Effects of the 2021 La Palma volcanic eruption on groundwater hydrochemistry: Geochemical modelling of endogenous CO2 release to surface reservoirs, water-rock interaction and influence of thermal and seawater.

Volcanic islands face unique challenges in protecting and managing their water resources due to their small size, limited freshwater availability, and vulnerability to natural hazards. The recent 2021 eruption of the Tajogaite volcano on La Palma Island in the Canary Islands, Spain, raised concerns regarding the potential impact on groundwater hydrochemistry. This work aimed to characterize and model the processes that lead to the measured hydrochemical impacts in the groundwater of La Palma as a consequence of the volcanic eruption. The study involved conducting three groundwater sampling campaigns during the eruption, and six after the eruption ceased. A total of 15 monitored points, including piezometers, wells, water galleries, and the main gully collector of the island, all relatively close (2 to15 km) to the erupted volcano, were sampled for the analysis of major solutes and SiO2. Unpublished hydrochemical data previous to the eruption were provided by the local water management authorities of La Palma (CIALP) and the Geological Survey of Spain (IGME). Statistical analyses were performed to assess the differences in groundwater composition before, during, and after the eruption, and a Principal Component Analysis (PCA) mixing model was calculated. Three compositional extreme waters were defined as end members in the system: (1) a high SiO2 computed thermal end member; (2) a low salinity computed fresh groundwater; (3) and seawater. The results of the mixing model showed two main events of maximum mixing ratios in the fresh groundwater reservoirs of La Palma after the eruption; the first one of seawater in July 2022, and the next one of thermal fluids in December 2022. This water mixing during and after the eruption, together with a volcanic CO2 input to the reservoirs, led to significant increases in the concentrations of Na, Ca, SiO2 and SO4 in fresh groundwater, as well as a drop in pH. The significance of these findings relies in improving our understanding of the effects of volcanic eruptions on groundwater, emphasizing the necessity for frequent monitoring and evaluation, given the scarcity and vulnerability of groundwater resources in volcanic islands.

Comparative study of emerging pollutants of interest in the groundwater of the volcanic islands of La Palma and El Hierro (Canary Islands).

Emerging pollutants (EPs) include a wide array of chemical compounds, as well as some microorganisms, which presence was unknown or unmeasurable until recently, or have recently started to be considered a threat towards the environment or animal and human health. No clear or homogeneous regulations exist for their measurement or control, and efforts should be made to assess their presence and offer solutions for their safe management, as well as to achieve an optimal protection of water resources. A previous study performed by our research group thoroughly studied a wide profile of EPs in El Hierro Island (Canary Islands) for the first time. Now, we present the study of the same panel of 70 EPs in La Palma Island (Canary Islands). 14 samples were collected in 2021, at different locations in La Palma island, representing seven municipalities (Los Llanos de Aridane, Santa Cruz de la Palma, El Paso, Breña Baja, Tazacorte, Barlovento and Fuencaliente) and four installation types (Piezometers/Wells, Wastewater Treatment Plant (WWTP), Water Gallery and Water Springs). High performance liquid chromatography-mass spectrometry (HPLC-MS) was performed to analyse the EP array, which included five chemical families: UV filters, UV blockers/stabilizers, parabens, Pharmaceutical Active Compounds (PhACs) and pesticides. Subsequently, a comprehensive descriptive and statistical analysis, including different tests was performed on the data obtained. Heterogeneous concentration levels of the EPs studied were found based on municipality and installation type among the island, with some of the PhACs and UV blockers/stabilizers showing very high levels, especially at Breña Baja and wastewater treatment plants (WWTPs). It is worth noting that some of the samples comprised within the WWTPs category were collected outside the treatment plant, after water has been treated, so they should not bear dangerous concentrations of any hazardous compound. The high presence of two pesticides, imidacloprid (ranging from 68.7 to 24,896.5 ng⋅L-1) and acetamiprid (ranging from 1010.7 to 5168.1 ng⋅L-1) was worth highlighting too. In addition, three EP concentration clusters were found to virtually divide the island based on mathematical percentiles of EP mean concentrations, which can help gain more insight into the contamination status of the island and measures that could be taken for their management. Finally, a comparison between La Palma results and the profile observed at El Hierro by our research group was presented. Altogether, the study performed calls for a need to take actions towards avoiding entrance of EPs in the water cycle, and not just focusing on remediation strategies once they have reached the groundwater, freshwater or soil.

First emerging pollutants profile in groundwater of the volcanic active island of El Hierro (Canary Islands).

Emerging pollutants (EPs) are substances present in wastewater that have not been studied, previously, leading to ambiguity in regulations for their presence in water resources. Territories that are highly dependent on groundwater resources are at a high risk of suffering the consequences of EP contamination due to their dependence on good quality groundwater for agriculture, drinking, and other uses. A relevant example is El Hierro (Canary Islands), which was declared a biosphere reserve by the UNESCO in 2000 and is almost completely powered by renewable energies. Using high performance liquid chromatography-mass spectrometry, the concentrations of 70 EPs were assessed at 19 sampling points on El Hierro. The results indicated that no pesticides were present in groundwater; however, varied concentration levels of ultraviolet (UV) filters, UV stabilizers/blockers and pharmaceutically active compounds (PhACs) were found, with La Frontera being the most contaminated municipality. With regard to the different installation types, piezometers and wells were the ones showing the highest concentrations for most EPs. Interestingly, the depth of sampling correlated positively with EP concentration, and four different clusters virtually dividing the island into two areas could be identified based on the presence of each EP. More studies should be performed to ascertain why a few of the EPs showed considerably high concentrations at different depths. The results obtained highlight the need to, not only implement remediation measures once EPs have reached the soil and aquifers, but also to avoid their incorporation into the water cycle via homes, animal husbandry, agriculture, industry, and wastewater treatment plants (WWTPs).

Stormwater management in urban areas using dry gallery infiltration systems.

The increase in the frequency of extreme precipitation events due to climate change, together with the continuous development of cities and surface sealing that hinder water infiltration into the subsoil, is accelerating the search for new facilities to manage stormwater. The Canary Islands (Spain) are taking advantage of the knowledge acquired in the construction of water mines to exploit a novel stormwater management facility, which we have defined as a dry gallery. Dry galleries are constituted by a vertical well connected to a horizontal gallery dug into highly permeable volcanic layers of the vadose zone, from where infiltration takes place. However, the lack of scientific knowledge about these facilities prevents them from being properly dimensioned and managed. In this work, we simulate for the first time the infiltration process and the wetting front propagation from dry galleries based on a 3D unsaturated flow model and provide some recommendations for the installation and sizing of these facilities. The fastest advance of the wetting front takes place during the earliest times of infiltration (<2 h), with plausible propagation velocities and infiltration rates higher than 1000 m∙d-1 and 2 m3∙s-1. As time progresses, the propagation velocity and infiltration rate decrease as a consequence of the hydraulic gradient attenuation between the gallery and the aquifer. Therefore, stormwater infiltration is a highly transient process in which a sizing underestimation of 100% may be committed if unsaturated conditions or geological configuration are neglected.

Defining the exploitation patterns of groundwater heat pump systems.

Shallow geothermal systems are the most efficient and clean technology for the air-conditioning of buildings and constitutes an emergent renewable energy resource in the worldwide market. Undisturbed systems are capable of efficiently exchanging heat with the subsurface and transferring it to human infrastructures, providing the basis for the successful decarbonisation of heating and cooling demands of cities. Unmanaged intensive use of groundwater for thermal purposes as a shallow geothermal energy (SGE) resource in urban environments threatens the resources' renewability and the systems' performance, due to the thermal interferences created by a biased energy demand throughout the year. The exploitation regimes of 27 groundwater heat pump systems from an alluvial aquifer were firstly examined using descriptive statistics. Linear relationships between abstraction and injection temperatures of the systems were assessed by calculating Pearson's r correlation coefficient, and used as an evidence of thermal interferences. Then, time series of flow rate, operation temperature and energy transfer were modelled by means of spectral analysis and sinusoidal regression methods, followed by the definition of the relative exploitation patterns. The exploitation regimes examined presented a clear cooling bias and a similar cyclicality. The amplitudes correlated with the different end-user's activities (e.g. medical centres) when high frequency cycles were observed, while climatization strategies (e.g. constant flow rates and modulation of injection temperatures) did so when low frequency cycles were detected. The time series models allowed defining the relative operational pattern of a system and the groups of systems following such patterns. The biases in exploitation regimes of groundwater heat pump systems existing in Mediterranean areas require correction measures to ensure a more balanced exploitation of the SGE resources. The definition of the characteristic exploitation pattern proposed could be applied to guide resource managers by identifying unbalanced systems, understanding existent exploitation strategies and proposing corrective alternative plans.

Decreased waterborne pathogenic bacteria in an urban aquifer related to intense shallow geothermal exploitation.

The implications of intensive use of shallow geothermal energy resources in shallow urban aquifers are still not known for waterborne pathogens relevant to human health. Firstly, we hypothesized that waterborne enteric pathogens would be relatively increased in heated groundwater plumes. To prove this, microbiological sampling of 31 piezometers covering the domain of an urban groundwater body affected by microbiological contamination and energetically exploited by 70 groundwater heat pump systems was performed. Mean differences of pathogenic bacteria contents between impacted and non-impacted monitoring points were assessed with a two-tailed independent Student's t-test or Mann-Whitney U and correlation coefficients were also calculated. Surprisingly, the results obtained revealed a significant and generalized decrease in waterborne pathogen contents in thermally impacted piezometers compared to that of non-impacted piezometers. This decrease is hypothesized to be caused by a heat shock to bacteria within the heat exchangers. The statistically significant negative correlations obtained between waterborne pathogen counts and temperature could be explained by the spatial distribution of the bacteria, finding that bacteria start to recover with increasing distance from the injection point. Also, different behavior groups fitting exponential regression models were found for the bacteria species studied, justified by the different presence and influence of several aquifer parameters and major, minor and trace elements studied, as well as the coexistence with other bacteria species. The results obtained from this work reinforce the concept of shallow geothermal resources as a clean energy source, as they could also provide the basis to control the pathogenic bacteria contents in groundwater bodies.