Occurrence of emerging contaminants in three river basins impacted by wastewater treatment plant effluents: Spatio-seasonal patterns and environmental risk assessment.

The concern on the fate and distribution of contaminants of emerging concern (CECs) is a burning topic due to their widespread occurrence and potential harmful effects. Particularly, antibiotics have received great attention due to their implications in antimicrobial resistance occurrence. The impact of wastewater treatment plants (WWTP) is remarkable, being one of the main pathways for the introduction of CECs into aquatic systems. The combination of novel analytical methodologies and risk assessment strategies is a promising tool to find out environmentally relevant compounds posing major concerns in freshwater ecosystems impacted by those wastewater effluents. Within this context, a multi-target approach was applied in three Spanish river basins affected by different WWTP treated effluents for spatio-temporal monitoring of their chemical status. Solid phase extraction followed by ultra-high-performance liquid chromatography were used for the quantification of a large panel of compounds (n = 270), including pharmaceuticals and other consumer products, pesticides and industrial chemicals. To this end, water samples were collected in four sampling campaigns at three locations in each basin: (i) upstream from the WWTPs; (ii) WWTP effluent discharge points (effluent outfall); and (iii) downstream from the WWTPs (500 m downriver from the effluent outfall). Likewise, 24-h composite effluent samples from each of the WWTPs were provided in all sampling periods. First the occurrence and distribution of these compounds were assessed. Diverse seasonal trends were observed depending on the group of emerging compounds, though COVID-19 outbreak affected variations of certain pharmaceuticals. Detection frequencies and concentrations in effluents generally exceeded those in river samples and concentrations measured upstream WWTPs were generally low or non-quantifiable. Finally, risks associated with maximum contamination levels were evaluated using two different approaches to account for antibiotic resistance selection as well. From all studied compounds, 89 evidenced environmental risk on at least one occasion in this study.

Spatio-seasonal patterns of the impact of wastewater treatment plant effluents on antibiotic resistance in river sediments.

There is a growing concern about the risk of antibiotic resistance emergence and dissemination in the environment. Here, we evaluated the spatio-seasonal patterns of the impact of wastewater treatment plant (WWTP) effluents on antibiotic resistance in river sediments. To this purpose, sediment samples were collected in three river basins affected by WWTP effluents in wet (high-water period) and dry (low-water period) hydrological conditions at three locations: (i) upstream the WWTPs; (ii) WWTP effluent discharge points (effluent outfall); and (iii) downstream the WWTPs (500 m downriver from the effluent outfall). The absolute and relative abundances of 9 antibiotic resistance genes (ARGs), 3 mobile genetic element (MGE) genes, and 4 metal resistance genes (MRGs) were quantified in sediment samples, as well as a variety of physicochemical parameters, metal contents, and antibiotic concentrations in both sediment and water samples. In sediments, significantly higher relative abundances of most genes were observed in downstream vs. upstream sampling points. Seasonal changes (higher values in low-water vs. high-water period) were observed for both ARG absolute and relative abundances in sediment samples. Chemical data revealed the contribution of effluents from WWTPs as a source of antibiotic and metal contamination in river ecosystems. The observed positive correlations between ARG and MGE genes relative abundances point out to the role of horizontal gene transfer in antibiotic resistance dissemination. Monitoring plans that take into consideration spatio-temporal patterns must be implemented to properly assess the environmental fate of WWTP-related emerging contaminants in river ecosystems.

Global carbon sequestration through continental chemical weathering in a climatic change context.

This study simulates carbon dioxide (CO2) sequestration in 300 major world river basins (about 70% of global surface area) through carbonates dissolution and silicate hydrolysis. For each river basin, the daily timescale impacts under the RCP 2.6 and RCP 8.5 climate scenarios were assessed relative to a historical baseline (1969-1999) using a cascade of models accounting for the hydrological evolution under climate change scenarios. Here we show that the global temporal evolution of the CO2 uptake presents a general increase in the annual amount of CO2 consumed from 0.247 ± 0.045 Pg C year-1 to 0.261 and 0.273 ± 0.054 Pg C year-1, respectively for RCP 2.6 and RCP 8.5. Despite showing a general increase in the global daily carbon sequestration, both climate scenarios show a decrease between June and August. Such projected changes have been mapped and evaluated against changes in hydrology, identifying hot spots and moments for the annual and seasonal periods.

Combining punctual and high frequency data for the spatiotemporal assessment of main geochemical processes and dissolved exports in an urban river catchment.

The assessment of dissolved loadings and the sources of these elements in urban catchments' rivers is usually measured by punctual sampling or through high frequency sensors. Nevertheless, the combination of both methodologies has been less common even though the information they give is complementary. Major ion (Ca2+, Mg2+, Na+, K+, Cl-, SO42-, and alkalinity), organic matter (expressed as Dissolved Organic Carbon, DOC), and nutrients (NO3-, and PO43-) are punctually measured in the Deba river urban catchment (538 km2), in the northern part of the Iberian Peninsula (draining to the Bay of Biscay). Discharge, precipitation, and Electrical Conductivity (EC) are registered with a high frequency (10 min) in three gauging stations. The combination of both methodologies has allowed the assessment of major geochemical processes and the extent of impact of anthropogenic input on major composition of riverine water, as well as its spatial and temporal evolution. Three methodologies for loading estimation have been assessed and the error committed in the temporal aggregation is quantified. Results have shown that, even though carbonates dominate the draining area, the water major ion chemistry is governed by an evaporitic spring in the upper part of the catchment, while anthropogenic input is specially noted downstream of three wastewater treatment plants, in all nutrients and organic matter. The results of the present work illustrate how the combination of two monitoring methodologies allows for a better assessment of the spatial and temporal evolution on the major water quality in an urban catchment.

Multivariate statistical analyses for water and sediment quality index development: A study of susceptibility in an urban river.

In this study, multivariate statistical analyses were performed to develop water and sediment quality indexes, allowing us (i) to select with reliability the most appropriate chemical variables for the evaluation of river quality susceptibility; (ii) to weight the influence of each variable based on monitored data; (iii) to consider possible synergism or antagonism derived from the combined effect of several pollutants; and (iv) to express the quality as a deviation from selected site-specific reference conditions. For the establishment of these threshold/maximum values, combining two biological indicators related to denitrifying bacteria in sediments turned out to be applicable to ensure compliance with the European water quality standard. The joint implementation of water and sediment quality indexes assisted us in the rapid detection of the deleterious effect of different anthropogenic contamination sources, as well as the influence of hydrological regime seasonality on river quality. In addition, metal-dependent water quality appeared to be coupled to sediment dynamics, since they were preferentially adsorbed onto sediments during low flow seasons, whereas there was potential for metal mobilization to water during sediment resuspension in high flow seasons. Therefore, an annual determination of sediment quality index was also recommended as suitable tool for prospective monitoring water quality, identifying those sites which could deserve special attention during certain periods, and planning future strategies for river quality improvement. However, two limitations were found: (1) sediment was not appropriate for water physicochemical quality early monitoring due to organic matter and nutrient continuous transformation; and (2) a multimetric index did not provide a concise and definitive quality information, thus a new tool for combining with quality index was proposed for specifically evaluate the water and sediment quality by identifying pollutant/s of concern at each location.

Implications of denitrification in the ecological status of an urban river using enzymatic activities in sediments as an indicator.

A better understanding of the effects of a number of environmental factors on denitrification is vital for analyzing its role as nitrogen sink and providing deeper knowledge about the ecological status of a nitrate-rich ecosystem. Since few studies have addressed the occurrence and implications of denitrification in river sediments, and complexity of interactions among all these environmental factors makes comprehension of the process difficult, the potential of sediments from the Deba River to attenuate nitrate excess through denitrification was investigated. For this purpose, we adapted an in vitro method to measure activities of two enzymes contributing to the entire multiple-step nitrate reduction: Nitrate Reductase and Nitrite Reductase. The environmental features that influence both or single enzymatic activities were identified as oxygen availability, regulated directly by the moisture content or indirectly through the aerobic respiration, organic matter and nitrate content of sediments, and electrical conductivity and exchangeable sodium percentage of water. Additionally, our results showed that Nitrate Reductase catalyzes the principal limiting step of denitrification in sediments. Therefore, taking this enzymatic activity as an indicator, the southern part of the Deba River catchment presented low potential to denitrify but nitrate-limited sediments, whereas the middle and northern parts were characterized by high denitrification potential but nitrate-rich sediments. In general, this study on denitrifying enzymatic activities in sediments evaluates the suitability of the management of the effluents from wastewater treatment plants and municipal sewages to ensure a good ecological status of the Deba River.

Evaluating the role of particle size on urban environmental geochemistry of metals in surface sediments.

In this study, non-destructive techniques (X-ray Diffraction, Infrared and Scanning Electron Microscopy with Energy Dispersive spectroscopies) and invasive procedures (pseudo-total and sequential metal extraction methodologies) were used to highlight the significance of evaluating different particle sizes of sediments for assessing the potential environmental and health implications of metal geochemistry in an urban ecosystem. The variability in composition and properties between bulk (<2 mm) and fine (<63 µm) fractions influenced the availability, and by extension, the toxicity of metals. Indeed, the fine fraction presented not only higher metal pseudo-contents, but also greater available metal percentages. Besides the larger surface area per unit of mass and the high content of clay minerals, it was observed that it was principally Fe/Mn oxyhydroxides that favour adsorption of metals on the fine surface sediments. However, although we demonstrated that the origin of metals in the bulk surface sediments was predominantly lithogenic, use of the <2 mm fraction proved to be a useful tool for identifying different sources of available metals throughout the Deba River catchment. Specifically, discharges of untreated industrial and urban wastewaters, and even effluents from wastewater treatment plants were considered to greatly increase the health risk associated with metal availability. Finally, an evaluation of sediment dynamics in different hydrological conditions has highlighted the role played by each particle size as a vector of metal transport towards the coastal area. While resuspension of fine surface sediments notably induced significantly higher particulate metal concentrations in water during the dry season, resuspension of bulk surface sediments and, fundamentally, downstream transport of suspended particulate matter became more relevant and lowered the ecological risk during the wet season. Greater attention therefore needs to be paid to the new hydrological scenarios forecast to result from climate change, in which longer seasons with low river discharges are forecast.

Links between data on chemical and biological quality parameters in wastewater-impacted river sediment and water samples.

In many urban catchments, the discharge of effluents from wastewater treatment plants (WWTPs), as well as untreated wastewaters (UWWs), presents a major challenge for the maintenance of river sediment and water quality. The discharge of these effluents cannot only increase the concentration of metals, nutrients and organic compounds in fluvial ecosystems, but also alter the abundance, structure and function of river bacterial communities. Here, we present data on chemical and biological quality parameters in wastewater-impacted and non-impacted river surface sediment and water samples. Overall, the concentration of nutrients (inorganic nitrogen) and some heavy metals (Zn, Ni and Cr) was positively correlated with the nirS/16S rRNA ratio, while nirK- and nosZ-denitrifier populations were negatively affected by the presence of ammonium in sediments. Bacterial community structure was significantly correlated with the (i) combined influence of nutrient and metal concentrations, (ii) the contamination level (non-impacted vs. impacted sites), (iii) type of contamination (WWTP or UWW), and (iv) location of the sampling sites. Moreover, the higher abundance of five genera of the family Rhodocyclaceae detected in wastewater-impacted sites is also likely to be an effect of effluent discharge. The data presented here complement a broader study (Martínez-Santos et al., 2018) [1] and they are particularly useful for those interested in understanding the impact of wastewater effluents on the abundance, structure and function of river bacterial communities involved in nitrogen cycling.

Treated and untreated wastewater effluents alter river sediment bacterial communities involved in nitrogen and sulphur cycling.

Studying the dynamics of nitrogen and sulphur cycling bacteria in river surface sediments is essential to better understand their contribution to global biogeochemical cycles. Evaporitic rocks settled at the headwater of the Deba River catchment (northern Spain) lead to high values of sulphate concentration in its waters. Besides, the discharge of effluents from untreated and treated residual (urban and industrial) wastewaters increases the concentration of metals, nutrients and organic compounds in its mid- and low-water courses. The aim of this study was to assess the impact of anthropogenic contamination from untreated and treated residual and industrial wastewaters on the structure and function of bacterial communities present in surface sediments of the Deba River catchment. The application of a quantitative functional approach (qPCR) based on denitrification genes (nir: nirS+nirK; and nosZ), together with a 16S rRNA gene metabarcoding structural analysis, revealed (i) the high relevance of the sulphur cycle at headwater surface sediments (as reflected by the abundance of members of the Syntrophobacterales order, and the Sulfuricurvum and Thiobacillus genera) and (ii) the predominance of sulphide-driven autotrophic denitrification over heterotrophic denitrification. Incomplete heterotrophic denitrification appeared to be predominant in surface sediments strongly impacted by treated and untreated effluents, as reflected by the lower values of the nosZ/nir ratio, thus favouring N2O emissions. Understanding nitrogen and sulphur cycling pathways has profound implications for the management of river ecosystems, since this knowledge can help us determine whether a specific river is acting or not as a source of greenhouse gases (i.e., N2O).

Chemical and physiological metal bioaccessibility assessment in surface bottom sediments from the Deba River urban catchment: Harmonization of PBET, TCLP and BCR sequential extraction methods.

In the present study, the physiologically based extraction test PBET (gastric and intestinal phases) and two chemical based extraction methods, the toxicity characteristic leaching procedure (TCLP) and the sequential extraction procedure BCR 701 (Community Bureau of Reference of the European Commission) have been used to estimate and evaluate the bioaccessibility of metals (Fe, Mn, Zn, Cu, Ni, Cr and Pb) in sediments from the Deba River urban catchment. The statistical analysis of data and comparison among physiological and chemical methods have highlighted the relevance of simulate the gastrointestinal tract environment since metal bioaccessibility seems to depend on water and sediment properties such as pH, redox potential and organic matter content, and, primordially, on the form in which metals are present in the sediment. Indeed, metals distributed among all fractions (Mn, Ni, Zn) were the most bioaccessible, followed by those predominantly bound to oxidizable fraction (Cu, Cr and Pb), especially near major urban areas. Finally, a toxicological risk assessment was also performed by determining the hazard quotient (HQ), which demonstrated that, although sediments from mid- and downstream sampling points presented the highest metal bioaccessibilities, were not enough to have adverse effects on human health, Cr being the most potentially toxic element.

Influence of anthropogenic inputs and a high-magnitude flood event on metal contamination pattern in surface bottom sediments from the Deba River urban catchment.

The purpose of this study was to assess the influence of anthropogenic factors (infrastructure construction and industrial and wastewater inputs) and hydrological factors (high-magnitude flood events) on metal and organic contamination and on the source variability of sediments taken from the Deba River and its tributaries. The pollution status was evaluated using a sequential extraction procedure (BCR 701), enrichment factor, individual and global contamination factors and a number of statistical analysis methods. Zn, Cu and Cr were found to have significant input from anthropogenic sources, with moderately severe enrichment, together with an extremely high potential risk of contamination. The principal scavenger of Cu and Cr was organic matter, whereas Zn was uniformly distributed among all non-residual fractions. For Fe, the anthropogenic contribution was more obviously detected in bulk sediments (<2 mm) than in fine fractions (<63 µm). Finally, the recent construction of a rail tunnel traversing Wealden Facies evaporites, together with intense rainfalls, was the main reason for the change in the source variability of bottom sediments and metal distribution in headwaters. The occurrence of a high-magnitude flood event resulted in a washout of the river bed and led to a general decrease in fine-grained sediment and metal concentrations in labile fractions of channel-bottom sediments, and a consequent downstream transfer of the pollution.

Non-target effects of three formulated pesticides on microbially-mediated processes in a clay-loam soil.

An experiment was performed to study non-target effects of difenoconazole (fungicide), deltamethrin (insecticide) and ethofumesate (herbicide) on microbial parameters in a clay-loam soil. Pesticides were applied as commercial formulations to soil samples at different concentrations (5, 50 and 500 mg kg(-1) DW soil) and then incubated under laboratory conditions for 3 months. Throughout the incubation period, microbial parameters were determined at days 7, 30, 60 and 90. At 5 mg kg(-1) DW soil, none of the three pesticides caused significant changes in soil microbial parameters. In contrast, at 500 mg kg(-1) DW soil, pesticide application decreased overall soil microbial activity, negatively affecting the activity of soil enzymes. Similarly, at 500 mg kg(-1) DW soil, difenoconazole and ethofumesate, but not deltamethrin, caused a pesticide-induced stress on soil microbial communities, as reflected by the respiratory quotient. Besides, deltamethrin and ethofumesate at 50 and 500 mg kg(-1) DW soil resulted in lower values of denitrification potential. It was concluded that, although pesticide concentration had a somewhat inconsistent and erratic effect on soil microbial parameters, pesticide application at 500 mg kg(-1) DW soil did have an impact on many of the microbial parameters studied here.

Nitrogen transformations and greenhouse gas emissions from a riparian wetland soil: an undisturbed soil column study.

Riparian wetlands bordering intensively managed agricultural fields can act as biological filters that retain and transform agrochemicals such as nitrate and pesticides. Nitrate removal in wetlands has usually been attributed to denitrification processes which in turn imply the production of greenhouse gases (CO(2) and N(2)O). Denitrification processes were studied in the Salburua wetland (northern Spain) by using undisturbed soil columns which were subsequently divided into three sections corresponding to A-, Bg- and B2g-soil horizons. Soil horizons were subjected to leaching with a 200 mg NO3⁻L⁻¹ solution (rate: 90 mL day⁻¹) for 125 days at two different temperatures (10 and 20°C), using a new experimental design for leaching assays which enabled not only to evaluate leachate composition but also to measure gas emissions during the leaching process. Column leachate samples were analyzed for NO3⁻concentration, NH(4)(+) concentration, and dissolved organic carbon. Emissions of greenhouse gases (CO2 and N2O) were determined in the undisturbed soil columns. The A horizon at 20°C showed the highest rates of NO3⁻ removal (1.56 mg N-NO3⁻kg⁻¹ DW soil day⁻¹) and CO2 and N2O production (5.89 mg CO2 kg⁻¹ DW soil day⁻¹ and 55.71 µg N-N2O kg⁻¹ DW soil day⁻¹). For the Salburua wetland riparian soil, we estimated a potential nitrate removal capacity of 1012 kg N-NO3⁻ha⁻¹ year⁻¹, and potential greenhouse gas emissions of 5620 kg CO2 ha⁻¹ year⁻¹ and 240 kg N-N2O ha⁻¹ year⁻¹.