Study of the presence and environmental risk of organic contaminants policed by the European Union and other organic compounds in the water resources of a region overlapping protected areas: The Guadiaro River basin (southern Spain).

The study presented here is a first qualitative assessment of the occurrence of organic contaminants contemplated and not yet contemplated in European Union environmental legislation in water resources in the little anthropized Guadiaro River basin (70% of its area is covered by natural vegetation), in southern Spain. Water samples were collected from four carbonate aquifers, two detrital aquifers and four surface water courses and were analyzed for (i) 171 organic contaminants, (ii) major ions and (iii) stable isotopes (δ18OH2O, δ2HH2O, δ13CDIC). An environmental risk assessment was conducted through calculation of risk quotients comparing measured concentrations with ecotoxicological data found in the literature. Twenty-five organic contaminants were detected, at least once, including pesticides, pharmaceuticals, drugs of abuse and polycyclic aromatic hydrocarbons (PAHs). Cocaine and its main metabolite were detected in 85% and 95% of water samples, respectively (0.001-0.18 µg/L and 0.004-0.6 µg/L, respectively). Pyrene (PAH) was found in all water samples (0.001-0.015 µg/L) and forest fires were pointed out as a potential diffuse source. Relationship between rivers and aquifers is reflected by the distribution of organic contaminants, essentially the drugs of abuse. Concentration of contaminants were generally higher in groundwater samples, especially from detrital aquifers, potentially due to an accumulation process promoted by irrigation-return flows and by its slow dynamic compared to that of karstic systems. Pyrene concentration was also higher in some springs from karstic aquifers. Hence, calculated risk quotients were in general higher in groundwater, meaning that the threat to surface aquatic systems can grow as aquifers increase their influence on the water courses as the dry season progresses. The relationship between δ13CDIC and most organic contaminants (especially pyrene) reveal the role of the soil as storage media.

No transmission of SARS-CoV-2 in a patient undergoing allogeneic hematopoietic cell transplantation from a matched-related donor with unknown COVID-19.

The Hematology Department and its Hematopoietic Cell Transplantation (HCT) program implemented several measures during COVID-19 outbreak in order to keep clinical activities with the maximum security for both donors and recipients. Nevertheless, there was a lack of evidence whether blood products and specifically bone marrow can cause transfusion-transmitted infection. Initially, there were many uncertainties and did not exist formal recommendations. Before official statements were available, we performed an allogeneic HCT in a 57-year-old male from a related matched donor in the incubation period of COVID-19 where the patient did not develop the disease. Actual epidemiology data suggest that transmission may occur early in the course of infection, even from asymptomatic patients in the incubation period. In our knowledge this is the first case report of an adult hematopoietic cell donor with COVID-19 in the incubation period where the transplant is successfully completed with no transmission of SARS-CoV-2. The low concentration of viral RNA in plasma of patients with COVID-19 could support the safety of blood products, including peripheral blood hematopoietic cells. In conclusion, blood products including hematopoietic stem cells are safe in the context of COVID-19 pandemic.

Discriminating organic carbon from endokarstic moonmilk-type deposits by LIBS. The case of a natural carbonated Martian analogue.

Moonmilk-type deposits exemplify carbonated Martian analogues existing in the subsurface of Earth, an endokarstic speleothem with a possible biochemical origin composed principally by carbonates, mainly huntite and dolomite. In this work, samples of moonmilk located in Nerja Cave (southern Spain) have been studied by LIBS with the aim of identifying carbon of biogenic origin by establishing a relationship between a molecular emission indicator, CN signal, and the organic carbon content. The characterization of this kind of carbonate deposit with a multiple mineralogical composition has been completed using scanning electron microscopy (SEM), energy dispersive X-ray (EDX) and X-ray diffraction techniques for qualitative and semi-quantitative analysis. The information attained from LIBS regarding energy thresholds and time-resolved kinetics of CN emissions provides useful insight into the identification of different molecular emitters, namely organic and inorganic CN, depending on the laser irradiance and time settings conditions. These promising results are of application in the search and identification of biosignatures in upcoming planetary missions with astrobiological purposes.

Coronavirus pandemic: An opportunity to study the anthropogenic impact on micro-climate conditions and CaCO3 crystal morphology in the Nerja Cave (SE Spain).

Following the declaration of the COVID-19 pandemic, the Spanish Government restricted non-essential movements of all citizens and closed all public spaces, such as the Nerja Cave, until May 31, 2020. This particular condition of the closure of the cave provided a unique opportunity to study the micro-climate conditions and carbonate precipitation in this tourist cave without the presence of visitors. Our results show the significant effect of visitors on the air isotopic signature of the cave and on the genesis of the extensive dissolution features affecting the carbonate crystals formed in the tourist sector of the cave, alerting us to the possible corrosion of the speleothems located there. The movement of visitors within the cave also favours the mobilisation of aerial fungi and bacterial spores and their subsequent sedimentation simultaneously with the abiotic precipitation of carbonates from the drip water. The traces of these biotic elements could be the origin of the micro-perforations previously described in the carbonate crystals formed in the tourist galleries of the cave, but they are subsequently enlarged due to abiotic dissolution of the carbonates through these weaker zones.

Assessment of a wide array of contaminants of emerging concern in a Mediterranean water basin (Guadalhorce river, Spain): Motivations for an improvement of water management and pollutants surveillance.

This study investigates the occurrence and distribution of 185 organic contaminants (regulated pollutants and contaminants of emerging concern; CECs) in surface and groundwater of the Guadalhorce River basin (southern Spain) providing the most detailed dataset regarding organic pollution presented so far in this area. Up to 63 contaminants were detected in a monitoring campaign conducted in March 2016. Most contaminants were detected more frequently in surface water where they generally present higher concentrations suggesting the prevalence of wastewater discharges into streams as the main pollutant sources. In general, hydrophobic CECs presented the highest frequencies of detection and concentrations, which can be a consequence of several factors: (1) hydrophobic compounds show a higher retardation factor, which result, along with a continuous contaminant input, in a widespread and homogeneous distribution. In contrast, hydrophilic contaminants are more easily transported by water flows towards the lower basin and potentially accumulate as driven by groundwater flow and because of low renewal rates in the detrital aquifers caused by re-pumping and irrigation return flows in agricultural lands; (2) hydrophobic CECs studied in this research are mainly personal care products and organophosphate esters flame retardants and plasticizers, which are present in many different products and are used in large amounts; Also, (3) use of biosolids (reclaimed sewer sludge) as fertilizer for crops is potentially an additional diffuse source of organic pollutants in the study area contributing to a widespread distribution, especially for hydrophobic compounds. Obtained results highlight the need to better define the potential risk of non-regulated contaminants in water resources as well as the great impact of untreated wastewater discharges.

Coupling air temperature records and gravimetric data to interpret ventilation patterns in a Mediterranean karstic system (Nerja-Pintada caves, southern Spain).

Microclimate and geophysical studies are commonly applied to the characterization of karst systems although they are usually used separately. The main purpose of this manuscript is to show how the analysis of the data from both these research methods is a useful tool in the characterization of karst systems and we present the analysis of a specific case study: the Nerja- Pintada caves system. The joint analysis of the Nerja Cave and external air data (mainly temperatures) and the pre-existing gravimetric data of its surroundings (residual gravity anomaly map) have allowed us: 1) to postulate the existence of an unknown great cavity located near to the Nerja Cave and with direct influence in its ventilation and 2) to propose a new model of the Nerja-Pintada caves ventilation based on the changing connection between a "main cavity" system (Nerja Cave), with basically a transmissive function of airflows and an "annex cavities" sub-system, with different functioning as far as the airflow is concerned: transmissive in the case of Pintada Cave and capacitive in the case of the geophysically-located cave.

Contribution of isotopic research techniques to characterize high-mountain-Mediterranean karst aquifers: The Port del Comte (Eastern Pyrenees) aquifer.

Water resources in high mountain karst aquifers are usually characterized by high rainfall, recharge and discharge that lead to the sustainability of the downstream ecosystems. Nevertheless, these hydrological systems are vulnerable to the global change impact. The mean transit time (MTT) is a key parameter to describe the behavior of these hydrologic systems and also to assess their vulnerability. This work is focused on estimating MTT by using environmental tracers in the framework of high-mountain karst systems with a very thick unsaturated zone (USZ). To this end, it is adapted to alpine zones a methodology that combines a semi-distributed rainfall-runoff model to estimate recharge time series, and a lumped-parameter model to obtain ΜΤΤ. The methodology has been applied to the Port del Comte Massif (PCM) hydrological system (Southeastern Pyrenees, NE Spain), a karst aquifer system with an overlying 1000 m thick USZ. Six catchment areas corresponding to most important springs of the system are considered. The obtained results show that hydrologically the behavior of the system can be described by an exponential flow model (EM), with MTT ranging between 1.9 and 2.9 years. These ΜΤΤ values are shorter than those obtained by considering a constant recharge rate along time, which is the easiest and most applied aquifer recharge hypothesis when estimating ΜΤΤ through lumped-parameter models.

Multi-tracing of recharge seasonality and contamination in groundwater: A tool for urban water resource management.

In this study, sources of recharge and contamination in urban groundwater and in groundwater underneath a forest in the same aquifer were determined and compared. Data on hydro-chemical parameters and stable isotopes of water were collected in urban and forest springs in the Kharkiv region, Ukraine, over a period of 12 months. Groundwater transit time and precipitation contribution were calculated using hydrogeological data and stable isotopes of water to delineate groundwater recharge conditions. Hydro-chemical data, stable isotopes and emerging contaminants were used to trace anthropogenic groundwater recharge and approximate sewage and tap water contributions to the aquifer. The results indicated that each spring had unique isotopic signatures that could be explained by recharge conditions, groundwater residence time, and specific mixing patterns with sewage and water leaks. Elevated nitrate content, stable isotopes of nitrate, and the presence of emerging pollutants (mainly illicit drugs) in most of the urban springs confirmed mixing of urban groundwater with sewage leaks. These leaks amounted to up to 25% of total recharge and exhibited seasonal variations in some springs. Overall, the results show that urban groundwater receives variable seasonal contributions of anthropogenic components that increase the risk to the environment and human health, and reduce its usability for drinking water production. The multi-tracing approach presented can be useful for other cities worldwide that have similar problems of poor water management and inadequate sewage and water supply infrastructure.

Highlighting the importance of transitional ventilation regimes in the management of Mediterranean show caves (Nerja-Pintada system, southern Spain).

This study shows the utilization of the air CO2 exhaled by a very high number of visitors in the Nerja Cave as both a tracer and an additional tool to precisely evaluate the air circulation through the entire karst system, which includes non-touristic passages, originally free of anthropogenic CO2. The analysis of the temporal - spatial evolution of the CO2 content and other monitoring data measured from January 2015 to December 2016 in the Nerja-Pintada system, including air microbiological controls, has allowed us to define a new general ventilation model, of great interest for the conservation of the subterranean environment. During the annual cycle four different ventilation regimes and two ventilation modes (UAF-mode and DAF-mode) exist which determine the significance of the anthropogenic impact within the caves. During the winter regime, the strong ventilation regime and the airflow directions from the lowest to the highest entrance (UAF-mode) contribute to the rapid elimination of anthropogenic CO2, and this affects the whole karstic system. During the summer regime the DAF-mode ventilation (with airflows from the highest to the lowest entrances) is activated. Although the number of visitors is maximum and the natural ventilation of the karstic system is the lowest of the annual cycle, the anthropogenic impact only affects the Tourist Galleries. The transitional ventilation regimes -spring and autumn- are the most complex of the annual cycle, with changing air-flow directions (from UAF-mode to DAF-mode and vice versa) at diurnal and poly diurnal scale, which conditions the range of the anthropogenic impact in each sector of the karst system. The activation of the DAF-mode has been observed when the temperature difference between the external and air cave is higher than 5°C.

Groundwater dynamics in a hydrologically-modified alpine watershed from an ancient managed recharge system (Sierra Nevada National Park, Southern Spain): Insights from hydrogeochemical and isotopic information.

In many of the alpine watersheds of Sierra Nevada (Southern Spain) exists an ancient network of dug canals that collect, transport and facilitate the recharge the snowmelt in the underlying aquifer during the spring season. This practice, known as careos, in the lower part of the watersheds supply drinking water as spring discharge during the dry season. To study how this managed recharge technique modifies the natural response of these basins this work focuses on characterizing the hydrological behavior of one of the sites, the Berchules watershed. The mechanisms for mineralization of groundwater are based on geochemical processes such as evapo-concentration in the soil layer and silicate mineral weathering due to dissolved CO2 originated from both soil biogenic processes and the atmosphere. Groundwater presents a main hydrogeochemical calcium­magnesium-bicarbonate type facies, which is associated to groundwater flowing through the upper weathered silicates and quickly drained through springs located in the uplands and in the intermediate altitude catchment zone. Additionally, in the lower part of the basin some springs discharge mineralized groundwater with a sodium-calcium-bicarbonate composition associated to regional groundwater flow. In natural conditions, this hydrogeological system behaves as a sloping aquifer, occurring recharge between 1400 and 2500 m a.s.l. The springs discharge groundwater with an isotopic content and temperature in coherence with the local rainfall isotopic and thermal atmospheric altitudinal lines. Nevertheless, once the careo recharge begins the affected springs reveal the fingerprint of the concentrated recharge system by blurring the fingerprint of both the isotopic and thermal altitudinal dependence in the springs discharge. This validates the previous conceptual model and supports average recharge values of 141 ±â€¯140 mm/yr and total average water resources of 181 ±â€¯111 mm/yr which include a 40% increase in the study period due to the effect of the acequias de careo.