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.

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.

Application of hydrochemical and multi-isotopic (87Sr/86Sr, δ13C-DIC, δ2H-H2O, δ18O-H2O) tools to determine contamination sources and processes in the Guadalhorce River Basin, southern Spain.

The integrated use of multi-isotopic (87Sr/86Sr, δ13C-DIC, δ2H-H2O, δ18O-H2O) and hydrochemical data was applied in the highly anthropized Guadalhorce river basin, southern Spain, to improve the knowledge about water contamination sources and processes and to achieve improved water resource management. The results obtained highlight the importance of the use of isotopes as tracers of pollutants. DIC, δ2H-H2O, δ18O-H2O and δ13C-DIC allowed differentiating two water recharge end members: direct rainwater, infiltrated into the upper and lower detritic aquifers of the sub-basins, and the Guadalhorce dam system, which act as a source in some groundwater and surface waters of the lower sub-basin. 87Sr/86Sr data supported the existing conclusions in relation to pollution sources in the study area. The Triassic basement (evaporites) of the carbonate and detritic aquifers of the basin generally controls the natural 87Sr/86Sr composition in waters of the upper sub-basin. Only one groundwater sample reflects the influence of a human organic source (sewage) in its composition. On the other hand, mixing of human inorganic (fertilizers and detergents) strontium sources is required to explain the 87Sr/86Sr contents of the lower sub-basin waters. Discriminating the use of domestic detergents as another anthropogenic source of strontium and sulphate in waters is a novel finding in this research. The conclusions reached can be extrapolated to other anthropized basins.

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.

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.

SAR interferometry monitoring of subsidence in a detritic basin related to water depletion in the underlying confined carbonate aquifer (Torremolinos, southern Spain).

This research underlines the need to improve water management policies for areas linked to confined karstic aquifers subjected to intensive exploitation, and to develop additional efforts towards monitoring their subsidence evolution. We analyze subsidence related to intensive use of groundwater in a confined karstic aquifer, through the use of the InSAR technique, by the southern coast of Spain (Costa del Sol). Carbonates are overlain by an unconfined detritic aquifer with interlayered high transmissivity rocks, in connection with the Mediterranean Sea, where the water level is rather stable. Despite this, an accumulated deformation in the line-of-sight (LOS) direction greater than -100 mm was observed by means of the ERS-1/2 (1992-2000) and Envisat (2003-2009) satellite SAR sensors. During this period, the Costa del Sol experienced a major population increase due to the expansion of the tourism industry, with the consequent increase in groundwater exploitation. The maximum LOS displacement rates recorded during both time spans are respectively -6 mm/yr and -11 mm/yr, respectively. During the entire period, there was an accumulated descent of the confined water level of 140 m, and several fluctuations of more than 80 m correlating with the subsidence trend observed for the whole area. Main sedimentary depocenters (up to 800 m), revealed by gravity prospecting, partly coincide with areas of subsidence maxima; yet ground deformation is also influenced by other factors, the main ones being the fine-grained facies distribution and rapid urbanization due to high touristic pressure.