Indirect potable water reuse to face drought events in Barcelona city. Setting a monitoring procedure to protect aquatic ecosystems and to ensure a safe drinking water supply.

The climate change and increasing anthropogenic pressures are expected to limit the availability of water resources. Hence, active measures must be planned in vulnerable regions to ensure a sustainable water supply and minimize environmental impacts. A pilot test was carried out in the Llobregat River (NE Spain) aiming to provide a useful procedure to cope with severe droughts through indirect water reuse. Reclaimed water was used to restore the minimum flow of the lower Llobregat River, ensuring a suitable water supply downstream for Barcelona. A monitoring was performed to assess chemical and microbiological threats throughout the water treatment train, the river and the final drinking water, including 376 micropollutants and common microbiological indicators. The effects of water disinfection were studied by chlorinating reclaimed water prior to its discharge into the river. Data showed that 10 micropollutants (bromodichloromethane, dibromochloromethane, chloroform, EDDP, diclofenac, iopamidol, ioprimid, lamotrigine, ofloxacin and valsartan) posed a potential risk to aquatic life, whereas one solvent (1,4-dioxane) could affect human health. The chlorination of reclaimed water mitigated the occurrence of pharmaceuticals but, conversely, the concentration of halogenated disinfection by-products increased. From a microbiological perspective, the microbial load decreased along wastewater treatments and, later, along drinking water treatment, ultimately reaching undetectable values in final potable water. Non-chlorinated reclaimed water showed a lower log reduction of E. coli and coliphages than chlorinated water. However, the effect of disinfection vanished once reclaimed water was discharged into the river, as the basal concentration of microorganisms in the Llobregat River was comparable to that of non-chlorinated reclaimed water. Overall, our study indicates that indirect water reuse can be a valid alternative source of drinking water in densely populated areas such as Barcelona (Catalonia - NE Spain). A suitable monitoring procedure is presented to assess the related risks to human health and the aquatic ecosystem.

Could we estimate industrial wastewater flows composition using the UN-ISIC classification system?

Although we have extensive datasets on the location and typology of industries, we do not know much on their generated and discharged wastewater. This lack of information compromises the achievement of the sustainable development goals focused on water (Sustainable Development Goal 6) in Europe and globally. Thus, our goal was to assess to which degree the chemical composition of industrial wastewater could be estimated based on the industry's typology according to its International Standard Industrial Classification of All Economic Activities (ISIC) class. We collected wastewater effluent water samples from 60 industrial wastewater effluents (before any wastewater treatment process), accounting for 5 samples each of 12 ISIC classes, analyzed the composition of key contaminants (i.e. European Commission rated priority compounds and watchlist), and statistically assessed the similarities and differences amongst ISIC classes using ordination and random forest analyses. The results showed statistically significant linkages between most ISIC classes and the composition of produced wastewater. Among the analytical parameters measured, the random forest methodology allowed identifying a sub-set particularly relevant for classification or eventual contamination prediction based on ISIC class. This is an important applied research topic with strong management implications to (i) determine pollution emission caps for each individual ISIC class, (ii) define monitoring schemes to sample and analyze industrial wastewater, and (iii) enable predicting pollutant loads discharged in river basins with scarce information. These encouraging results urge us to expand our work into other ISIC classes and water quality parameters to draw a full picture of the relationship between ISIC classes and produced wastewater.

Individual body mass and length dataset for over 12,000 fish from Iberian streams.

We provide a unique fish individual body size dataset collected from our own sampling and public sources in north-eastern Spain. The dataset includes individual body size measures (fork length and mass) of 12,288 individuals of 24 fish species within 10 families collected at 118 locations in large rivers and small streams. Fish were caught by one-pass electrofishing following European standard protocols. The fish dataset has information on the local instream conditions including climatic variables (i.e., temperature and precipitation), topography (i.e., altitude), nutrient concentration (i.e., total phosphorus and nitrates), and the IMPRESS values (a measure of cumulative human impacts in lotic ecosystems). The potential uses of this new fish dataset are manifold, including developing size-based indices to further estimate the ecological status of freshwater ecosystems, allometric models, and analysis of variation in body size structure along environmental gradients.

The Catalan Surveillance Network of SARS-CoV-2 in Sewage: design, implementation, and performance.

Wastewater-based epidemiology has shown to be an efficient tool to track the circulation of SARS-CoV-2 in communities assisted by wastewater treatment plants (WWTPs). The challenge comes when this approach is employed to help Health authorities in their decision-making. Here, we describe the roadmap for the design and deployment of SARSAIGUA, the Catalan Surveillance Network of SARS-CoV-2 in Sewage. The network monitors, weekly or biweekly, 56 WWTPs evenly distributed across the territory and serving 6 M inhabitants (80% of the Catalan population). Each week, samples from 45 WWTPs are collected, analyzed, results reported to Health authorities, and finally published within less than 72 h in an online dashboard ( https://sarsaigua.icra.cat ). After 20 months of monitoring (July 20-March 22), the standardized viral load (gene copies/day) in all the WWTPs monitored fairly matched the cumulative number of COVID-19 cases along the successive pandemic waves, showing a good fit with the diagnosed cases in the served municipalities (Spearman Rho = 0.69). Here we describe the roadmap of the design and deployment of SARSAIGUA while providing several open-access tools for the management and visualization of the surveillance data.

Fate of N-nitrosodimethylamine and its precursors during a wastewater reuse trial in the Llobregat River (Spain).

In summer 2019, a full-scale trial was carried out to investigate the effects in drinking water quality when tertiary treated wastewater was discharged into the Llobregat River upstream of the intake of one of the major drinking water treatment plants of Barcelona and its metropolitan area. Two scenarios were investigated, i.e. discharging the reclaimed water with and without chemical disinfection with chlorine. This study investigates the concentration of N-nitrosodimethylamine (NDMA) as the specific disinfection conditions employed in this trial may favor its formation. To this aim, both NDMA and NDMA formation potential, were measured. The river contained NDMA at very low concentrations, but the concentration of NDMA precursors was already high. The NDMA concentration was reduced from discharge to the river to drinking water intake probably due to a combined effect of dilution and photolysis. The formation potential was also reduced probably due to dilution and biodegradation. The concentration of NDMA in the drinking water was always low (<7.3 ng/L), although the formation potential was above 10 ng/L in one sample. Dissolved organic matter characterization by high resolution mass spectrometry revealed differences between the nature of the organic matter in the river before and after reclaimed water discharge.

Combining multi-isotopic and molecular source tracking methods to identify nitrate pollution sources in surface and groundwater.

Nitrate (NO3-) pollution adversely impacts surface and groundwater quality. In recent decades, many countries have implemented measures to control and reduce anthropogenic nitrate pollution in water resources. However, to effectively implement mitigation measures at the origin of pollution,the source of nitrate must first be identified. The stable nitrogen and oxygen isotopes of NO3- (ẟ15N and ẟ18O) have been widely used to identify NO3- sources in water, and their combination with other stable isotopes such as boron (ẟ11B) has further improved nitrate source identification. However, the use of these datasets has been limited due to their overlapping isotopic ranges, mixing between sources, and/or isotopic fractionation related to physicochemical processes. To overcome these limitations, we combined a multi-isotopic analysis with fecal indicator bacteria (FIB) and microbial source tracking (MST) techniques to improve nitrate origin identification. We applied this novel approach on 149 groundwater and 39 surface water samples distributed across Catalonia (NE Spain). A further 18 wastewater treatment plant (WWTP) effluents were also isotopically and biologically characterized. The groundwater and surface water results confirm that isotopes and MST analyses were complementary and provided more reliable information on the source of nitrate contamination. The isotope and MST data agreed or partially agreed in most of the samples evaluated (79 %). This approach was especially useful for nitrate pollution tracing in surface water but was also effective in groundwater samples influenced by organic nitrate pollution. Furthermore, the findings from the WWTP effluents suggest that the use of literature values to define the isotopic ranges of anthropogenic sources can constrain interpretations. We therefore recommend that local sources be isotopically characterized for accurate interpretations. For instance, the detection of MST inferred animal influence in some WWTP effluents, but the ẟ11B values were higher than those reported in the literature for wastewater. The results of this study have been used by local water authorities to review uncertain cases and identify new vulnerable zones in Catalonia according to the European Nitrate Directive (91/676/CEE).

Occurrence of regulated pollutants in populated Mediterranean basins: Ecotoxicological risk and effects on biological quality.

Chemical stressors co-occur in mixtures into watercourses and this complicates predicting their effects on their ecological status. Our knowledge of river basin specific pollutants (RBSPs) is still limited, but it remains necessary to ensure the good chemical and ecological status. We performed an exercise on Mediterranean river sites exposed to urban and industrial pressures in order to, i) prioritize the occurring chemicals, ii) assessing the site's specific chemical risk (RQsite), and iii) relating the chemical risk to the biological quality, using as evidences invertebrates and diatom indices. Mediterranean rivers suffer from strong pressures which lead to a poor dilution ability, which makes the inhabiting biota highly vulnerable. The most frequent pollutants in the 89 sites surveyed included pharmaceutical products such as the antibiotics azithromycin, clarithromycin, and erythromycin, and the anti-inflammatory diclofenac, and products of industrial origin such as perfluorinated PFOS, nickel, and nonylphenol. Both the diatom index IPS and the macroinvertebrate index IBMWP hold strong negative correlations to RQsite, indicating a significant contribution of chemicals to biological impairment. Chemical contaminants (but not nutrients or dissolved organic carbon) were associated with significant changes to the taxonomic composition of invertebrate communities, but not to that of diatom communities. Our analyses indeed reveal that the impact of co-occurring chemicals translates onto negative effects in the biological quality. Our approach may be of use to evidence impacts on water resources and water quality in rivers under strong human pressure.

Biomonitoring of intermittent rivers and ephemeral streams in Europe: Current practice and priorities to enhance ecological status assessments.

Intermittent rivers and ephemeral streams (IRES) are common across Europe and dominate some Mediterranean river networks. In all climate zones, IRES support high biodiversity and provide ecosystem services. As dynamic ecosystems that transition between flowing, pool, and dry states, IRES are typically poorly represented in biomonitoring programmes implemented to characterize EU Water Framework Directive ecological status. We report the results of a survey completed by representatives from 20 European countries to identify current challenges to IRES status assessment, examples of best practice, and priorities for future research. We identify five major barriers to effective ecological status classification in IRES: 1. the exclusion of IRES from Water Framework Directive biomonitoring based on their small catchment size; 2. the lack of river typologies that distinguish between contrasting IRES; 3. difficulties in defining the 'reference conditions' that represent unimpacted dynamic ecosystems; 4. classification of IRES ecological status based on lotic communities sampled using methods developed for perennial rivers; and 5. a reliance on taxonomic characterization of local communities. Despite these challenges, we recognize examples of innovative practice that can inform modification of current biomonitoring activity to promote effective IRES status classification. Priorities for future research include reconceptualization of the reference condition approach to accommodate spatiotemporal fluctuations in community composition, and modification of indices of ecosystem health to recognize both taxon-specific sensitivities to intermittence and dispersal abilities, within a landscape context.

Comparing the response of biochemical indicators (biomarkers) and biological indices to diagnose the ecological impact of an oil spillage in a Mediterranean river (NE Catalunya, Spain).

Three biomarkers of hydrocarbon exposure, liver 7-ethoxyresourfin-O-deethylase activity (EROD), fluorescent hydrocarbon compounds (FACs) in bilis, and the liver antioxidant enzyme catalase (CAT) were examined in the autochthonous fish species Barbus meridionalis collected in the river Fluvià (NE Catalunya, Spain) after an oil spillage. Four different locations were sampled, including the impacted site, upstream and downstream sites and a reference site. Biomarker responses were compared with diatom and macroinvertebrate community assemblage metrics (Specific Pollution Sensitivity index - IPS, and Iberian Biological Monitoring Working Party - IBMWP, respectively). Chemical analyses denoted that polycyclic aromatic hydrocarbon levels in sediment were much higher at the impacted site than in downstream reaches. Four fold increase of EROD activity together with increased levels of biliary FACs in barbs collected at the spilled site indicated exposure of inhabiting fish to the oil. Additionally, CAT activity was significantly depressed (four fold) when compared to other stations, thus suggesting that fish collected from the impacted sites could be more susceptible to suffer oxidative stress. Biological indices (particularly that of the diatom community IPS) showed slight significant effects between control and impacted sites, indicating that more tolerant taxa were favoured because of the oil spillage. These results support the need to include biochemical responses measured in local species in monitoring programmes aimed to diagnose specific pollution effects in stressed river ecosystems.

TREHS: An open-access software tool for investigating and evaluating temporary river regimes as a first step for their ecological status assessment.

When the regime of a river is not perennial, there are four main difficulties with the use of hydrographs for assessing hydrological alteration: i) the main hydrological features relevant for biological communities are not quantitative (discharges) but qualitative (phases such as flowing water, stagnant pools or lack of surface water), ii) stream flow records do not inform on the temporal occurrence of stagnant pools, iii) as most of the temporary streams are ungauged, their regime has to be evaluated by alternative methods such as remote sensing or citizen science, and iv) the biological quality assessment of the ecological status of a temporary stream must follow a sampling schedule and references adapted to the flow- pool-dry regime. To overcome these challenges within an operational approach, the freely available software tool TREHS has been developed within the EU LIFE TRIVERS project. This software permits the input of information from flow simulations obtained with any rainfall-runoff model (to set an unimpacted reference stream regime) and compares this with the information obtained from flow gauging records (if available) and interviews with local people, as well as instantaneous observations by individuals and interpretation of ground-level or aerial photographs. Up to six metrics defining the permanence of water flow, the presence of stagnant pools and their temporal patterns of occurrence are used to determine natural and observed river regimes and to assess the degree of hydrological alteration. A new regime classification specifically designed for temporary rivers was developed using the metrics that measure the relative permanence of the three main phases: flow, disconnected pools and dry stream bed. Finally, the software characterizes the differences between the natural and actual regimes, diagnoses the hydrological status (degree of hydrological alteration), assesses the significance and robustness of the diagnosis and recommends the best periods for biological quality samplings.

Managing water quality under drought conditions in the Llobregat River Basin.

The primary effects of droughts on river basins include both depleted quantity and quality of the available water resources, which can render water resources useless for human needs and simultaneously damage the environment. Isolated water quality analyses limit the action measures that can be proposed. Thus, an integrated evaluation of water management and quality is warranted. In this study, a methodology consisting of two coordinated models is used to combine aspects of water resource allocation and water quality assessment. Water management addresses water allocation issues by considering the storage, transport and consumption elements. Moreover, the water quality model generates time series of concentrations for several pollutants according to the water quality of the runoff and the demand discharges. These two modules are part of the AQUATOOL decision support system shell for water resource management. This tool facilitates the analysis of the effects of water management and quality alternatives and scenarios on the relevant variables in a river basin. This paper illustrates the development of an integrated model for the Llobregat River Basin. The analysis examines the drought from 2004 to 2008, which is an example of a period when the water system was quantitative and qualitatively stressed. The performed simulations encompass a wide variety of water management and water quality measures; the results provide data for making informed decisions. Moreover, the results demonstrated the importance of combining these measures depending on the evolution of a drought event and the state of the water resources system.

Regime shift from phytoplankton to macrophyte dominance in a large river: Top-down versus bottom-up effects.

The lower Ebro River (Catalonia, Spain) has recently undergone a regime shift from a phytoplankton-dominated to a macrophyte-dominated system. This shift is well known in shallow lakes but apparently it has never been documented in rivers. Two initial hypotheses to explain the collapse of the phytoplankton were considered: a) the diminution of nutrients (bottom-up); b) the filtering effect due to the colonization of the zebra mussel (top-down). Data on water quality, hydrology and biological communities (phytoplankton, macrophytes and zebra mussel) was obtained both from existing data sets and new surveys. Results clearly indicate that the decrease in phosphorus is the main cause of a dramatic decrease in chlorophyll and large increase in water transparency, triggering the subsequent colonization of macrophytes in the river bed. A Generalized Linear Model analysis showed that the decrease in dissolved phosphorus had a relative importance 14 times higher than the increase in zebra mussel density to explain the variation of total chlorophyll. We suggest that the described changes in the lower Ebro River can be considered a novel ecosystem shift. This shift is triggering remarkable changes in the biological communities beyond the decrease of phytoplankton and the proliferation of macrophytes, such as massive colonization of Simulidae (black fly) and other changes in the benthic invertebrate communities that are currently investigated.

Assessing the effects of tertiary treated wastewater reuse on the presence emerging contaminants in a Mediterranean river (Llobregat, NE Spain).

PURPOSE: The Llobregat River, which is characterized by important fluctuations of the flow rates, receives treated waters from WWTPs. During the years 2007 and 2008, the Llobregat River basin suffered from a severe drought which affected the supply of drinking water facilities (DWF) that rely on the exploitation of the river water. The Catalan Water Agency implemented a water reuse experiment with the objective of maintaining the river flow rate at sufficiently high level so as to ensure the supply of raw water to Barcelona's major DWF. METHOD: A total of 103 emerging contaminants belonging to the groups of pharmaceuticals (74), illicit drugs (17) and oestrogens (12) were determined using LC-MS/MS methods in river water samples during the water reuse campaign. The effect of the reclaimed water discharge on the river water quality, in terms of contamination loads and environmental risk (based on the concentration addition mode), is discussed. RESULTS: Fifty-eight pharmaceuticals out of 74 monitored were detected at least in one sample. In river water upstream (site R0) majority of compounds were detected at low nanograms per litre levels, while downstream of discharge of tertiary effluent only few compounds were detected at levels higher than 100 ng L(-1) (i.e. acetaminophen, diclofenac, erythromycin, sulfamethazine), but never exceeding 500 ng L(-1). The total concentration of illicit drugs was found to be very low at both sampling sites (<50 ng L(-1)). No relevant ecotoxicity risks were identified, except for pharmaceuticals vs. algae. CONCLUSIONS: In general, the discharge of reclaimed water in the river influenced perceptibly in terms of concentrations, mass loads and environmental risk, especially for pharmaceuticals and in less extent for illicit drugs. Nevertheless, it was not very significant in any case.

Water toxicity assessment and spatial pollution patterns identification in a Mediterranean River Basin District. Tools for water management and risk analysis.

In compliance with the requirements of the EU Water Framework Directive, monitoring of the ecological and chemical status of Catalan river basins (NE Spain) is carried out by the Catalan Water Agency. The large amount of data collected and the complex relationships among the environmental variables monitored often mislead data interpretation in terms of toxic impact, especially considering that even pollutants at very low concentrations might contribute to the total toxicity. The total dataset of chemical monitoring carried out between 2007 and 2008 (232 sampling stations and 60 pollutants) has been analyzed using sequential advanced modeling techniques. Data on concentrations of contaminants in water were pre-treated in order to calculate the bioavailable fraction, depending on substance properties and local environmental conditions. The resulting values were used to predict the potential impact of toxic substances in complex mixtures on aquatic biota and to identify hot spots. Exposure assessment with Species Sensitivity Distribution (SSD) and mixture toxicity rules were used to compute the multi-substances Potentially Affected Fraction (msPAF). The combined toxicity of the pollutants analyzed in the Catalan surface waters might potentially impact more than 50% of the species in 10% of the sites. In order to understand and visualize the spatial distribution of the toxic risk, Self Organising Map (SOM), based on the Kohonen's Artificial Neural Network (ANN) algorithm, was applied on the output data of these models. Principal Component Analysis (PCA) was performed on top of Neural Network results in order to identify main influential variables which account for the pollution trends. Finally, predicted toxic impacts on biota have been linked and correlated to field data on biological quality indexes using macroinvertebrate and diatom communities (IBMWP and IPS). The methodology presented could represent a suitable tool for water managers in environmental risk assessment and management.

Wastewater reuse in Mediterranean semi-arid areas: The impact of discharges of tertiary treated sewage on the load of polar micro pollutants in the Llobregat river (NE Spain).

The presence of sewage-borne micro contaminants in environmental waters is directly related to the discharge of treated effluents from wastewater treatment plants (WWTP) and the flow rate of the receiving river waters. Mediterranean rivers, in particular, are characterized by important fluctuations in the flow rates and heavy pollution pressures resulting from extensive urban, industrial and agricultural activities. This translates into contamination levels in these rivers often higher than those in other larger European basins. The present work provides an overview of the occurrence of five groups of organic contaminants (131 compounds) namely pharmaceuticals, illicit drugs, polar pesticides, estrogens, alkylphenols and related ethoxylates in WWTP tertiary treatment effluents. Data gathered during a period of water reuse carried out in the lower stretch of the Llobregat river (NE Spain), in the surroundings of the town of Barcelona as a consequence of the severe drought that took place along the years 2007-2008 are presented as illustrative example. In general, measured concentrations of the target compounds were in the low to mid ngL(-1) range. The total concentration of each compound class downstream to the discharge point was similar or slightly higher than that found upstream. Regarding the loads calculated for each compound, the relative contribution from the river upstream and the tertiary effluent were highly compound depending with no apparent trend. However, estimation of the overall bulk loads for each compound class determined in the Llobregat river showed the following rank order: pharmaceuticals>alkylphenols>pesticides>illicit drugs≫estrogens.

Defining river types in a Mediterranean area: a methodology for the implementation of the EU Water Framework Directive.

The Water Framework Directive (WFD), approved at the end of 2000 by the European Union, proposes the characterization of river types through two classification systems (A and B) (Annex II of the WFD), thereby obtaining comparable reference sites and improving the management of aquatic systems. System A uses fixed categories of three parameters to classify rivers: three altitude ranges, four basin size ranges, and three geological categories. In the other hand, System B proposes to establish river types analyzing different factors considered as obligatory and optional. Here, we tested Systems A and B in the Catalan River Basin District (NE Spain). The application of System A results in 26 river types: 8 in the Pyrenees and 18 in the Iberic-Macaronesian ecoregions. This number would require the establishment of a complex management system and control of the ecological status in a relatively small river basin district. We propose a multivariant system to synthesize the environmental descriptors and to define river types using System B. We use five hydrological, seven morphological, five geological, and two climatic variables to discriminate among river types. This method results in fewer river type categories than System A but is expected to achieve the same degree of differentiation because of the large number of descriptors considered. Two levels are defined in our classification method using System B. Five "river types," defined at large scale (1:1,000,000), are mainly discriminated by annual runoff coefficient, air temperature, and discharge. This level is useful and could facilitate comparisons of results among European river basin districts. The second level defines 10 "subtypes of river management," mainly discriminated by geology in the basin and flow regime. This level is more adequate at local scale (1:250,000) and provides a useful tool for management purposes in relatively small and heterogeneous river basin districts.