Emission factor estimation of ca. 160 emerging organic microcontaminants by inverse modeling in a Mediterranean river basin (Llobregat, NE Spain)

Starting from measured river concentrations, emission factors of 158 organic compounds out of 199 analyzed belonging to different groups of priority and emerging contaminants [pesticides (25), pharmaceuticals and hormones (81), perfluoroalkyl substances (PFASs) (18), industrial compounds (12), drugs of abuse (8) and personal care products (14)] have been estimated by inverse modeling. The Llobregat river was taken as case study representative of Mediterranean rivers. Industrial compounds and pharmaceuticals are the dominant groups (range of 104mg·1000inhab-1·d-1). Personal care products, pesticides, PFASs and illegal drugs showed a load approximately one order of magnitude smaller. Considered on a single compound basis industrial compounds still dominate (range of ca. 103mg·1000inhab-1·d-1) over other classes. Generally, the results are within the range when compared to previously published estimations for other river basins. River attenuation expressed as the percentage fraction of microcontaminants eliminated was quantified. On average they were around 60-70% of the amount discharged for all classes, except for PFASs, that are poorly eliminated (ca. 20% on average). Uncertainties associated with the calculated emissions have been estimated by Monte-Carlo methods (15,000 runs) and typically show coefficients of variation of ca. 120%. Sensitivities associated with the various variables involved in the calculations (river discharge, river length, concentration, elimination constant, hydraulic travel time and river velocity) have been assessed as well. For the intervals chosen for the different variables, all show sensitivities exceeding unity (1.14 to 3.43), tending to amplify the variation of the emission. River velocity and basin length showed the highest sensitivity value. Even considering the limitations of the approach used, inverse modeling can provide a useful tool for management purposes facilitating the quantification of release rates of chemicals into the aquatic environment.This study has been financially supported by the EU through the FP7 project GLOBAQUA (Grant Agreement No. 603629), by the Spanish Ministry of Economyand Competitiveness [project Consolider-Ingenio 2010 SCARCE CSD2009-00065] and by the Generalitat de Catalunya (Consolidated Research Groups: 2014 SGR 418−Water and Soil Quality Unit and 2014 SGR 291−ICRA). It reflects only the author’s views. The Community is not liable for any use that may be made of the information contained therein. MK acknowledges an AGAUR fellowship from the Generalitat de Catalunya (Spain).Peer reviewe

Emerging risks in recycling and waste: Perfluorinated compounds in plastic pellets and nanomaterials in contaminated soil

Ponencia presentada en la Final RISKCYCLE conference, titulada "Risk-Based Management of Chemicals and Products in a circular economy at a global scale",celebrada en Dresden (Alemania) el 8 y 8 de mayo de 2012.According to the European Parliament over 1.8 billion tonnes of waste are generated each year in Europe (3.5 tonnes per person) and less than a third of it is recycled. United States produces approximately 200 million tons of garbage each year, according to the Environmental Protection Agency.Peer reviewe

Repercusiones sanitarias de la calidad del agua: los residuos de medicamentos en el agua

This manuscript summarizes the main results obtained in various monitoring studies conducted in the Llobregat and the Ebro River basins to evaluate the occurrence of pharmaceuticals and drugs of abuse in their aquatic environments and the potentially derived risks for environmental and human health. The occurrence of these compounds in surface waters, located downstream the point of discharge of sewage treatment plants (STP), points out STPs effluents as the main source of these substances in the aquatic environment. Both river basins had similar pharmaceutical contamination patterns. However, hazard quotients (HQ) calculated for three different trophic levels (algae, daphnia and fish) pointed out sulfamethoxazol (sulfamide antibiotic) for algae, gemfibrozil (lipid regulator) for algae and fish, clofibric acid (lipid regulator) and erythromycine (macrolide antibiotic) for daphnia, and ibuprofen (analgesic anti-inflammatory) for all investigated tropic levels, as the compounds with the highest ecotoxicological risk in the Llobregat. In the Ebro River, the most problematic pharmaceuticals were sulfamethoxazol for algae, and erythromycine, clofibric acid and fluoxetine (anti-depressive) for daphnids. Levels of drugs of abuse measured in surface waters of the Ebro River were one and two orders of magnitude lower than those observed in effluent and influent sewage waters, respectively. Lack of data about their ecotoxicity does not allow calculation of HQ for these compounds. The presence of pharmaceuticals and drugs of abuse in surface and drinking waters is not subjected to regulation; hence, they are not considered priority pollutants to be included in monitoring programs. However, due to their possible harmful outcomes in wildlife, research on their potential effects in human health is indispensable.Este trabajo resume varios estudios de monitorización de fármacos y drogas de abuso llevados a cabo en el medio ambiente acuático de las cuencas de los ríos Llobregat y Ebro con el fin de evaluar la calidad del agua en relación a la presencia de estas substancias y su potencial riesgo para la salud ambiental y pública. La identificación de estos compuestos aguas abajo del punto de vertido de las plantas depuradoras apunta a la descarga de agua residual tratada como la principal fuente de emisión de estos contaminantes en el medio acuático. El perfil de contaminación por fármacos fue bastante similar en ambas cuencas. No obstante, los índices de riesgo (HQ) calculados para los fármacos en diferentes niveles tróficos (algas, dáfnidos y peces) indican que los compuestos que presentan un mayor riesgo ecotóxico en el Llobregat son el sulfametoxazol (antibiótico sulfamida) para las algas, el gemfibrozil (regulador de lípidos) para las algas y los peces, el ácido clofíbrico (regulador de lípidos) y la eritromicina (antibiótico macrólido) para los dáfnidos, y el ibuprofeno (analgésico anti-inflamatorio) para todos los eslabones tróficos. En el Ebro, los compuestos más problemáticos son el sulfametoxazol para las algas, y la eritromicina, el ácido clofíbrico y la fluoxetina (antidepresivo) para los dáfnidos.Los niveles de drogas de abuso (y sus metabolitos) determinados en la cuenca del Ebro son aproximadamente uno y dos órdenes de magnitud más bajos respectivamente que los determinados en las aguas de salida y de entrada a las depuradoras. Sin embargo, debido a la falta de datos sobre su ecotoxicidad, no se han podido calcular índices de riesgo.La presencia de estos compuestos (fármacos y drogas) en aguas superficiales y de bebida aun no está regulada y, por lo tanto, no constituyen parámetros de obligado control. Aún es imprescindible seguir investigando para poder evaluar su posible efecto en la salud humana

Shifts of environmental and phytoplankton variables in a regulated river: A spatial-driven analysis

The longitudinal structure of the environmental and phytoplankton variables was investigated in the Ebro River (NE Spain), which is heavily affected by water abstraction and regulation. A first exploration indicated that the phytoplankton community did not resist the impact of reservoirs and barely recovered downstream of them. The spatial analysis showed that the responses of the phytoplankton and environmental variables were not uniform. The two set of variables revealed spatial variability discontinuities and river fragmentation upstream and downstream from the reservoirs. Reservoirs caused the replacement of spatially heterogeneous habitats by homogeneous spatially distributed water bodies, these new environmental conditions downstream benefiting the opportunist and cosmopolitan algal taxa. The application of a spatial auto-regression model to algal biomass (chlorophyll-a) permitted to capture the relevance and contribution of extra-local influences in the river ecosystem

Quality assessment of river waters using risk indexes for substances and sites, based on the COMMPS procedure

The well established risk assessment COMMPS methodology (Fraunhofer Institut, Schmallenberg, Germany) developed at a European basin scale to identify priority pollutants based on their exposure and effects, has been applied at a local scale along a double step process: (a) first, the corresponding adapted list of priority pollutants has been obtained from monitoring data at a regional scale; (b) second, a new site pollution risk index has been developed for the relative comparison of the chemical pollution status of the investigated geographical region. As a case study, representative of the Mediterranean area, the process has been applied to 17 Catalan rivers (NE Spain), using the monitoring data collected between 1997 and 2006 in 207 different sampling sites. After an appropriate selection procedure, 52 parameters were finally used for the calculation of the local priority substance and site risk indexes. From the exposure point of view the most relevant substances at the Catalan scale were volatile organohalogen compounds (VOX) and volatile aromatic hydrocarbons (toluene and xylene), whereas the priority substance risk index points to dibromomethane (volatile organohalogen compound) and benzo-a-anthracene (PAH) as the most concerning compounds. The local and European priority substance indexes have been compared, showing minor differences. Finally, site risk indexes have been calculated and utilized for comparison of the chemical status of different sites. They can be conveniently displayed in quality geographical maps and are considered a valuable tool for the environmental management and risk assessment of the region under study.We are grateful to the Catalan Water Agency (Agencia Catalana de l’Aigua, ACA) for allowing access to monitoring data and to Ministerio de Ciencia e Inovación, Spain, for the CTQ2009-11572 research grant.Peer reviewe

Discovery of large molecules as new biomarkers in wastewater using environmental proteomics and suitable polymer probes

The capability of monitoring large molecules as possible biomarkers in wastewater will be an important contribution to the new field of sewage epidemiology. Here, we explore the use of polymer probes together with untargeted proteomics for large scale protein analysis in sewage and treated water. Polymeric probes were immersed in the influent, anoxic reactor and effluent waters of a Spanish WWTP during 11 days. Proteins sorbed were extracted and identified by mass spectrometry. A total of 690 proteins from bacteria, plants and animals, including human, were identified showing different proteome profiles in the different sites. Bacterial proteins (510) pointed at 175 genera distributed in 22 bacteria classes. The most abundant were EF-Tu, GroEL and ATP synthase which were contributed by a high number of species. Human was the species contributing the greatest number of identified proteins (57), some in high abundance like keratins. Human proteins dominated in the influent water and were efficiently removed at the effluent. Several of the proteins identified (S100A8, uromodulin, defensins) are known disease biomarkers. This study provides the first insight into the proteome profiles present in real wastewater.The Proteomics Laboratory CSIC/UAB is a member of Proteored -PRB3 and is supported by Grant PT17/0019/0008 of the PE I+D+I 2013-2016, funded by ISCIII and FEDER. This work was supported by the Spanish Ministry of Science and Innovation (Project CEX2018-000794-S).Peer reviewe

Simultaneous determination of methyl tert.-butyl ether and its degradation products, other gasoline oxygenates and benzene, toluene, ethylbenzene and xylenes in Catalonian groundwater by purge-and-trap-gas chromatography-mass spectrometry

14 pages, 5 figures, 4 tables.-- PMID: 12800934 [PubMed].-- Available on line May 8, 2003.-- Erratum published in: Journal of Chromatography A 1007(1-2): 209-210 (Jul 25, 2003).In Catalonia (northeast Spain), a monitoring program was carried out to determine methyl tert.-butyl ether (MTBE), its main degradation products, tert.-butyl alcohol (TBA), tert.-butyl formate (TBF), and other gasoline additives, the oxygenate dialkyl ethers ethyl tert.-butyl ether, tert.-amyl methyl ether and diisopropyl ether and the aromatic compounds benzene, toluene, ethylbenzene and xylene (BTEX) in 21 groundwater wells that were located near different gasoline point sources (a gasoline spill and underground storage tank leakage). Purge-and-trap coupled to gas chromatography–mass spectrometry was optimised for the simultaneous determination of the above mentioned compounds and enabled to detect concentrations at ng/l or sub-μg/l concentrations. Special attention was given to the determination of polar MTBE degradation products, TBA and TBF, since not much data on method performance and environmental levels are given on these compounds in groundwater. All samples analysed contained MTBE at levels between 0.3 and 70 μg/l. Seven contaminated hot spots were identified with levels up to US Environmental Protection Agency drinking water advisory (20–40 μg/l) and a maximum concentration of 670 μg/l (doubling the Danish suggested toxicity level of 350 μg/l). Samples with high levels of MTBE contained 0.1–60 μg/l of TBA, indicating (but not proving) in situ degradation of parent compound. In all cases, BTEX was at low concentrations or not detected showing less solubility and persistence than MTBE. This fact confirms the suitability of MTBE as a tracer or indicator of long-term gasoline contamination than the historically used BTEX.This research is part of the WATCH (EVK1-CT-2000-00059) EU project funded by the EU Environment and Sustainable Development sub-program and from the Ministerio de Ciencia y Tecnología (REN2001-5039-E).Peer reviewe

Removal of pharmaceuticals during wastewater treatment and environmental risk assessment using hazard indexes

In a long term study, which covered 4 sampling periods over three years, a total number of 84 samples, specifically 28 influent, effluent, from seven WWTP located in the main cities along the Ebro river Basin (North East of Spain), as well as receiving river waters, were analyzed to assess the occurrence of 73 pharmaceuticals covering several medicinal classes. Results indicated that pharmaceuticals are widespread pollutants in the aquatic environmental. Linking the calculation of removal rates with half-lives, assuming that compound degradation followed pseudo-first order kinetics, suggested that conventional wastewater treatments applied at the seven WWTP were unable to completely remove most of the pharmaceuticals under study. The evaluation of compound degradability, in terms of half-lives, is an important task to discuss integrated solutions for mitigation of pollutants entry into the water cycle. High half-lives observed for the majority of pharmaceuticals in WWTP suggest that, in order to enhance compound degradation, higher hydraulic retention times should be required. The wide spectrum of substances detected in receiving river waters indicates that WWTP outlets are major contributors of pharmaceuticals in the aquatic environment. However, municipal wastewater treatment represents an obligatory and final treatment step prior to their release into the aquatic media, since load of pharmaceuticals in outlets were considerably reduced after treatment. Finally, hazard posed by pharmaceuticals in both surface and effluent wastewaters was assessed toward different aquatic organisms, (algae, daphnids and fish). The overall relative order of susceptibility was estimated to be algae > daphnia > fish. Results indicate that no significant risks could be associated to the presence of pharmaceuticals in those matrices, indicating that reduction of compound concentration after wastewater treatment as well as dilution factor once pharmaceuticals are discharged in receiving river water efficiently mitigate possible environmental hazards.EU project AQUATERRA (GOCE 505428) and the Spanish Ministry of Science and Education Project CEMAGUA (CGL2007-64551)Peer reviewe

Presence of pyrethroid pesticides in water and sediments of Ebro River Delta

The distribution of pyrethroid insecticides of the Ebro River Delta (NE Spain) was assessed by measuring concentrations in surface water and sediment samples. Pyrethroid extraction from water was carried out by ultrasound-assisted emulsification–extraction (UAEE), while the sediment was sonicated and cleaned up using Florisil cartridge. Method detection of limits (MLODs) for the 12 pyrethroids analyzed by gas chromatography–mass spectrometer in negative chemical ionization (GC–NCI–MS) ranged from 0.03 to 35.8 ng L−1 for water and 2.6 to 62.4 pg g−1 for sediment. Recoveries values were in the range of 47–105% for water and 51–105% for sediments, showing satisfactory robustness of the method for analyzing pyrethroids in water and sediment samples. Cypermethrin was detected in 22 water samples collected from Ebro River Delta, while deltamethrin was present only in three water samples at concentrations ranging from 0.73 ng L−1 to 57.2 ng L−1 and 2 ng L−1 to 58.8 ng L−1 for cypermethrin and deltamethrin, respectively. These concentration levels were higher than median lethal concentration (LC50) values found for deltamethrin and lower than LC50 values found for cypermethrin when short time toxic effects are considered. In sediment samples only cypermethrin was detected at concentration levels ranged from 8.27 ng g−1 to 71.9 ng g−1. These levels were higher than its LC50 values. Environmental dynamic behaviour and fate were also evaluated for cypermethrin measuring the sediment/water partition coefficient (ranging from 5.0 to 6.3) and kinetic data (half-life ranging between 13 and 50 days). Results were in good agreement to those reported in literatureThe authors are grateful to Mr. Jaume Cabrera (Catalan Water Agency) for his help on the supply of water and sediment samples. This material is based upon work supported by the Spanish Ministerio de Ciencia, e Innovación CEMAGUA (CGL2007-64551/HID). The authors are particularly grateful to Roser Charler for technical assistance.Peer reviewe

Monitoring and toxicity of sulfonated derivatives of benzene and naphthalene in municipal sewage treatment plants

10 pages, 4 figures.-- PMID: 15896893 [PubMed].-- Printed version published Sep 2005.Monitoring benzenesulfonates (BS) and naphthalenesulfonates (NS) took place in five municipal sewage treatment plants (STP). A previously optimized method based on solid phase extraction with polymeric cartridges followed by ion-pair liquid chromatography-electrospray-mass spectrometry (SPE-IPC-ESI-MS) was used. This work confirmed the little or no effect of primary settlement on total organic carbon (TOC) and monosulfonated compounds removal, whereas the main reduction is obtained at the biological stage. However, the most polar compounds, such as naphthalenedisulfonates (NDS), were not effectively removed using the biological treatment. An aromatic sulfonated compound is suggested to be used as a tracer of the origin of industrial pollutants discharged into STPs. A bioluminescence inhibition test, Microtox® assay, allowed toxicity determination of the most relevant aromatic sulfonated compounds detected and toxicity comparison between primary and secondary effluents.Sulphonated organic pollutants enter sewage treatment plants and although they partly discharged into the river waters no toxic effects are observed when biological treatment is used.This work has been supported by the European Commission Project (P-THREE no EVK1-CT2002-0116) and the Spanish Ministerio de Ciencia y Tecnologia (PPQ2002-10945-E and PPQ2001-1805-CO3-01) and by the Catalan Water Agency (Agencia Catalana de l'Aigua) Contract (July 2000).Peer reviewe