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The eleven priority, EPA phenolic pollutants were determined by liquid chromatography followed by two detectors in series; UV and electrochemical. Three different adsorbents, Envi-Carb (a carbon black) and two functionalized polymeric resins, Bond Elut PPL and another synthesized in our laboratory with an ocarboxybenzoyl moiety, were compared for solid-phase extraction (SPE) to detect lower concentrations of the eleven phenolics in natural waters. Higher recoveries were obtained using the functionalized polymeric adsorbents compared with Envi-Carb. When real samples were analysed, the synthetic adsorbent gave lower interference than Bond Elut PPL and phenol was determined at low levels with no humic and fulvic acid inter-ference when Na2SO3 was added. The linearity range for most compounds in tap water was 0.05–20 μg L−1 and the limits of detection were <35 ng L−1. Repeatability and reproducibility between days for real samples spiked at 0.1 μg L−1, expressed as relative standard deviation, were <8% and 10%, respectively. [ABSTRACT FROM AUTHOR]

Benzothiazole, benzotriazole and benzenesulfonamide derivates are well-known aquatic contaminants, although very few studies have been published about their occurrence in sewage sludge samples. In this paper, a pressurised hot water extraction (PHWE) method has been developed for the simultaneous determination of these families of compounds. The compounds were determined by LC-Orbitrap-HRMS and several clean-up strategies such as in-cell PHWE and solid-phase extraction (SPE) were tested to reduce the high matrix effect that occurs when sludge samples are analysed. Absolute recoveries using the whole method were above 80% and the matrix effect was under -20% for most of the compounds studied. Repeatability and reproducibility were usually under 10% (%RSD, 50 and 250ngg-1 (d.w.), n=5), while LODs and LOQs were between 0.25 and 25ngg-1 (d.w.) and 0.5 and 50ngg-1 (d.w.), respectively. The PHWE/SPE/LC-HRMS method developed was used to analyse several sludge samples collected from five sewage treatment plants (STPs) in Catalonia that use different sewage treatments. The most frequently determined compounds were benzotriazole derivates and the most abundant compound found was 2-hydroxybenzothiazole. [ABSTRACT FROM AUTHOR]

The hydrological continuum in rivers can be altered by the presence of small dams that modify the water residence time (WRT) and prevailing habitat, turning lotic river sections into lentic ones and influencing downstream reaches. The structure and activity of the microbial community occurring in the benthic and planktonic compartments can be modified by these small dams. We studied the microbial community processing of organic C along a sequence of 4 lentic-lotic sections in a medium-size Mediterranean river during base flow (spring) and low flow (summer). We hypothesized that longitudinal anomalies in WRT would influence the relative contribution of benthic vs planktonic compartments and their relevance in C processing along the river network, particularly during low flows. The biomass of free-living and particle-associated bacterioplankton was higher in the lentic sections, which had longer WRT, resulting in higher organic C processing (enzymatic activities and respiration). Microbial aggregates occurred in the lentic sections especially during the low-flow period and resulted in hotspots of organic C processing. The lotic reaches received a significant contribution of C in the form of bacterio- and phytoplankton. The small dams subsidized the lotic sections downstream and increased their respiration activity. Our results reveal the influence of small dams on organic C processing along the river network. Accounting for their effect, together with that of large dams, may be essential for accurate estimations of organicmatter transformation in river networks. [ABSTRACT FROM AUTHOR]

Abstract: The headwaters of the Llobregat and Ter Rivers are the main sources of water resources for the metropolitan areas of Barcelona and Girona. The historical discharge records of the headwater basins of these rivers during the period 1940–2000 have been analysed in relation with the changes in climate forcing and land cover occurring in these South Eastern Pyrenees catchments. Flow records showed high inter-annual variability, with a succession of decadal wet and dry spells, which made the detection of long-term trends in most of the gauging stations difficult. A comparison of the measured flows with those simulated by two rainfall–runoff models from climatic records showed some clear divergences. The trends of the measured flows for the study periods were negative whereas those explained by climate forcing had practically no trend. Analyses of other data periods may show negative and positive trends. Differences found between observed and simulated flows showed negative trends that were attributed to land use changes. Indeed, middle mountains in the study catchments have undergone an important increase of forest cover in the last decades. The main change observed in the area was an improvement of forest from sparse to dense coverage, and secondarily the change of land use from agriculture to pasture and forestry. The foreseeable effect of this land cover change is an increase of land evaporation caused by the increase in forest cover, not taken into account by the models used. The conclusion is that, although stream flows showed great decadal variability and significant trends driven by climate during some decadal-scale periods, water resources modelled from climate data for the whole period 1940–2000 did not show significant trends. In contrast, actual water resources experienced an annual decrease of about 0.25% of the mean annual resources during the same time span, due to an increase in forest cover in the headwaters. [Copyright &y& Elsevier]

Abstract: Water resources are directly and indirectly affected by anthropogenic activities (e.g., changes in land use) and natural factors (e.g., climate change), that is, global change. The Mediterranean basin is one of the most vulnerable regions of the world to global change, and one of the “hot spots” for forthcoming problems of water availability. The present review provides an overview about the relationship between chemical quality (especially concerning organic microcontaminants) and water scarcity, particularly in the Mediterranean area. We include an overview of environmental contaminants and analytical methodologies and consider the fate and the behavior of organic contaminants, and the effects of pollutants on ecosystems. [Copyright &y& Elsevier]

• Chemical pharmaceuticals fate model was calibrated for diclofenac at the Global scale. • 2.7% of the global river network has concentrations exceeding the EU limit of 100 ng DCL L-1. • Under business-as-usual scenarios, Global change will increase the DCL concentration. • Sanitation improvements won't suffice to mitigate impact on pharmaceuticals occurrence. • Source control mitigation actions need to be considered. Human consumption of pharmaceuticals leads to high concentrations of pharmaceuticals in wastewater, which is usually not or insufficiently collected and treated before release into freshwater ecosystems. There, pharmaceuticals may pose a threat to aquatic biota. Unfortunately, occurrence data of pharmaceuticals in freshwaters at the global scale is scarce and unevenly distributed, thus preventing the identification of hotspots, the prediction of the impact of Global Change (particularly streamflow and population changes) on their occurrence, and the design of appropriate mitigation actions. Here, we use diclofenac (DCL) as a typical pharmaceutical contaminant, and a global model of DCL chemical fate based on wastewater sanitation, population density and hydrology to estimate current concentrations in the river network, the impact of future changes in runoff and population, and potential mitigation actions in line with the Sustainable Development Goals. Our model is calibrated against measurements available in the literature. We estimate that 2.74 ± 0.63% of global river network length has DCL concentrations exceeding the proposed EU Watch list limit (100 ng L-1). Furthermore, many rivers downstream from highly populated areas show values beyond 1000 ng L-1, particularly those associated to megacities in Asia lacking sufficient wastewater treatment. This situation will worsen with Global Change, as streamflow changes and human population growth will increase the proportion of the river network above 100 ng L-1 up to 3.10 ± 0.72%. Given this background, we assessed feasible source and end-of-pipe mitigation actions, including per capita consumption reduction through eco-directed sustainable prescribing (EDSP), the implementation of the United Nations Sustainable Development Goal (SDG) 6 of halving the proportion of population without access to safely managed sanitation services, and improvement of wastewater treatment plants up to the Swiss standards. Among the considered end-of-pipe mitigation actions, implementation of SDG 6 was the most effective, reducing the proportion of the river network above 100 ng L-1 down to 2.95 ± 0.68%. However, EDSP brought this proportion down to 2.80 ± 0.64%. Overall, our findings indicate that the sole implementation of technological improvements will be insufficient to prevent the expected increase in pharmaceuticals concentration, and that technological solution need to be combined with source mitigation actions. [ABSTRACT FROM AUTHOR]

Changes in rainfall patterns driven by climate change affect the transport of dissolved organic matter (DOM) and nutrients through runoff to freshwater systems. This presents challenges for drinking water providers. DOM, which is a heterogeneous mix of organic molecules, serves as a critical precursor for disinfection by-products (DBPs) which are associated with adverse health effects. Predicting DBP formation is complex due to changes in DOM concentration and composition in source waters, intensified by altered rainfall frequency and intensity. We employed a novel mesocosm approach to investigate the response of DBP precursors to variability in DOM composition and inorganic nutrients, such as nitrogen and phosphorus, export to lakes. Three distinct pulse event scenarios, mimicking extreme, intermittent, and continuous runoff were studied. Simultaneous experiments were conducted at two boreal lakes with distinct DOM composition, as reflected in their color (brown and clear lakes), and bromide content, using standardized methods. Results showed primarily site-specific changes in DBP precursors, some heavily influenced by runoff variability. Intermittent and daily pulse events in the clear-water mesocosms exhibited higher haloacetonitriles (HANs) formation potential linked to freshly produced protein-like DOM enhanced by light availability. In contrast, trihalomethanes (THMs), associated with humic-like DOM, showed no significant differences between pulse events in the brown-water mesocosms. Elevated bromide concentration in the clear mesocosms critically influenced THMs speciation and concentrations. These findings contribute to understanding how changing precipitation patterns impact the dynamics of DBP formation, thereby offering insights for monitoring the mobilization and alterations of DBP precursors within catchment areas and lake ecosystems., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Authors. Published by Elsevier Ltd.. All rights reserved.)

Healthy freshwater ecosystems can provide vital ecosystem services (ESs), and this capacity may be hampered due to water quality deterioration and climate change. In the currently available ES modeling tools, ecosystem processes are either absent or oversimplified, hindering the evaluation of impacts of restoration measures on ES provisioning. In this study, we propose an ES modeling tool that integrates lake physics, ecology and service provisioning into a holistic modeling framework. We applied this model to a Dutch quarry lake, to evaluate how nine ESs respond to technological-based (phosphorus (P) reduction) and nature-based measures (wetland restoration). As climate change might be affecting the future effectiveness of restoration efforts, we also studied the climate change impacts on the outcome of restoration measures and provisioning of ESs, using climate scenarios for the Netherlands in 2050. Our results indicate that both phosphorus reduction and wetland restoration mitigated eutrophication symptoms, resulting in increased oxygen concentrations and water transparency, and decreased phytoplankton biomass. Delivery of most ESs was improved, including swimming, P retention, and macrophyte habitat, whereas the ES provisioning that required a more productive system was impaired (sport fishing and bird watching). However, our modeling results suggested hampered effectiveness of restoration measures upon exposure to future climate conditions, which may require intensification of restoration efforts in the future to meet restoration targets. Importantly, ESs provisioning showed non-linear responses to increasing intensity of restoration measures, indicating that effectiveness of restoration measures does not necessarily increase proportionally. In conclusion, the ecosystem service modeling framework proposed in this study, provides a holistic evaluation of lake restoration measures on ecosystem services provisioning, and can contribute to development of climate-robust management strategies., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 The Authors. Published by Elsevier Ltd.. All rights reserved.)

Lakes are significant emitters of methane to the atmosphere, and thus are important components of the global methane budget. Methane is typically produced in lake sediments, with the rate of methane production being strongly temperature dependent. Local and regional studies highlight the risk of increasing methane production under future climate change, but a global estimate is not currently available. Here, we project changes in global lake bottom temperatures and sediment methane production rates from 1901 to 2099. By the end of the 21st century, lake bottom temperatures are projected to increase globally, by an average of 0.86-2.60°C under Representative Concentration Pathways (RCPs) 2.6-8.5, with greater warming projected at lower latitudes. This future warming of bottom waters will likely result in an increase in methane production rates of 13%-40% by the end of the century, with many low-latitude lakes experiencing an increase of up to 17 times the historical (1970-1999) global average under RCP 8.5. The projected increase in methane production will likely lead to higher emissions from lakes, although the exact magnitude of the emission increase requires more detailed regional studies., (© 2022 The Authors. Global Change Biology published by John Wiley & Sons Ltd.)

Despite substantial advances in quantifying greenhouse gas (GHG) emissions from dry inland waters, existing estimates mainly consist of carbon dioxide (CO 2 ) emissions. However, methane (CH 4 ) may also be relevant due to its higher Global Warming Potential (GWP). We report CH 4 emissions from dry inland water sediments to i) provide a cross-continental estimate of such emissions for different types of aquatic systems (i.e., lakes, ponds, reservoirs, and streams) and climate zones (i.e., tropical, continental, and temperate); and ii) determine the environmental factors that control these emissions. CH 4 emissions from dry inland waters were consistently higher than emissions observed in adjacent uphill soils, across climate zones and in all aquatic systems except for streams. However, the CH 4 contribution (normalized to CO 2 equivalents; CO 2 -eq) to the total GHG emissions of dry inland waters was similar for all types of aquatic systems and varied from 10 to 21%. Although we discuss multiple controlling factors, dry inland water CH 4 emissions were most strongly related to sediment organic matter content and moisture. Summing CO 2 and CH 4 emissions revealed a cross-continental average emission of 9.6 ± 17.4 g CO 2 -eq m -2  d -1 from dry inland waters. We argue that increasing droughts likely expand the worldwide surface area of atmosphere-exposed aquatic sediments, thereby increasing global dry inland water CH 4 emissions. Hence, CH 4 cannot be ignored if we want to fully understand the carbon (C) cycle of dry sediments., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2021 Elsevier B.V. All rights reserved.)

Seasonal climate forecasts produce probabilistic predictions of meteorological variables for subsequent months. This provides a potential resource to predict the influence of seasonal climate anomalies on surface water balance in catchments and hydro-thermodynamics in related water bodies (e.g., lakes or reservoirs). Obtaining seasonal forecasts for impact variables (e.g., discharge and water temperature) requires a link between seasonal climate forecasts and impact models simulating hydrology and lake hydrodynamics and thermal regimes. However, this link remains challenging for stakeholders and the water scientific community, mainly due to the probabilistic nature of these predictions. In this paper, we introduce a feasible, robust, and open-source workflow integrating seasonal climate forecasts with hydrologic and lake models to generate seasonal forecasts of discharge and water temperature profiles. The workflow has been designed to be applicable to any catchment and associated lake or reservoir, and is optimized in this study for four catchment-lake systems to help in their proactive management. We assessed the performance of the resulting seasonal forecasts of discharge and water temperature by comparing them with hydrologic and lake (pseudo)observations (reanalysis). Precisely, we analysed the historical performance using a data sample of past forecasts and reanalysis to obtain information about the skill (performance or quality) of the seasonal forecast system to predict particular events. We used the current seasonal climate forecast system (SEAS5) and reanalysis (ERA5) of the European Centre for Medium Range Weather Forecasts (ECMWF). We found that due to the limited predictability at seasonal time-scales over the locations of the four case studies (Europe and South of Australia), seasonal forecasts exhibited none to low performance (skill) for the atmospheric variables considered. Nevertheless, seasonal forecasts for discharge present some skill in all but one case study. Moreover, seasonal forecasts for water temperature had higher performance in natural lakes than in reservoirs, which means human water control is a relevant factor affecting predictability, and the performance increases with water depth in all four case studies. Further investigation into the skillful water temperature predictions should aim to identify the extent to which performance is a consequence of thermal inertia (i.e., lead-in conditions)., (Copyright © 2021 The Authors. Published by Elsevier Ltd.. All rights reserved.)

This study presents a novel mixed-mode weak cation-exchange (WCX) material. This material was prepared by means of the functionalization of a mesoporous divinylbenzene (DVB) resin with maleic acid (maleic acid-DVB), which yielded a high carboxylic moiety content resulting in WCX interactions as well as suitable specific surface area for reversed-phase interactions. After the optimization of the solid-phase extraction (SPE) protocol to enhance the selectivity of the sorbent, this material was evaluated as a novel WCX sorbent in the SPE of a group of drugs from environmental water samples. The method is based on SPE followed by liquid chromatography (LC) coupled to high resolution mass spectrometry (HRMS) with an Orbitrap analyzer, and was validated and applied for the determination of basic drugs in river, effluent and influent wastewater samples. Maleic acid-DVB sorbent yielded suitable recovery rates (57% to 89%) and an acceptable matrix effect (<32%) thanks to the effective washing step included when these environmental waters were loaded through the novel resin. The method was applied to different environmental water samples and some basic drugs were suitably quantified in these environmental samples., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2021. Published by Elsevier B.V.)

One of the most important physical characteristics driving lifecycle events in lakes is stratification. Already subtle variations in the timing of stratification onset and break-up (phenology) are known to have major ecological effects, mainly by determining the availability of light, nutrients, carbon and oxygen to organisms. Despite its ecological importance, historic and future global changes in stratification phenology are unknown. Here, we used a lake-climate model ensemble and long-term observational data, to investigate changes in lake stratification phenology across the Northern Hemisphere from 1901 to 2099. Under the high-greenhouse-gas-emission scenario, stratification will begin 22.0 ± 7.0 days earlier and end 11.3 ± 4.7 days later by the end of this century. It is very likely that this 33.3 ± 11.7 day prolongation in stratification will accelerate lake deoxygenation with subsequent effects on nutrient mineralization and phosphorus release from lake sediments. Further misalignment of lifecycle events, with possible irreversible changes for lake ecosystems, is also likely.

Many inland waters exhibit complete or partial desiccation, or have vanished due to global change, exposing sediments to the atmosphere. Yet, data on carbon dioxide (CO 2 ) emissions from these sediments are too scarce to upscale emissions for global estimates or to understand their fundamental drivers. Here, we present the results of a global survey covering 196 dry inland waters across diverse ecosystem types and climate zones. We show that their CO 2 emissions share fundamental drivers and constitute a substantial fraction of the carbon cycled by inland waters. CO 2 emissions were consistent across ecosystem types and climate zones, with local characteristics explaining much of the variability. Accounting for such emissions increases global estimates of carbon emissions from inland waters by 6% (~0.12 Pg C y -1 ). Our results indicate that emissions from dry inland waters represent a significant and likely increasing component of the inland waters carbon cycle.

Artificial water bodies like ditches, fish ponds, weirs, reservoirs, fish ladders, and irrigation channels are usually constructed and managed to optimize their intended purposes. However, human-made aquatic systems also have unintended consequences on ecosystem services and biogeochemical cycles. Knowledge about their functioning and possible additional ecosystem services is poor, especially compared to natural ecosystems. A GIS analysis indicates that currently only ~ 10% of European surface waters are covered by the European Water Framework directive, and that a considerable fraction of the excluded systems are likely human-made aquatic systems. There is a clear mismatch between the high possible significance of human-made water bodies and their low representation in scientific research and policy. We propose a research agenda to build an inventory of human-made aquatic ecosystems, support and advance research to further our understanding of the role of these systems in local and global biogeochemical cycles as well as to identify other benefits for society. We stress the need for studies that aim to optimize management of human-made aquatic systems considering all their functions and to support programs designed to overcome barriers of the adoption of optimized management strategies.

In this paper, we build a preliminary inventory of dissolved phase water emissions of 36 of the 45 chemical priority substances under the European Union's Water Framework Directive. For point sources, we consider the European Pollutant Release and Transfer Register (E-PRTR) containing reported emissions from major industrial facilities. We consider all other sources as diffuse, and we estimate European average chemical emission factors from available measurements of dissolved phase concentrations, assuming simple emission patterns such as population and agricultural land. The emission inventory enables modelling concentrations, which have been compared with independent measurements. Due to the way they are estimated, they cannot withstand a point-by-point comparison. However, predicted concentrations exhibit a frequency distribution and order of magnitude compatible with observations, and match a fair proportion of independently reported exceedances of environmental quality standards for many of the substances studied. While apparently a preliminary picture based on crude simplifications, our representation suggests that simple drivers such as population and agriculture are useful to describe chemical pollution at European scale. From our preliminary inventory, E-PRTR industrial point emissions seem to account for a relatively small share of total emissions. Consequently, apart from specific measures such as upgrades to urban wastewater treatment plants in certain high impact areas, the management of priority substances may require a more strategic approach to emission control, addressing chemical use across sectors and the management of out-phased, legacy chemicals. At the same time, we advocate that improving emission inventories requires monitoring data reflecting the variability of emission patterns across Europe, as presently available monitoring data do not enable a catchment-specific estimation of emissions., (Copyright © 2019 The Authors. Published by Elsevier B.V. All rights reserved.)

Human appropriation of water resources may induce water stress in freshwater ecosystems when ecosystem needs are not met. Intensive abstraction and regulation cause river ecosystems to shift towards non-natural flow regimes, which might have implications for their water quality, biological structure and functioning. We performed a meta-analysis of published studies to assess the potential effects of water stress on nutrients, microcontaminants, biological communities (bacteria, algae, invertebrates and fish), and ecosystem functions (organic matter breakdown, gross primary production and respiration). Despite the different nature of the flow regime changes, our meta-analysis showed significant effects of human-driven water stress, such as significant increases in algal biomass and metabolism and reduced invertebrate richness, abundance and density and organic matter decomposition. Water stress also significantly decreased phosphate concentration and increased the concentration of pharmaceutical compounds. The magnitude of significant effects was dependent on climate, rainfall regime, period of the year, river size and type of water stress. Among the different causes of water stress, flow regulation by dams produced the strongest effects, followed by water abstraction and channelization.

Insight into how environmental change determines the production and distribution of cyanobacterial toxins is necessary for risk assessment. Management guidelines currently focus on hepatotoxins (microcystins). Increasing attention is given to other classes, such as neurotoxins (e.g., anatoxin-a) and cytotoxins (e.g., cylindrospermopsin) due to their potency. Most studies examine the relationship between individual toxin variants and environmental factors, such as nutrients, temperature and light. In summer 2015, we collected samples across Europe to investigate the effect of nutrient and temperature gradients on the variability of toxin production at a continental scale. Direct and indirect effects of temperature were the main drivers of the spatial distribution in the toxins produced by the cyanobacterial community, the toxin concentrations and toxin quota. Generalized linear models showed that a Toxin Diversity Index (TDI) increased with latitude, while it decreased with water stability. Increases in TDI were explained through a significant increase in toxin variants such as MC-YR, anatoxin and cylindrospermopsin, accompanied by a decreasing presence of MC-LR. While global warming continues, the direct and indirect effects of increased lake temperatures will drive changes in the distribution of cyanobacterial toxins in Europe, potentially promoting selection of a few highly toxic species or strains., Competing Interests: The authors declare no conflict of interest.

This study was aimed to determine the abundance of four antibiotic resistance genes (bla TEM , ermB, qnrS and sulI), as well as bacterial community composition associated with the intestinal mucus of wild freshwater fish species collected from the Foix and La Llosa del Cavall reservoirs, which represent ecosystems with high and low anthropogenic disturbance, respectively. Water and sediments from these reservoirs were also collected and analyzed to determine the pollution level by antibiotics. The bla TEM gene was only detected in brown trout and Ebro barbel, which were collected from La Llosa del Cavall reservoir. In contrast, the sulI and qnrS genes were only detected in common carp, which were collected from the Foix reservoir. Although the ermB gene was also detected in common carp, the values were below the limit of quantification. Likewise, water and sediment samples from the Foix reservoir had higher concentrations and more classes of antibiotics than those from La Llosa del Cavall. Pyrosequencing analysis of 16S rRNA genes revealed significant differences in bacterial communities associated with the intestinal mucus of fish species. Therefore, these findings suggest that anthropogenic activities are not only increasing the pollution of aquatic environments, but also contributing to the emergence and spread of antibiotic resistance in organisms that inhabit such environments., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

Despite the increasing understanding of the magnitude and drivers of carbon gas emissions from inland waters, the relevance of water fluctuation and associated drying on their dynamics is rarely addressed. Here, we quantified CO 2 and CH 4 fluxes from a set of temporary ponds across seasons. The ponds were in all occasion net CO 2 emitters irrespective of the presence or absence of water. While the CO 2 fluxes were in the upper range of emissions for freshwater lentic systems, CH 4 fluxes were mostly undetectable. Dry habitats substantially contributed to these emissions and were always a source of CO 2 , whereas inundated habitats acted either as a source or a sink of atmospheric CO 2 along the year. Higher concentrations of coloured and humic organic matter in water and sediment were linked to higher CO 2 emissions. Composition of the sediment microbial community was related both to dissolved organic matter concentration and composition, but we did not find a direct link with CO 2 fluxes. The presence of methanogenic archaea in most ponds suggested the potential for episodic CH 4 production and emission. Our results highlight the need for spatially and temporally inclusive approaches that consider the dry phases and habitats to characterize carbon cycling in temporary systems.

Synthetic cathinones have become popular in recent years, which would explain why their determination in influent sewage samples has already been documented. In the present study a method based on solid-phase extraction followed by liquid chromatography and high resolution mass spectrometry is developed, validated and applied to determine twelve cathinones and one of their metabolites in different environmental samples including influent and effluent sewage and river water. Two cation-exchange sorbents (Oasis MCX and Oasis WCX) were compared, with better results achieved with Oasis WCX in terms of apparent recoveries (70-100%) and matrix effects (lower than -34%). The method was validated with effluent sewage samples providing suitable figures of merit, with method quantification limits ranging from 1ng/L to 5ng/L and method detection limits from 0.1ng/L to 0.5ng/L for all the compounds. Of the different cathinones studied, three, namely methylone, mephedrone metabolite and methylenedioxypyrovalerone, were quantified at concentration levels of low ng/L in each of the different samples analysed, while a number of the other cathinones were also detected in some of the samples., (Copyright © 2017 Elsevier B.V. All rights reserved.)

Archaea inhabiting marine and freshwater sediments have a relevant role in organic carbon mineralization, affecting carbon fluxes at a global scale. Despite current evidences suggesting that freshwater sediments largely contribute to this process, few large-scale surveys have been addressed to uncover archaeal diversity and abundance in freshwater sedimentary habitats. In this work, we quantified and high-throughput sequenced the archaeal 16S rRNA gene from surficial sediments collected in 21 inland waterbodies across the Iberian Peninsula differing in typology and trophic status. Whereas methanogenic groups were dominant in most of the studied systems, especially in organic-rich sediments, archaea affiliated to widespread marine lineages (the Bathyarchaeota and the Thermoplasmata) were also ubiquitous and particularly abundant in euxinic sediments. In these systems, Bathyarchaeota communities were dominated by subgroups Bathyarchaeota-6 (87.95 ± 12.71%) and Bathyarchaeota-15 (8.17 ± 9.2%) whereas communities of Thermoplasmata were mainly composed of members of the order Thermoplasmatales. Our results also indicate that Archaea accounted for a minor fraction of sedimentary prokaryotes despite remarkable exceptions in reservoirs and some stratified lakes. Copy numbers of archaeal and bathyarchaeotal 16S rRNA genes were significantly different when compared according to system type (i.e., lakes, ponds, and reservoirs), but no differences were obtained when compared according to their trophic status (from oligotrophy to eutrophy). Interestingly, we obtained significant correlations between the abundance of reads (Spearman r = 0.5, p = 0.021) and OTU richness (Spearman r = 0.677, p < 0.001) of Bathyarchaeota and Thermoplasmata across systems, reinforcing the hypothesis of a potential syntrophic interaction between members of both lineages.

Models of microcontaminant fate and transport in wastewater treatment plants (WWTPs) and rivers have been developed and used to assist decision-making in the field of water management. These models come with parameter uncertainties that must be properly incorporated in the decision-making process. The main goal of this study is to evaluate how the magnitudes of key model parameter uncertainties influence the selection of end-of-pipe interventions (at WWTPs) designed to reduce the microcontaminant loads in rivers. We developed a model that describes the fate and removal of pharmaceuticals in WWTPs and the river network based on 3 key parameters: human pharmaceutical consumption and excretion (F) and the pharmaceutical degradation constants in WWTPs (k WWTP ) and rivers (k river ). We modelled the fate and transport of diclofenac in the Llobregat River basin (NE Spain). We calibrated the model using a Bayesian approach, which resulted in an accurate prediction of measured diclofenac loads at 9 locations along the Llobregat River and at the influents and effluents of 2 WWTPs (R 2  = 0.95). Using different scenarios, we evaluated three levels of uncertainty in the key model parameters. The first level of uncertainty corresponded to the reference distributions obtained from the Bayesian calibration. Then, for each parameter, we generated a narrower PDF (decreased uncertainty with respect to the reference) and a wider PDF (increased uncertainty). For each level of uncertainty, we evaluated increasing removal efficiencies of diclofenac at the WWTPs, from 38% to 98%. We assumed that removal efficiencies of up to 75% can be achieved by upgrading secondary treatment; beyond 75%, tertiary treatment is needed. The scenario analysis showed that achieving diclofenac removal efficiencies corresponding to tertiary treatment results in apparent concentration reductions (statistically significant differences relative to the reference situation), regardless of the level of uncertainty applied to the model parameters. However, upgrades in the secondary treatment resulted in apparent reductions only in the case of reduced uncertainty. We concluded that model uncertainty greatly influences the decisions that river basin authorities must make to reduce the microcontaminant loads released by WWTPs into rivers. In addition, we discussed research priorities to help reduce model uncertainty and thereby make more appropriate decisions., (Copyright © 2017 The Authors. Published by Elsevier Ltd.. All rights reserved.)

Recent technological developments have increased the number of variables being monitored in lakes and reservoirs using automatic high frequency monitoring (AHFM). However, design of AHFM systems and posterior data handling and interpretation are currently being developed on a site-by-site and issue-by-issue basis with minimal standardization of protocols or knowledge sharing. As a result, many deployments become short-lived or underutilized, and many new scientific developments that are potentially useful for water management and environmental legislation remain underexplored. This Critical Review bridges scientific uses of AHFM with their applications by providing an overview of the current AHFM capabilities, together with examples of successful applications. We review the use of AHFM for maximizing the provision of ecosystem services supplied by lakes and reservoirs (consumptive and non consumptive uses, food production, and recreation), and for reporting lake status in the EU Water Framework Directive. We also highlight critical issues to enhance the application of AHFM, and suggest the establishment of appropriate networks to facilitate knowledge sharing and technological transfer between potential users. Finally, we give advice on how modern sensor technology can successfully be applied on a larger scale to the management of lakes and reservoirs and maximize the ecosystem services they provide.

We used a short-term microcosm approach to investigate the influence of two different subinhibitory concentrations of ciprofloxacin (0.01 and 0.1 μg/ml) on both the abundance of a plasmid-mediated quinolone resistance determinant (qnrS) and the structure and composition of bacterial communities from impaired and pristine water supply reservoirs. The results showed that the abundance of the qnrS gene increases in water samples exposed to both subinhibitory concentrations of ciprofloxacin, especially in water samples from La Llosa del Cavall, which represents the pristine system. Subinhibitory ciprofloxacin concentrations also induced changes in bacterial community composition as indicated by the relative abundances of each operational taxonomic unit (OTU) across treatments. Therefore, our findings may be of significant importance because subinhibitory ciprofloxacin concentrations may promote antibiotic resistance and affect bacterial community composition in environmental settings., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

The occurrence of sweeteners in the environment has become a matter of concern due to the possibility of adverse effects on human health and wildlife species. One of the routes by which sweeteners enter the environment is through sewage sludge. Therefore, a method was developed with a selective-pressurized liquid extraction (S-PLE) followed by liquid chromatography-tandem mass spectrometry for the simultaneous determination of eight sweeteners in sewage sludge. The chromatographic separation was achieved in less than ten minutes using an amide polar-embedded reversed-phase column. Due to the high matrix effect present in the sample, an extensive study was conducted in order to overcome this issue, with C18 in-cell and solid-phase extraction (Oasis HLB) as a clean-up method. S-PLE/SPE recoveries at two levels of concentration (50μg/kg and 1000μg/kg in dry weight (d.w.), n=5) were higher than 61%. Repeatability and reproducibility at the same concentrations (%RSD, n=5) were lower than 11% and 16%, respectively. The limits of detection were 10μg/kg (d.w) for all compounds, except for cyclamate (5μg/kg (d.w.)). The method was successfully applied to sewage sludge samples from three sewage treatment plants located in Catalonia (Spain). Of the eight compounds, five were determined in all of the samples analysed, with acesulfame and saccharine being recorded at the highest concentrations of up to 481μg/kg and 591μg/kg (d.w.), respectively., (Copyright © 2015 Elsevier B.V. All rights reserved.)

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 10(4) mg·1000 inhab(-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. 10(3) mg·1000 inhab(-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., (Copyright © 2015 The Authors. Published by Elsevier B.V. All rights reserved.)