Occurrence and fate of perfluoroalkyl and polyfluoroalkyl substances (PFAS) in an urban aquifer located at the Besòs River Delta (Spain).

Urban aquifers are at risk of contamination from persistent and mobile organic compounds (PMOCs), especially per- and polyfluoroalkyl substances (PFAS), which are artificial organic substances widely used across various industrial sectors. PFAS are considered toxic, mobile and persistent, and have therefore gained significant attention in environmental chemistry. Moreover, precursors could transform into more recalcitrant products under natural conditions. However, there is limited information about the processes which affect their behaviour in groundwater at the field-scale. In this context, the aim of this study is to assess the presence of PFAS in an urban aquifer in Barcelona, and identify processes that control their evolution along the groundwater flow. 21 groundwater and 6 river samples were collected revealing the presence of 16 PFAS products and 3 novel PFAS. Short and ultra-short chain PFAS were found to be ubiquitous, with the highest concentrations detected for perfluorobutanesulfonic acid (PFBS), trifluoroacetic acid (TFA) and trifluoromethanesulfonic acid (TFSA). Long chain PFAS and novel PFAS were found to be present in very low concentrations (<50 ng/L). It was observed that redox conditions influence the behaviour of a number of PFAS controlling their attenuation or recalcitrant behaviour. Most substances showed accumulation, possibly explained by sorption/desorption processes or transformation processes, highlighting the challenges associated with PFAS remediation. In addition, the removal processes of different intensities for three PFAS were revealed. Our results help to establish the principles of the evolution of PFAS along the groundwater flow, which are important for the development of conceptual models used to plan and adopt site specific groundwater management activities (e.g., Managed Aquifer Recharge).

Combination of multivariate data analysis and mixing modelling to assess tracer potential of contaminants of emerging concern in aquifers.

Collected evidence has shown that contaminants of emerging concern (CECs) in conjunction with more conventional tracers (major ions, nutrients, isotopes etc.) can be used to trace pollution origin in aquatic systems. However, in highly mixed aquifer systems signals obtained from conventional tracers overlap diminishing their potential to be used as tracers. In this study, we present an approach that incorporates multivariate statistical analysis (principal component analysis (PCA) and Kohonen's Self-Organizing Map method (SOM)) and mixing modelling to identify the most suitable CECs to be employed as anthropogenic tracers. The study area is located in the Besòs River Delta (Barcelona, NE Spain) and represents the highly mixed aquifer system. A one-year monthly based monitoring campaign was performed to collect the information about the concentrations of 105 CECs as well as major and minor ions in the river and along the groundwater flow. The dimensionality of the obtained dataset was reduced to 25 CECs, based on their estimated health risk effects, for multivariate data analysis. The obtained results showed the overlap of conventional tracers' signals obtained from PCA. In case of CECs, PCA revealed differences in their distributions allowing the differentiation of the roles of natural attenuation processes, local and regional flows on their occurrence in different parts of the aquifer. This was not possible to do using solely CECs' distribution profiles. SOMs provided the lacking information about the modality of the distribution of each CECs, revealing their ability to represent factors controlling the groundwater hydrochemistry, which assist in defining their tracer potential. Based on the obtained results four identified persistent CECs, two with unimodal (lamotrigine and 5-Desamino-5-oxo-lamotrigine) and two with bimodal (carbamazepine and diazepam (higher modality was not revealed)) distributions, were selected to run a mixing model to compare their tracer performance.

Contaminants of emerging concern in the urban aquifers of Barcelona: Do they hamper the use of groundwater?

Urban aquifers are an alternative to obtain freshwater, but they are frequently polluted by contaminants of emerging concern (CECs). Therefore, there is a need to ascertain whether CECs are a water management challenge as they might limit the use of groundwater as safe drinking water even at ng L-1 concentration levels. To answer this question, it is required to evaluate human health-risk effects of measured CECs in the groundwater and to understand their behaviour at a field-scale. This study compiles data about the presence of CECs in the aquifers of Barcelona and its metropolitan area, evaluates health risk effects of measured CECs in the groundwater and presents approaches implemented to identify and quantify the coupled hydro-thermo-chemical processes that govern their fate in the subsurface. Some CECs might be harmful to humans, such as 5-methyl-1H-benzotriazole and the pharmaceuticals azithromycin valsartan, valsartan acid, lamotrigine, gabapentin, venlafaxine and lidocaine, which show very high to intermediate health risk effects. The number of harmful CECs and the level of their hazard increase from the groups of adults and 14-18 years old teens to the groups of 4-8 years old and 1-2 years old children. Thus, some CECs can limit the use of groundwater in Barcelona as potential drinking water source. Finally, knowledge gaps in understanding the integration of these processes into urban water resources management plans are identified, which will help to define groundwater potential uses and to assure the adequate protection of the human health and the environment.

Dynamics of nitrous oxide with depth in groundwater: Insights from ambient groundwater and laboratory incubation experiments (Hesbaye chalk aquifer, Belgium).

Aquifers under agricultural areas are considered to be an indirect source of nitrous oxide emission (N2O) to the atmosphere, which is the greenhouse gas (GHGs) characterized with the highest global warning potential and acts as a stratospheric ozone depletion agent. Previous investigations performed in the Cretaceous Hesbaye chalk aquifer in Eastern Belgium suggested that the dynamics of N2O in the aquifer is controlled by overlapping biochemical processes such as nitrification and denitrification. The current study aims to obtain better insight concerning the factors controlling the distribution of N2O concentration along a vertical dimension in the aquifer, and to capture and quantify the occurrence of nitrification and denitrification processes in the groundwater system. Low-flow groundwater sampling technique was undertaken at different depths in the aquifer to collect groundwater samples aiming at obtaining information about ambient aquifer hydrogeochemical conditions and their effect on the accumulation of GHGs. Afterwards, laboratory stable isotope experiments, using NO3- and NH4+ compounds labeled with heavy 15N isotope, were applied to quantify the rates of nitrification and denitrification processes. Ambient studies suggest that the occurrence of N transformation was related to denitrification while laboratory incubation experiments did not detect it. Such controversial results might be explained by the discrepancy between real aquifer conditions and lab design studies. Thus, additional in situ tracer experiments should be carried out in areas where natural groundwater fluxes do not flush the injected tracer too rapidly. In addition, it would be useful to conduct microbiological studies to obtain better insight into the nature of subsurface biofilm biotope.

Isotopic composition of nitrogen species in groundwater under agricultural areas: A review.

This work reviews applications of stable isotope analysis to the studies of transport and transformation of N species in groundwater under agricultural areas. It summarizes evidence regarding factors affecting the isotopic composition of NO3-, NH4+ and N2O in subsurface, and discusses the use of 11B, 18O, 13C, 34S, 87Sr/86Sr isotopes to support the analysis of δ15N values. The isotopic composition of NO3-, NH4+ and N2O varies depending on their sources and dynamics of N cycle processes. The reported δ15N-NO3- values for sources of NO3- are: soil organic N - +3‰-+8‰, mineral fertilizers - -8‰-+7‰; manure/household waste - +5‰ to +35‰. For NH4+ sources, the isotopic signature ranges are: organic matter - +2.4-+4.1‰, rainwater - -13.4-+2.3‰, mineral fertilizers - -7.4-+5.1‰, household waste - +5-+9‰; animal manure - +8-+11‰. For N2O, isotopic composition depends on isotopic signatures of substrate pools and reaction rates. δ15N values of NO3- are influenced by fractionation effects occurring during denitrification (ɛ=5-40‰), nitrification (ɛ=5-35‰) and DNRA (ɛ not reported). The isotopic signature of NH4+ is also affected by nitrification and DNRA as well as mineralization (ɛ=1‰), sorption (ɛ=1-8‰), anammox (ɛ=4.3-7.4‰) and volatilization (ɛ=25‰). As for the N2O, production of N2O leads to its depletion in 15N, whereas consumption - to enrichment in 15N. The magnitude of fractionation effects occurring during the considered processes depends on temperature, pH, DO, C/NO3- ratio, size of the substrate pool, availability of electron donors, water content in subsoil, residence time, land use, hydrogeology. While previous studies have accumulated rich data on isotopic composition of NO3- in groundwater, evidence remains scarce in the cases of NH4+ and N2O. Further research is required to consider variability of δ15N-NH4+ and δ15N-N2O in groundwater across agricultural ecosystems.