Disinfection by-product formation potential in response to variability in dissolved organic matter and nutrient inputs: Insights from a mesocosm study.

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.

Process-based modeling for ecosystem service provisioning: Non-linear responses to restoration efforts in a quarry lake under climate change.

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.

Global increase in methane production under future warming of lake bottom waters.

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.

Cross-continental importance of CH4 emissions from dry inland-waters.

Despite substantial advances in quantifying greenhouse gas (GHG) emissions from dry inland waters, existing estimates mainly consist of carbon dioxide (CO2) emissions. However, methane (CH4) may also be relevant due to its higher Global Warming Potential (GWP). We report CH4 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. CH4 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 CH4 contribution (normalized to CO2 equivalents; CO2-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 CH4 emissions were most strongly related to sediment organic matter content and moisture. Summing CO2 and CH4 emissions revealed a cross-continental average emission of 9.6 ± 17.4 g CO2-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 CH4 emissions. Hence, CH4 cannot be ignored if we want to fully understand the carbon (C) cycle of dry sediments.

Forecasting water temperature in lakes and reservoirs using seasonal climate prediction.

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).

Phenological shifts in lake stratification under climate change.

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.

Hidden treasures: Human-made aquatic ecosystems harbour unexplored opportunities.

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.

River pollution by priority chemical substances under the Water Framework Directive: A provisional pan-European assessment.

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.

Effects of human-driven water stress on river ecosystems: a meta-analysis.

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.

Dry habitats sustain high CO2 emissions from temporary ponds across seasons.

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 CO2 and CH4 fluxes from a set of temporary ponds across seasons. The ponds were in all occasion net CO2 emitters irrespective of the presence or absence of water. While the CO2 fluxes were in the upper range of emissions for freshwater lentic systems, CH4 fluxes were mostly undetectable. Dry habitats substantially contributed to these emissions and were always a source of CO2, whereas inundated habitats acted either as a source or a sink of atmospheric CO2 along the year. Higher concentrations of coloured and humic organic matter in water and sediment were linked to higher CO2 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 CO2 fluxes. The presence of methanogenic archaea in most ponds suggested the potential for episodic CH4 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.

Abundance of antibiotic resistance genes and bacterial community composition in wild freshwater fish species.

This study was aimed to determine the abundance of four antibiotic resistance genes (blaTEM, 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 blaTEM 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.

Abundance and Co-Distribution of Widespread Marine Archaeal Lineages in Surface Sediments of Freshwater Water Bodies across the Iberian Peninsula.

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.

Automatic High Frequency Monitoring for Improved Lake and Reservoir Management.

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.

Effects of subinhibitory ciprofloxacin concentrations on the abundance of qnrS and composition of bacterial communities from water supply reservoirs.

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.

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 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.

Distribution of dissolved organic matter in freshwaters using excitation emission fluorescence and Multivariate Curve Resolution.

Multivariate Curve Resolution Alternating Least Squares (MCR-ALS) method with the trilinearity constraint is proposed for the analysis of excitation-emission fluorescence data from Dissolved Organic Matter (DOM) in fresh water natural systems, and the results obtained are compared with those obtained with PARAFAC. The effects of different number of components and constraints on the stability of the proposed models are compared. MCR-ALS is shown to be an effective way to characterize and resolve DOM sources in natural fresh water systems from EEM data, with good correlation with experimentally measured DOM concentration values. MATLAB georeferenced mapping is used to illustrate the geographical distribution of resolved DOM contributions. MCR-ALS resolved EEM spectra are used to recognize the corresponding chemical groups assigned to possible DOM sources. Relationships between human activities and the environmental situation of the river system are discussed from these possible DOM sources.

Assessment of the water supply:demand ratios in a Mediterranean basin under different global change scenarios and mitigation alternatives.

Spatial differences in the supply and demand of ecosystem services such as water provisioning often imply that the demand for ecosystem services cannot be fulfilled at the local scale, but it can be fulfilled at larger scales (regional, continental). Differences in the supply:demand (S:D) ratio for a given service result in different values, and these differences might be assessed with monetary or non-monetary metrics. Water scarcity occurs where and when water resources are not enough to meet all the demands, and this affects equally the service of water provisioning and the ecosystem needs. In this study we assess the value of water in a Mediterranean basin under different global change (i.e. both climate and anthropogenic changes) and mitigation scenarios, with a non-monetary metric: the S:D ratio. We computed water balances across the Ebro basin (North-East Spain) with the spatially explicit InVEST model. We highlight the spatial and temporal mismatches existing across a single hydrological basin regarding water provisioning and its consumption, considering or not, the environmental demand (environmental flow). The study shows that water scarcity is commonly a local issue (sub-basin to region), but that all demands are met at the largest considered spatial scale (basin). This was not the case in the worst-case scenario (increasing demands and decreasing supply), as the S:D ratio at the basin scale was near 1, indicating that serious problems of water scarcity might occur in the near future even at the basin scale. The analysis of possible mitigation scenarios reveals that the impact of global change may be counteracted by the decrease of irrigated areas. Furthermore, the comparison between a non-monetary (S:D ratio) and a monetary (water price) valuation metrics reveals that the S:D ratio provides similar values and might be therefore used as a spatially explicit metric to valuate the ecosystem service water provisioning.

Modelling the emerging pollutant diclofenac with the GREAT-ER model: application to the Llobregat River Basin.

The present research aims at giving an insight into the increasingly important issue of water pollution due to emerging contaminants. In particular, the source and fate of the non-steroidal anti-inflammatory drug diclofenac have been analyzed at catchment scale for the Llobregat River in Catalonia (Spain). In fact, water from the Llobregat River is used to supply a significant part of the Metropolitan Area of Barcelona. At the same time, 59 wastewater treatment plants discharge into this basin. GREAT-ER model has been implemented in this basin in order to reproduce a static balance for this pollutant for two field campaigns data set. The results highlighted the ability of GREAT-ER to simulate the diclofenac concentrations in the Llobregat Catchment; however, this study also pointed out the urgent need for longer time series of observed data and a better knowledge of wastewater plants outputs and their parameterization in order to obtain more reliable results.

The combined impact of land use change and aquaculture on sediment and water quality in oligotrophic Lake Rupanco (North Patagonia, Chile, 40.8°S).

Water and sediment quality in North Patagonia's large, oligotrophic lakes are expected to suffer as native forest continues to be fragmented and degraded by its conversion to cropping and pasture land uses. These changes in land use are expected to increase diffuse nutrient loads to the region's lakes. In addition, these lakes are home to the world's second largest salmon aquaculture industry which provides additional point sources of nutrients within the lakes. We studied the combined influences of land use change and salmon farming on the nutrient concentrations in a North Patagonian lake (Lake Rupanco, 233 km(2) water surface, 163 m average depth) in four sub-watersheds ranging in disturbance from near-pristine forest to 53% converted to cropping and pasture. Nitrogen exports from the tributary sub-watersheds increased from 33 kg TN/km(2)/y to 621 kg TN/km(2)/y as the proportion of crop and pasture land increased. The combined nutrient load from land use change and salmon farming has led to significant differences in the nitrogen concentrations of the lake's water column and sediments in the near-shore zones across the lake. Total nitrogen concentrations in the sediments varied from 37 ± 18 mg/kg in near-pristine sub-watersheds without salmon farming to 6400 ± 698 mg/kg where the sub-watershed was dominated by crop and pasture lands combined with the presence of salmon farming. These results demonstrate the importance of considering the impacts of both salmon farming and land use on water and sediment quality for future environmental planning, management and decision making.