later elution than predicted by L/B. Third, highly nonplanar methyl-PASHs (i.e., 1-Me and 11-MeBbN12T) elute prior to the parent PASH (BbN12T).
Asunto(s)
Alquilación , Cromatografía de Fase Inversa/métodos , Hidrocarburos Policíclicos Aromáticos/química , Hidrocarburos Policíclicos Aromáticos/aislamiento & purificación , Azufre/química , Azufre/aislamiento & purificaciónRESUMEN
Quantitative measurement of drug consumption biomarkers in wastewater can provide objective information on community drug use patterns and trends. This study presents the measurement of alcohol consumption in 20 cities across 11 countries through the use of wastewater-based epidemiology (WBE), and reports the application of these data for the risk assessment of alcohol on a population scale using the margin of exposure (MOE) approach. Raw 24-h composite wastewater samples were collected over a one-week period from 20 cities following a common protocol. For each sample a specific and stable alcohol consumption biomarker, ethyl sulfate (EtS) was determined by liquid chromatography coupled to tandem mass spectrometry. The EtS concentrations were used for estimation of per capita alcohol consumption in each city, which was further compared with international reports and applied for risk assessment by MOE. The average per capita consumption in 20 cities ranged between 6.4 and 44.3L/day/1000 inhabitants. An increase in alcohol consumption during the weekend occurred in all cities, however the level of this increase was found to differ. In contrast to conventional data (sales statistics and interviews), WBE revealed geographical differences in the level and pattern of actual alcohol consumption at an inter-city level. All the sampled cities were in the "high risk" category (MOE<10) and the average MOE for the whole population studied was 2.5. These results allowed direct comparisons of alcohol consumption levels, patterns and risks among the cities. This study shows that WBE can provide timely and complementary information on alcohol use and alcohol associated risks in terms of exposure at the community level.
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Consumo de Bebidas Alcohólicas , Medición de Riesgo/métodos , Aguas Residuales/análisis , Australia , Canadá , Ciudades , Europa (Continente)RESUMEN
Etoposide susceptibility to microbiological breakdown was studied in a batch biotransformation system, in the presence or absence of artificial wastewater containing nutrients, salts and activated sludge at two concentration levels. The primary focus of the present study was to study etoposide transformation products by ultra-high performance liquid chromatography coupled to high-resolution hybrid quadrupole-Orbitrap tandem mass spectrometry (MS/MS). Data-dependent experiments combining full-scan MS data with product ion spectra were acquired to identify the molecular ions of etoposide transformation products, to propose the molecular formulae and to elucidate their chemical structures. Due to the complexity of the matrix, visual inspection of the chromatograms showed no clear differences between the controls and the treated samples. Therefore, the software package MZmine was used to facilitate the identification of the transformation products and speed up the data analysis. In total, we propose five transformation products; among them, four are described as etoposide transformation products for the first time. Even though the chemical structures of these new compounds cannot be confirmed due to the lack of standards, their molecular formulae can be used to target them in monitoring studies.
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Antineoplásicos/metabolismo , Etopósido/metabolismo , Aguas Residuales/análisis , Contaminantes Químicos del Agua/metabolismo , Biodegradación Ambiental , Cromatografía Líquida de Alta Presión , Espectrometría de Masas en TándemRESUMEN
The residues of antineoplastic drugs are considered as new and emerging pollutants in aquatic environments. Recent experiments showed relatively high toxicity of 5-fluorouracil (5-FU), imatinib mesylate (IM), etoposide (ET) and cisplatin (CP) that are currently among most widely used antineoplastic drugs, against phytoplankton species. In this study, we investigated the toxic potential of the mixture of 5-FU + IM + ET against green alga Pseudokirchneriella subcapitata and cyanobacterium Synechococcus leopoliensis, and the stability and sorption of these drugs to algal cells. Toxic potential of the mixture was predicted by the concepts of 'concentration addition' and 'independent action' and compared to the experimentally determined toxicity. In both test species, the measured toxicity of the mixture was at effects concentrations EC10-EC50 higher than the predicted, whereas at higher effect concentration (EC90), it was lower. In general, P. subcapitata was more sensitive than S. leopoliensis. The stability studies of the tested drugs during the experiment showed that 5-FU, IM and CP are relatively stable, whereas in the cultures exposed to ET, two transformation products with the same mass as ET but different retention time were detected. The measurements of the cell-linked concentrations of the tested compounds after 72 h exposure indicated that except for CP (1.9 % of the initial concentration), these drugs are not adsorbed or absorbed by algal cells. The results of this study showed that in alga and cyanobacteria exposure to the mixture of 5-FU + ET + IM, in particular at low effect concentration range, caused additive or synergistic effect on growth inhibition, and they suggest that single compound toxicity data are not sufficient for the proper toxicity prediction for aquatic primary producers.
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Antineoplásicos/toxicidad , Chlorophyta/efectos de los fármacos , Synechococcus/efectos de los fármacos , Contaminantes Químicos del Agua/toxicidad , Etopósido/toxicidad , Fluorouracilo/toxicidad , Mesilato de Imatinib/toxicidad , Fitoplancton/efectos de los fármacosRESUMEN
The results of an inter-laboratory comparison exercise to determine cytostatic anticancer drug residues in surface water, hospital wastewater and wastewater treatment plant effluent are reported. To obtain a critical number of participants, an invitation was sent out to potential laboratories identified to have the necessary knowledge and instrumentation. Nine laboratories worldwide confirmed their participation in the exercise. The compounds selected (based on the extent of use and laboratories capabilities) included cyclophosphamide, ifosfamide, 5-fluorouracil, gemcitabine, etoposide, methotrexate and cisplatinum. Samples of spiked waste (hospital and wastewater treatment plant effluent) and surface water, and additional non-spiked hospital wastewater, were prepared by the organising laboratory (Jozef Stefan Institute) and sent out to each participant partner for analysis. All analytical methods included solid phase extraction (SPE) and the use of surrogate/internal standards for quantification. Chemical analysis was performed using either liquid or gas chromatography mass (MS) or tandem mass (MS/MS) spectrometry. Cisplatinum was determined using inductively coupled plasma mass spectrometry (ICP-MS). A required minimum contribution of five laboratories meant that only cyclophosphamide, ifosfamide, methotrexate and etoposide could be included in the statistical evaluation. z-score and Q test revealed 3 and 4 outliers using classical and robust approach, respectively. The smallest absolute differences between the spiked values and the measured values were observed in the surface water matrix. The highest within-laboratory repeatability was observed for methotrexate in all three matrices (CV ≤ 12 %). Overall, inter-laboratory reproducibility was poor for all compounds and matrices (CV 27-143 %) with the only exception being methotrexate measured in the spiked hospital wastewater (CV = 8 %). Random and total errors were identified by means of Youden plots.
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Antineoplásicos/análisis , Monitoreo del Ambiente/métodos , Contaminantes Químicos del Agua/análisis , Cromatografía Liquida/métodos , Cromatografía de Gases y Espectrometría de Masas/métodos , Reproducibilidad de los Resultados , Espectrometría de Masas en Tándem/métodosRESUMEN
Environmental quality monitoring of water resources is challenged with providing the basis for safeguarding the environment against adverse biological effects of anthropogenic chemical contamination from diffuse and point sources. While current regulatory efforts focus on monitoring and assessing a few legacy chemicals, many more anthropogenic chemicals can be detected simultaneously in our aquatic resources. However, exposure to chemical mixtures does not necessarily translate into adverse biological effects nor clearly shows whether mitigation measures are needed. Thus, the question which mixtures are present and which have associated combined effects becomes central for defining adequate monitoring and assessment strategies. Here we describe the vision of the international, EU-funded project SOLUTIONS, where three routes are explored to link the occurrence of chemical mixtures at specific sites to the assessment of adverse biological combination effects. First of all, multi-residue target and non-target screening techniques covering a broader range of anticipated chemicals co-occurring in the environment are being developed. By improving sensitivity and detection limits for known bioactive compounds of concern, new analytical chemistry data for multiple components can be obtained and used to characterise priority mixtures. This information on chemical occurrence will be used to predict mixture toxicity and to derive combined effect estimates suitable for advancing environmental quality standards. Secondly, bioanalytical tools will be explored to provide aggregate bioactivity measures integrating all components that produce common (adverse) outcomes even for mixtures of varying compositions. The ambition is to provide comprehensive arrays of effect-based tools and trait-based field observations that link multiple chemical exposures to various environmental protection goals more directly and to provide improved in situ observations for impact assessment of mixtures. Thirdly, effect-directed analysis (EDA) will be applied to identify major drivers of mixture toxicity. Refinements of EDA include the use of statistical approaches with monitoring information for guidance of experimental EDA studies. These three approaches will be explored using case studies at the Danube and Rhine river basins as well as rivers of the Iberian Peninsula. The synthesis of findings will be organised to provide guidance for future solution-oriented environmental monitoring and explore more systematic ways to assess mixture exposures and combination effects in future water quality monitoring.
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Conservación de los Recursos Naturales/métodos , Monitoreo del Ambiente/métodos , Contaminantes Químicos del Agua/análisis , Recursos Hídricos/estadística & datos numéricos , Calidad del Agua/normasRESUMEN
Daphnia magna individuals were transplanted across 12 sites from three Spanish river basins (Llobregat, Ebro, Jucar) showing different sources of pollution. Gene transcription, feeding and biochemical responses in the field were assessed and compared with those obtained in re-constituted water treatments spiked with organic eluates obtained from water samples collected at the same locations and sampling periods. Up to 166 trace contaminants were detected in water and classified by their mode of action into 45 groups that included metals, pharmaceuticals, pesticides, illicit drugs, and other industrial compounds. Physicochemical water parameters differentiated the three river basins with Llobregat having the highest levels of conductivity, metals and pharmaceuticals, followed by Ebro, whereas the Jucar river had the greatest levels of illicit drugs. D. magna grazing rates and cholinesterase activity responded similarly than the diversity of riparian benthic communities. Transcription patterns of 13 different genes encoding for general stress, metabolism and energy processes, molting and xenobiotic transporters corroborate phenotypic responses differentiated sites within and across river basins. Principal Component Analysis and Partial Least Square Projections to Latent Structures regression analyses indicated that measured in situ responses of most genes and biomarkers and that of benthic macroinvertebrate diversity indexes were affected by distinct environmental factors. Conductivity, suspended solids and fungicides were negatively related with the diversity of macroinvertebrates cholinesterase, and feeding responses. Gene transcripts of heat shock protein and metallothionein were positively related with 11 classes of organic contaminants and 6 metals. Gene transcripts related with signaling paths of molting and reproduction, sugar, protein and xenobiotic metabolism responded similarly in field and lab exposures and were related with high residue concentrations of analgesics, diuretics, psychiatric drugs, ß blockers, illicit drugs, trizoles, bisphenol A, caffeine and pesticides. These results indicate that application of omic technologies in the field is a promising subject in water management.
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Monitoreo del Ambiente/métodos , Animales , Biomarcadores/metabolismo , Daphnia , Plaguicidas/toxicidad , España , Contaminantes Químicos del Agua/toxicidadRESUMEN
This study describes the biotransformation of cytostatic and immunosuppressive pharmaceutical methotrexate. Its susceptibility to microbiological breakdown was studied in a batch biotransformation system, in presence or absence of carbon source and at two activated sludge concentrations. The primary focus of the present study are methotrexate biotransformation products, which were tentatively identified by the ultra-high performance liquid chromatography-quadrupole--Orbitrap-MS. Data-dependent experiments, combining full-scan MS data with product ion spectra were acquired, in order to identify the molecular ions of methotrexate transformation products, to propose the molecular formulae and to elucidate their chemical structures. Among the identified transformation products 2,4-diamino-N10-methyl-pteroic acid is most abundant and persistent. Other biotransformation reactions involve demethylation, oxidative cleavage of amine, cleavage of C-N bond, aldehyde to carboxylate transformation and hydroxylation. Finally, a breakdown pathway is proposed, which shows that most of methotrexate breakdown products retain the diaminopteridine structural segment. In total we propose nine transformation products, among them eight are described as methotrexate transformation products for the first time.
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Antimetabolitos Antineoplásicos/metabolismo , Inmunosupresores/metabolismo , Metotrexato/metabolismo , Aerobiosis , Biotransformación , Cromatografía Líquida de Alta Presión , Espectrometría de Masas/métodos , Aguas del Alcantarillado/microbiologíaRESUMEN
Water reuse is becoming a common practice in several areas in the world, particularly in those impacted by water scarcity driven by climate change and/or by rising human demand. Since conventional wastewater treatment plants (WWTPs) are not able to efficiently remove many organic contaminants and pathogens, more advanced water treatment processes should be applied to WWTP effluents for water reclamation purposes. In this work, a pilot plant based on microfiltration (MF) followed by reverse osmosis (RO) filtration was applied to the effluents of an urban WWTP. Both the WWTP and the pilot plant were investigated with regards to the removal of a group of relevant contaminants widely spread in the environment: 28 pharmaceuticals and 20 pesticides. The combined treatment by the MF-RO system was able to quantitatively remove the target micropollutants present in the WWTP effluents to values either in the low ng/L range or below limits of quantification. Monitoring of water quality of reclaimed water and water reclamation sources is equally necessary to design the most adequate treatment procedures aimed to water reuse for different needs.
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Plaguicidas/química , Preparaciones Farmacéuticas/química , Eliminación de Residuos Líquidos/métodos , Contaminantes Químicos del Agua/química , Purificación del Agua/métodos , Monitoreo del Ambiente , Filtración/métodos , Ósmosis , Plaguicidas/análisis , Preparaciones Farmacéuticas/análisis , Reciclaje , Contaminantes Químicos del Agua/análisisRESUMEN
Concerns about cytostatic anticancer drugs in the environment are increasing, mainly due to the lack of knowledge about the fate and impact of these cytotoxic compounds in the water cycle. In this context, the present work investigated the occurrence of 13 cytostatics and 4 metabolites in wastewater samples from various wastewater treatment plants (WWTPs) and from a large hospital from Spain. The target compounds belong to five different classes according to the Anatomical Therapeutic Classification (ATC), namely, alkylating agents, antimetabolites, plant alkaloids and other natural products, cytotoxic antibiotics and related substances, and other antineoplastic agents. Some of them have been classified as carcinogens in humans by the International Agency for Research on Cancer (IARC). These compounds were determined by an automated on line solid-phase extraction-liquid chromatography-tandem mass spectrometry (SPE-LC-MS/MS) method. Results showed the presence of methotrexate (MET), ifosfamide (IF), cyclophosphamide (CP), irinotecan (IRI), doxorubicin (DOX), capecitabine (CAP), tamoxifen (TAM) and the metabolites endoxifen (OH-D-TAM), hydroxytamoxifen (OH-TAM) and hydroxypaclitaxel (OH-PAC) at levels ranging from 2 ng L(-1) (for MET) to 180 ng L(-1) (for TAM). Some of these compounds were found to be efficiently removed after wastewater treatment, e.g. MET, DOX and IRI, whereas other compounds, such as TAM, CP and IF remained largely unaltered. The behaviour of the target compounds during the common filtration step of the water samples was also investigated with the finding that some compounds are strongly adsorbed to nylon filters, while cellulose acetate appears as the best choice for the filter material. The aquatic environmental risk associated to the detected compounds was also assessed. To the best of the authors' knowledge, this is the first report of the presence of the metabolites OH-D-TAM and OH-TAM in the water cycle.
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Citostáticos/análisis , Eliminación de Residuos Líquidos , Aguas Residuales/química , Contaminantes Químicos del Agua/análisis , Cromatografía Liquida , Monitoreo del Ambiente , Extracción en Fase Sólida , España , Espectrometría de Masas en TándemRESUMEN
Chemical pollution is typically characterized by exposure to multiple rather than to single or a limited number of compounds. Parent compounds, transformation products and other non-targeted compounds yield mixtures whose composition can only be partially identified by monitoring, while a substantial proportion remains unknown. In this context, risk assessment based on the application of additive ecotoxicity models, such as concentration addition (CA), is rendered somewhat misleading. Here, we show that ecotoxicity risk information can be better understood upon consideration of the probabilistic distribution of risk among the different compounds. Toxic units of the compounds identified in a sample fit a lognormal probability distribution. The parameters characterizing this distribution (mean and standard deviation) provide information which can be tentatively interpreted as a measure of the toxic load and its apportionment among the constituents in the mixture (here interpreted as mixture complexity). Furthermore, they provide information for compound prioritization tailored to each site and enable prediction of some of the functional and structural biological variables associated with the receiving ecosystem. The proposed approach was tested in the Llobregat River basin (NE Spain) using exposure and toxicity data (algae and Daphnia) corresponding to 29 pharmaceuticals and 22 pesticides, and 5 structural and functional biological descriptors related to benthic macroinvertebrates (diversity, biomass) and biofilm metrics (diatom quality, chlorophyll-a content and photosynthetic capacity). Aggregated toxic units based on Daphnia and algae bioassays provided a good indication of the pollution pattern of the Llobregat River basin. Relative contribution of pesticides and pharmaceuticals to total toxic load was variable and highly site dependent, the latter group tending to increase its contribution in urban areas. Contaminated sites' toxic load was typically dominated by fewer compounds as compared to cleaner sites where more compounds contribute.
Asunto(s)
Biomarcadores/análisis , Daphnia/efectos de los fármacos , Seguimiento de Parámetros Ecológicos/métodos , Microalgas/efectos de los fármacos , Medición de Riesgo/métodos , Contaminantes Químicos del Agua/análisis , Animales , Biopelículas/efectos de los fármacos , Biopelículas/crecimiento & desarrollo , Plaguicidas/análisis , Plaguicidas/toxicidad , Preparaciones Farmacéuticas/análisis , Ríos , España , Contaminantes Químicos del Agua/toxicidadRESUMEN
A sensitive and reliable method for the determination of 20 abused and illicit drugs and their metabolites in sewage sludge has been developed and validated. To the authors' knowledge, nine out of the 20 selected analytes, namely, cocaethylene, ephedrine, heroin, alprazolam, lysergic acid diethylamide (LSD), its metabolite 2-oxo-3-hydroxy-LSD, and the cannabinoids Δ(9)-tetrahydrocannabinol (THC), cannabinol (CBN) and cannabidiol (CBD), are investigated for the first time in this matrix. In the optimized approach, freeze-dried sewage sludge samples were extracted by means of pressurized liquid extraction, and the extracts were further cleaned-up by solid phase extraction. Analytes were determined by liquid chromatography coupled to tandem mass spectrometry. Method limits of quantification were below 3.3ng/g d.w. for all compounds but cannabinoids (8.2-22.5ng/g d.w.). Method repeatability was below 14% for most compounds. Overall method recoveries were low due to the presence of matrix interferences that could not be completely eliminated and suppressed the ionization of the target analytes between 26% and 89%. However, extraction losses and matrix effects were satisfactorily corrected through the use of isotopically labeled analogs as surrogate standards, ensuring reliable results. The method was applied to the analysis of various sewage sludge samples. Cannabinoids, methadone and its metabolite 2-ethylidene-1,5-dimethyl-3,3-diphenylpyrrolidine (EDDP) were the most ubiquitous and abundant compounds, showing maximum concentrations above 100ng/g d.w. in all cases (up to 579ng/g d.w. in the case of THC). This work is the first evidence of the presence of the cannabinoids CBN, CBD, and THC in sewage sludge.