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In recent decades, there has been a growing interest in accurately characterizing the process of fresh groundwater discharge into the coastal ocean since it represents a significant pathway for solute from land to sea. Although SGD research has focused on quantifying water and solute fluxes, little is known about the physical forces, mechanisms, and distribution of SGD.Investigating interaction processes between the fresh and saltwater under the sea bottom represents a logistical and technical challenge. Traditionally, electrical geophysical methods have been solely used in the terrestrial part, and during the last decades, the method techniques have been introduced to marine environments. However, these methods are limited by their characteristics in obtaining subsurface resistivity data in the first few meters of the coast. Especially in the land-sea transition zone of microtidal environments, where many of the most critical processes take place, this data is traditionally not available. In this study, we developed a combination of methods to bridge the data gap between the terrestrial and marine realms. This study aims to characterize the FSGD in two aquifers from different geological contexts (alluvial and karstic) on the Mediterranean coast near Barcelona.To study the transition zone of the aquifer with a good spatial resolution, the amphibious electrical tomography method has been chosen, combining a terrestrial and aquatic line fixed in contact with the marine sediment. Profiles perpendicular to the coastline has been made in a shallow water area to obtain electrical resistivity data of the seabed at a local scale. The configuration used is Dipole-Dipole and Wenner-Schlumberger, with an investigation depth of 10 m. Based on the results, designing a 3D model of electrical resistivity in marine sediments was possible. In parallel to getting electrical resistivity data, manual piezometers were used to bring porewater samples at different points.We have been able to measure the presence of freshwater or brine, and we have identified differences in the geometry depending on the geological context, where the karst environment is the one that presents a more significant proportion of freshwater saturating the marine sediments. Therefore, amphibious electrical tomography is a non-invasive method that detects resistive zones of marine sediments associated with discharge processes and can be instrumental in characterizing the presence and distribution of SGD. AcknowledgmentsThis work was partly funded by the Spanish Government (grant no. PID2019-110212RB-C22) and the project TerraMar (grant no. ACA210/18/00007) of the Catalan Water Agency.

Mar Menor, on the northern Mediterranean coast of Spain, is a coastal lagoon with a surface of 135 km2, surrounded by agriculture fields and several towns, that support an important touristic activity. In addition, mining has been an historical activity on the region. In order to elucidate the input of metals supplied by Submarine Groundwater Discharge (SGD) to the lagoon and the spatial and temporal distribution of potentially toxic elements in this coastal ecosystem, the concentrations of dissolved metals (V, Cr, Mn, Fe, Co, Ni, Cu, Zn, As and Cd) were measured in surficial water courses (“ramblas”), groundwaters (including piezometers and boreholes) and lagoon waters. Samples were collected in two sampling campaigns (July and November, 2021), representing contrasting climatic seasons. These results were combined with the estimation of SGD fluxes to the coastal lagoon, allowing evaluating the fluxes of the studied pollutants. Occurrence of these pollutants in water from the lagoon has been previously registered, but none of those works has studied at the same time, and under a holistic point of view, all the possible aquatic pathways of dissolved metals, including the role of SGD as a conveyor of these potentially toxic elements. Keywords: Metal release, Coastal pollution, Land-Sea interaction, Submarine Groundwater Discharge.

Submarine Groundwater Discharge (SGD) is recognized as a major source of water and solutes to the coastal ocean, and it is particularly relevant in arid or semi-arid zones. SGD is generally defined as the flow of groundwater from continental margins to the coastal ocean, including thus both fresh groundwater from aquifer recharge and seawater recirculation through the coastal aquifer. Due to its high heterogeneity both in space and time, SGD is difficult to detect and quantify. As a consequence, numerous methods to study SGD have been developed over the last decades. These approaches mainly include hydrogeological approaches, geophysical techniques, direct seepage measurements, and the use of geochemical tracers. Each method presents its challenges, limitations, and advantages and each one works on different spatial and temporal scales, thus targeting different components of SGD. Therefore, comparing SGD studies with estimates derived from different methods is often complex and misleading if the characteristics and assumptions of each quantification technique are not taken into account. This highlights the need to conduct studies comparing SGD derived from different methods, not only to obtain more accurate SGD estimates but also to obtain instrumental information on the characteristics of the estimated fluxes. To this aim, a combined use of different approaches to estimate SGD was applied in a Mediterranean coastal lagoon (Mar Menor, Spain), including direct measurements with seepage meters, radium isotopes, and radon mass balance, 224Ra/228Th disequilibrium in coastal sediments, radon vertical profiles in porewater sediments, and hydrologic modeling. Mar Menor is Europe's biggest saline coastal lagoon, and it is connected to a highly anthropized quaternary aquifer. In this coastal system, SGD is likely playing a major role in the eutrophication of the lagoon. However, despite the economic and biological importance of this lagoon, data about this system is still incomplete, and mostly only hydrological modeling has been performed. Keywords: Submarine Groundwater Discharge, radioactive tracers, seepage meters, porewater exchange, hydrological modeling.

The Mar Menor coastal lagoon (Spain) is a critical ecological and socioeconomic ecosystem and the first in Europe to be granted rights of personhood. However, pollution from past and present activities such as mining, agriculture, urbanization, and tourism threatens its health and ecological stability. Previous research has shown the importance of metal contamination in the lagoon and its link to nearby mining activities, but little consideration has been given to historical changes in this industry and in other potential metal sources. In this work, metal concentrations have been analyzed in 12 sediment cores dated with 210Pb, allowing the reconstruction of the recent (last ~150 years) metal contamination in the lagoon. The main metal sources have been identified by using multivariate statistical methods. Metal contamination from mining activities (point-source pollution) peaked in the mid-20th century, whereas nonpoint-source metal contamination reached its highest level in more recent decades. Despite the current decrease in metal deposition trends, concentrations in surface sediments still exceed sediment quality and ecotoxicological thresholds in areas close to former mining sites. Therefore, they need to be considered in future management strategies, which should also include the evaluation of sources and processes that are still supplying them to the lagoon.

Submarine Groundwater Discharge (SGD) is recognized as a fundamental hydrological process that supports many coastal biogeochemical cycles and social-ecological systems. However, very little has been investigated about how SGD affects society and human well-being. Coastal services provided by ecosystems dependent on SGD can be analyzed and clustered into the four main categories of Ecosystem Services (i.e., Provisioning, Supporting, Regulating and Cultural), which are divided into subcategories defined as outcomes. This enables identifying and discussing both benefits and threats to coastal societies resulting from SGD outcomes. Due to the lack of academic literature on this matter, here we explore the academic and local knowledge of the social perception toward SGD and its ecosystem services (ES). This research is conducted through two case studies, the island of Mallorca and the Region of Salento, to unravel the similarities and particularities of each Mediterranean society regarding the SGD-ES identified and their historical evolution. Such evolution transitions from the management of the fresh groundwaters for human consumption to the exploitation by the tourism industry of cultural ecosystem services related to the same discharge. Our review also shows how compiling different search possibilities (e.g., local languages, including paper-based documents; grey literature; local knowledge; academic literature) has resulted in a significant increase in the reported ES and its understanding. In this direction, combing traditional and academic knowledge are key to accessing society's perception of most cultural ES. Therefore, SGD-ES studies are extremely locally-dependent, and thus regional or global require an in-depth understanding of all areas comprehended in the study. Overall, the research presented in this study contributes to a better understanding of the complexity of the SGD and its social implications. Therefore, this research presents to the academic community new insights from traditional knowledge and an opportunity to integrate multidisciplinarity into a study subject that has usually only been looked from the prism of natural sciences.

The use of radiotracer techniques has been a fundamental tool for characterizing fluxes of solutes and water flows into the coastal ocean driven by submarine groundwater discharge (SGD). Indeed, the scientific interest in the use of radionuclides as tracers of SGD started developing in the late 90s when high activities of Ra isotopes and 222Rn in the coastal ocean were associated with groundwater inputs. Since then, the number of articles published about SGD has considerably grown and the technical improvements in radiotracer methods have often been accompanied by concurrent scientific advances in the understanding of the process. Although current research in SGD is conducted through multiple techniques (direct measurements, hydrological, geophysical, and geochemical techniques), the use of tracers such as Ra isotopes and 222Rn continues to be the most used and widespread method. Therefore SGD estimates are likely to be highly dependent on the methodological biases associated with radiotracer techniques. The aim of this study is to evaluate the main biases and assumptions relative to the use of Ra isotopes and 222Rn in SGD studies through a meta-analysis of the published academic literature. The results of this work highlight that a significant number of SGD studies using radionuclides as tracers are based on erroneous assumptions or inaccurate calculations leading to unreliable SGD quantifications, thus preventing its use for comparison with other studies or extrapolating from local to regional-global scale. These results also emphasize that the SGD community should seek comparison, reproducibility, and multiapproach studies that help to understand the complexity of SGD in multiple sites and bridge the gap between different quantification methods.

Submarine Groundwater Discharge (SGD) is recognized as a relevant source of pollutants to the sea, but little is known about its relevance as a source of chemicals of emerging concern (CECs). Here, both the presence and distribution of a wide range of CECs have been evaluated in the most comprehensive manner to date, in a well-characterized Mediterranean coastal aquifer near Barcelona (Spain). Samples from coastal groundwater and seawater allowed for the unique spatial characterization of the pollutants present in the land-ocean interface, an outstanding research gap that required attention. The main goals were (1) to determine CECs in the aquifer, so as to evaluate the SGD as a relevant source of marine pollution, and (2) to identify new tracers to improve our understanding of SGD dynamics. To this end, 92 CECs were located in the aquifer by using wide-scope analytical target methodologies (>2000 chemicals). Among them, the perfluoroalkyl and polyfluoroalkyl substances (PFAS), along with the pharmaceuticals carbamazepine and topiramate, were revealed to be good markers for tracing anthropogenic contamination in ground- and seawater, in concrete situations (e.g., highly contaminated sites). Additionally, non-target analysis expanded the number of potential tracers, making it a promising tool for identifying both the source and the fate of pollutants., This work was funded by the project “Mixing and dispersion in the transport of energy and solutes (MEDISTRAES)” coded as PID2019-110212RB-C21 of the Spanish Government (I+D+I Retos Investigación). We acknowledge the contribution of all the members of the MEDISTRAES I, II and III project, from the Groundwater Hydrology Group of the Technical University of Catalonia (UPC) and the Spanish National Research Council (CSIC), the Autonomous University of Barcelona (UAB), the University of Barcelona (UB), the Geosciences Montpellier Laboratory, CNRS and the University of Rennes, for their support during experimental laboratory tests, the Argentona site creation, the setup of the electrodes during piezometer installation and for ensuring site maintenance. IDAEA-CSIC authors would like to express their gratitude to The Spanish Ministry of Science and Innovation through the support received as “Centro de Excelencia Severo Ochoa 2019–2023″. P. Gago-Ferrero acknowledges his Ramón y Cajal fellowship (RYC2019-027913-I) from the AEI-MICI. V. Rodellas acknowledges financial support from the Beatriu de Pinós postdoctoral programme of the Catalan Government (2019-BP-00241).

75 pages, Radionuclides, both from natural and anthropogenic origin, are powerful ocean tracers that provide key information on fluxes, pathways and time scales of marine processes. Their added value compared to hydrographic parameters (e.g., temperature and salinity) relies either on their known rates of radioactive decay and production or on their time-variable releases from sources. Both aspects introduce a temporal dimension that allows quantifying rates or time scales of marine processes. Their wide range of half-lives and historical inputs, together with their physicochemical characteristics allow tracing a broad spectrum of marine processes. This chapter aims at providing an overview of the application of radionuclides as tracers of ocean processes. The chapter is structured in four sections: The first part reviews the main principles of radioactivity and the origin of radionuclides. The second section introduces the key aspects that allow using radionuclides as ocean tracers, followed by (third section) three real and contemporary instructive examples that cover different marine processes and require radionuclides with specific properties: i) thorium-234/uranium-238 (234Th/238U) pair to quantify the biological pump, ii) radium (Ra) isotopes to estimate the magnitude of submarine groundwater discharge, and iii) iodine-129 (129I) to investigate the large-scale ocean circulation. Finally, this chapter provides a summary of the different methods and techniques used to measure radionuclides in seawater

10 pages, 5 figures, 2 tables.-- Data availability: Data will be made available on request, Estimating 210Pb sources/sinks is significant for understanding the transport processes and chronology of sediment in coastal seas. Although submarine groundwater discharge (SGD) has been recognized as an important pathway for the transport of terrestrial chemical components, the 210Pb source in coastal seas from SGD is generally ignored. In the present work, we built the 210Pb budget by analyzing the 210Pb activity concentrations in submarine groundwater (i.e., coastal well water and pore water), river water, and seawater in a typical aquaculture bay along the Chinese coast in the Beibu Gulf (Qinzhou Bay). The results showed that the 210Pb activity concentrations (Bq/m3) in well water, porewater, seawater and river water were 6.0 ± 3.6 (n = 13), 3.8 ± 0.4 (n = 2), 1.2 ± 0.3 (n = 4), and 1.9 ± 0.6 (n = 3), respectively. The SGD-derived 210Pb flux was calculated to be (3.3 ± 0.4) × 1010 Bq/yr (approximately 1.4 times the river input flux), which accounted for ∼18% of the total 210Pb sources in Qinzhou Bay. Although most of the 210Pb (>66%) would be buried into the sediment of this coastal bay, SGD-discharged dissolved 210Pb can account for approximately half of the ocean mixing, which is the second most important 210Pb sink in Qinzhou Bay. Therefore, based on these estimates, we have shown that the 210Pb input from SGD can be an important source at the coastal sea scale and needs to be accounted for in coastal sea areas, This work was supported by the National Natural Science Foundation of China (No. 42206166, 41906150), the Science Research Foundation of the Third Institute of Oceanography, MNR (No. 2020017), the Science and Technology Plan Project of Guangxi Province (No. Gui Science AD19245147), the China Postdoctoral Science Foundation (No. 2021M693780), and the Foundation of Xiamen Institute of Marine Development (KFY202204). VP acknowledges the ‘Severo Ochoa Centre of Excellence’ accreditation (CEX2019-000928-S)

Submarine groundwater discharge (SGD) links terrestrial and marine systems, but has often been overlooked in coastal nutrient budgets because it is difficult to quantify. In this Review, we examine SGD nutrient fluxes in over 200 locations globally, explain their impact on biogeochemistry and discuss broader management implications. SGD nutrient fluxes exceed river inputs in ~60% of study sites, with median total SGD fluxes of 6.0 mmol m−2 per day for dissolved inorganic nitrogen, 0.1 mmol m−2 per day for dissolved inorganic phosphorus and 6.5 mmol m−2 per day for dissolved silicate. SGD nitrogen input (mostly in the form of ammonium and dissolved organic nitrogen) often mitigates nitrogen limitation in coastal waters, since SGD tends to have high nitrogen concentrations relative to phosphorus (76% of studies showed N:P values above the Redfield ratio). It is notable that most investigations do not distinguish saline and fresh SGD, although they have different properties. Saline SGD is a ubiquitous, diffuse pathway releasing mostly recycled nutrients to global coastal waters, whereas fresh SGD is occasionally a local, point source of new nutrients. SGD-derived nutrient fluxes must be considered in water quality management plans, as these inputs can promote eutrophication if not properly managed. Submarine groundwater discharge transports nutrients from terrestrial to marine systems, but is often ignored in coastal biogeochemistry. In this Review, the fluxes, impacts and management implications of this discharge are examined and compared with riverine fluxes globally.

International audience; Radium isotopes and radon are routinely used as tracers to quantify groundwater and porewater fluxes into coastal and freshwater systems. However, uncertainties associated with the determination of the tracer flux are often poorly addressed and often neglect all the potential errors associated with the conceptualization of the system (i.e., conceptual uncertainties). In this study, we assess the magnitude of some of the key uncertainties related to the determination of the radium and radon inputs supplied by groundwater and porewater fluxes into a waterbody (La Palme Lagoon, France). This uncertainty assessment is addressed through a single model ensemble approach, where a tracer mass balance is run multiple times with variable sets of assumptions and approaches for the key parameters determined through a sensitivity test. In particular, conceptual uncertainties linked to tracer concentration, diffusive fluxes, radon evasion to the atmosphere, and change of tracer inventory over time were considered. The magnitude of porewater fluxes is further constrained using a comparison of independent methods: (1) 224 Ra and (2) 222 Rn mass balances in overlying waters, (3) a model of 222 Rn deficit in sediments, and (4) a fluid-salt numerical transport model. We demonstrate that conceptual uncertainties are commonly a major source of uncertainty on the estimation of groundwater or porewater fluxes and they need to be taken into account when using tracer mass balances. In the absence of a general framework for assessing these uncertainties, this study provides a practical approach to evaluate key uncertainties associated to radon and radium mass balances.

20 pages, 8 figures, 2 tables, supporting Information https://doi.org/10.1111/mec.16695.-- Data availabitiy statement: DNA sequences and associated metadata: European Nucleotide Archive (ENA) under accession numbers PRJEB52186. The environmental metadata and the nonrarefied ASV and taxonomic tables are provided as Tables S2–S4, Subterranean estuaries are biogeochemically active coastal sites resulting from the underground mixing of fresh aquifer groundwater and seawater. In these systems, microbial activity can largely transform the chemical elements that may reach the sea through submarine groundwater discharge (SGD), but little is known about the microorganisms thriving in these land-sea transition zones. We present the first spatially-resolved characterization of the bacterial assemblages along a coastal aquifer in the NW Mediterranean, considering the entire subsurface salinity gradient. Combining bulk heterotrophic activity measurements, flow cytometry, microscopy and 16S rRNA gene sequencing we find large variations in prokaryotic abundances, cell size, activity and diversity at both the horizontal and vertical scales that reflect the pronounced physicochemical gradients. The parts of the transect most influenced by freshwater were characterized by smaller cells and lower prokaryotic abundances and heterotrophic production, but some activity hotspots were found at deep low-oxygen saline groundwater sites enriched in nitrite and ammonium. Diverse, heterogeneous and highly endemic communities dominated by Proteobacteria, Patescibacteria, Desulfobacterota and Bacteroidota were observed throughout the aquifer, pointing to clearly differentiated prokaryotic niches across these transition zones and little microbial connectivity between groundwater and Mediterranean seawater habitats. Finally, experimental manipulations unveiled large increases in community heterotrophic activity driven by fast growth of some rare and site-specific groundwater Proteobacteria. Our results indicate that prokaryotic communities within subterranean estuaries are highly heterogeneous in terms of biomass, activity and diversity, suggesting that their role in transforming nutrients will also vary spatially within these terrestrial–marine transition zones, This work was funded by the Spanish Ministry of Science, Innovation and Universities (MICINN) through the GRAMMI project (RTI2018-099740-J-I00), the Ramon y Cajal contract (RYC2019-026758-I) and partly by the project MEDISTRAES III (PID2019-110311RB-C22 and PID2019-110212RB-C21). Additional financial support was provided by grants SPIP2020-02595 (Ministry for the Ecological Transition and the Demographic Challenge [MITECO]) with funding from the Spanish government through the ‘Severo Ochoa Centre of Excellence’ accreditation (CEX2019-000928-S). JGO acknowledges the financial support of the Spanish Ministry of Science, Innovation and Universities, through the “Maria de Maeztu” programme for Units of Excellence (CEX2019-000940-M). VR acknowledges financial support from the Beatriu de Pinós postdoctoral programme of the Catalan Government (2019-BP-00241). AAK acknowledges financial support from ICTA “Unit of Excellence” (MinECo, MDM2015-0552-17-1) and PhD fellowship, BES-2017-080740. The coauthor AF is a Serra Húnter Fellow. MDF acknowledges the economic support from the FI-2017 fellowships of the Generalitat de Catalunya autonomous government (2017FI_B_00365). The authors would like to thank the support of the Generalitat de Catalunya to MERS (2017 SGR-1588), GHS (2017 SGR 1485) and 2017SGR/156, for additional fundin

Current Submarine Groundwater Discharge (SGD) studies are commonly conducted under aquifer baseflow conditions, neglecting the influence of episodic events that can significantly increase the supply of nutrients and water. This limits our understanding of the social, biogeochemical, and ecological impacts of SGD. In this study, we evaluated the influence of an extreme precipitation event (EPE) on the magnitude of both the terrestrial and marine components of SGD. To do so, three seawater sampling campaigns were performed at a Mediterranean ephemeral stream-dominated basin after an extreme precipitation event (~90 mm in few hours) and in baseflow conditions. Results indicate that the groundwater flows of terrestrial and marine SGD after the extreme precipitation event were 1 order of magnitude higher than those in baseflow conditions. SGD induced by extreme precipitation events, which only take place a few days per year, represented up to one third of the annual discharge of groundwater and associated nutrients at the study site. This work accentuates the need to account for episodic increases in the supply of water and nutrients when aiming at providing reliable annual SGD estimates, particularly in the current context of climate change, since the occurrence of such events is expected to increase worldwide. This work was partly funded by the projects PID2019-110212RB- C22, CGL2016-77122-C2-1-R/2-R and PID2019-110311RB-C21 of the Spanish Government and the project TerraMar ACA210/18/00007 of the Catalan Water Agency. The authors want to express their thanks for the support of the Generalitat de Catalunya for MERS (2017 SGR-1588) and GHS (2017 SGR 1485) for additional funding. The authors would like to thank Maravillas Abad from ICM-CSIC for the analysis of nutrients. M. Diego-Feliu acknowledges the economic support from the FI-2017 fellowships of the Generalitat de Catalunya autonomous government (2017FI_B_00365). V. Rodellas acknowledges financial support from the Beatriu de Pinós postdoctoral program of the Generalitat de Catalunya autonomous government (2019-BP-00241). A. Alorda-Kleinglass acknowledges financial support from ICTA “Unit of Excellence” (MinECo, MDM2015‐440 0552‐17‐1) and PhD fellowship, BES‐2017‐080740. Albert Folch is a Serra Hunter Fellow. We would like to thank all colleagues from the Grup de Recerca en Radioactivitat Ambiental de Barcelona - GRAB (Universitat Autònoma de Barcelona). We would like to thank SIMMAR (Serveis Integrals de Manteniment del Maresme) and the Consell Comarcal del Maresme for the construction of the research site.

Anchialine caves are common in Mediterranean karstic shorelines and elsewhere, delivering point-source fresh groundwater and nutrients to the coastal ocean. Here, we first quantified submarine groundwater discharge (SGD) in a typical karstic system (Zaton Bay, Croatia) receiving groundwater from anchialine caves using a radon (222Rn) mass balance model. We then combine our new observations with the literature to provide a Mediterranean-scale estimate of karstic fresh SGD nutrient fluxes. We found that SGD and related nutrient fluxes in the upper brackish layer were much higher than those in the underlying layer in Zaton Bay. In the upper brackish layer, both SGD (m d−1) and associated nutrient fluxes (mmol m−2 d−1) in the wet season (SGD: 0.29–0.40; DIN: 52; DIP: 0.27) were significantly higher than those in the dry season (SGD: 0.15; DIN: 22; DIP: 0.08). Red tides were observed in the wet season but not in the dry season. Nutrient budgets imply that SGD accounted for >98% of the total dissolved inorganic nitrogen (DIN) and phosphorous (DIP) sources into Zaton Bay. These large SGD nutrient fluxes with high N/P ratios (190–320) likely trigger and sustain red tide outbreaks. Combining our results with 30 previous studies in the region revealed that point-source DIN and DIP fluxes via karstic fresh SGD may account for 8–31% and 1–4%, respectively, of riverine inputs in the Mediterranean Sea. Overall, we demonstrate the importance of karstic SGD as a source of new nutrients with high N/P ratios to the Mediterranean Sea and emphasize how SGD lagging precipitation can drive red tide outbreaks.

Mining impacts on coastal environments have been extensively studied around the world. However, the role of Submarine Groundwater Discharge (SGD) and Porewater Exchange (PEX) as pathways for pollutants from mining waste deposits into seawater has been largely overlooked. Portmán Bay is located in the Cartagena-La Unión Pb-Zn sulphur mining district in Murcia, SE of Spain. The disposal of about 60 million tons of metal-rich mine tailings from 1957 to 1990 led to the infill of most of the bay. Although the effects of metals on indicator organisms have been shown previously, there is a major lack of knowledge on the release of dissolved metals from the emerged tailing deposit into the sea, more than 25 years after the closure of the mining activities. Samples for Ra isotopes (Ra, Ra, Ra and Ra) and dissolved metals (Ag, Cd, Co, Pb, Zn) were analyzed in porewaters and seawater in order to separately estimate SGD and PEX driven dissolved metal fluxes. Our results show a continuous release of dissolved metals into the sea driven by both PEX and SGD. Most of dissolved metals are remobilized and released into the water column by PEX, which is a ubiquitous mechanism acting along the shoreline. Although SGD only represents 13% of the water flow, it drives large fluxes of dissolved Fe into the sea, mainly restricted to the west side of the bay. Large inputs of dissolved Fe from the anoxic tailings deposit trigger a massive precipitation of iron hydroxides that enables the removal of most dissolved metals from the water column. This study highlights the role of PEX and SGD as significant mechanisms for the land to ocean transfer of dissolved metals from coastal mine tailings deposits., We want to express our gratefulness to “Liga de Vecinos” of Portmán Bay for their help. This project has been funded by the Spanish projects NUREIEV (CTM2013-44598-R) and NUREIEVA (CTM2016-75953-C2-1-R). The authors also acknowledge support from Generalitat de Catalunya autonomous government through its funding schema to excellence research groups (grants 2017 SGR 1588, 2014 SGR 1356 and 2017 SGR 315). This work is a contribution to ICTA ‘Unit of Excellence’ (MinECo, MDM2015-0552). V Rodellas acknowledges financial support from the Beatriu de Pinós postdoctoral programme of the Catalan Government (2017-BP-00334).

The naturally occurring Ra isotopes (223Ra; T1/2 = 11.4 d, 224Ra; T1/2 = 3.66 d, 226Ra; T1/2 = 1,600 y, and 228Ra; T1/2 = 5.7 y) and Rn (222Rn; T1/2 = 3.82 d) have been widely applied as environmental tracers. The application of these radioactive tracers has mainly been restricted to the evaluation of oceanographic and land-ocean interaction processes, although in recent years their use has also been extended to the study of groundwater systems. In this context, the activity ratios of 224Ra/228Ra and 222Rn/226Ra can be instrumental in providing key information on groundwater transit times in aquifers and those processes governing groundwater discharge into the coastal sea (often referred to as Submarine Groundwater Discharge or SGD). This work evaluates the potential use of these activity ratios as proxies for investigating groundwater systems through an advective transport model that integrates the radionuclides involved in these activity ratios (224Ra, 228Ra, 226Ra, and 222Rn) and their immediate parents into a single formulation. The results provided by the transport model indicate that the main factors controlling the 224Ra/228Ra and 222Rn/226Ra activity ratios are the alpha recoil supply, the retardation factor of Ra, and the groundwater transit times. The advective transport model and the activity ratios are used to present novel applications that interrelate the disciplines of hydrogeology and coastal oceanography. The main applications include the determination of groundwater transit times and the assessment of pathways and end-members related to submarine groundwater discharge processes. These applications were tested in a Mediterranean coastal aquifer., This work was partly funded by the projects PID2019-110212RB-C22, CGL2016-77122-C2-1-R/2-R and PID2019-110311RB-C21 of the Spanish Government and the project TerraMAr ACA210/18/00007 of the Catalan Water Agency. The authors want to thank the support of the Generalitat de Catalunya to MERS (2017 SGR-1588) and GHS (2017 SGR 1485) for additional funding. We would like to thank all the colleagues from the Laboratori de Radioactivitat Ambiental (Universitat Autònoma de Barcelona). We would also like to thank Leon Humphries for his detailed English corrections. We would like to thank SIMMAR (Serveis Integrals de Manteniment del Maresme) and the Consell Comarcal del Maresme in the construction of the research site. M. Diego‐Feliu acknowledges the economic support from the FI‐2017 fellowships of the Generalitat de Catalunya autonomous government (2017FI_B_00365). V. Rodellas acknowledges financial support from the Beatriu de Pinós postdoctoral program of the Generalitat de Catalunya autonomous government (2017‐BP‐00334). A. Alorda‐Kleinglass acknowledges financial support from ICTA “Unit of Excellence” (MinECo, MDM2015‐0552‐17‐1) and PhD fellowship, BES‐2017‐080740. T. Goyetche acknowledges PhD fellowship (BES‐2017‐080028) from the FPI Program by the Spanish Ministry of Economy, Industry and Competitiveness. A. Folch is a Serra Húnter Fellow.

Fluxes of nutrients, metals, contaminants, among others dissolved compounds transported from land to oceans have a direct impact on coastal biogeochemical cycles. One of these land-ocean interaction mechanisms, recently recognized as an important source of these compounds, is the flow of groundwater from continental margins to the coastal ocean, commonly known as Submarine Groundwater Discharge (SGD). The Mediterranean coastline is characterized by the presence of ephemeral streams, geomorphological settings that act as preferential flow paths for both runoff and groundwater towards the sea. The Mediterranean Basin is highly influenced by strong precipitation events (>50 mm) that commonly occur during fall and spring seasons such as isolated depression at high levels events, locally named ‘gota-freda’. In such situations, runoff causes several social and environmental impacts along ephemeral streams that have been long recognized. However, when the surface water flow ceases, the subterranean part of ephemeral streams may continue supplying water and solutes to the coastal ocean via SGD. This process and its effects for coastal ecosystems have been largely overlooked. In this study, we evaluated the influence of a ‘gota-freda’ event on both the role of ephemeral streams as preferential areas for groundwater discharge and on the magnitude of SGD and SGD-derived nutrient fluxes. To do so, three seawater sampling campaigns were performed in a Mediterranean coastal region dominated by ephemeral streams (Maresme, Catalunya) after heavy rainfall events (~50 mm) and in baseflow conditions. Results of this study indicate that SGD flows are between 5 and 7 times higher after a strong precipitation event than in baseflow conditions indicating that the supply of nutrients and other dissolved compounds to the Mediterranean Sea is highly dependent on these events. This study highlights that this mechanism is a relevant process for coastal biogeochemical cycles of semi-arid regions such as the Mediterranean basin.

Mar Menor (SE, Spain) is one of the largest coastal lagoons in the Mediterranean basin. Its ecological and economic significance has led to its inclusion in several protection programmes, both on a national and international level. In the last decades, this semiconfined habitat has been under high anthropogenic pressure from agricultural, mining and tourism activities, which have resulted in significant changes, such as eutrophic events and their cascading ecological effects. Previous research suggests that this degradation is linked to the introduction of nutrients and contaminants to this ecosystem, which are accumulated in the sediments of the lagoon. In this work, sediment cores from key locations of the Mar Menor were collected in order to estimate the amount of accumulated chemical compounds, such as metals and organic compounds. The results of this study are used to reconstruct the historical record of contaminants, which can fuel future contamination episodes in the lagoon.

Coastal environments have experienced a rapid transformation due to the expansion of tourism. This growth may enhance problems as over-saturation of spaces or environmental pollution. One of the main problems is associated with the collapse of environmental infrastructures, which may become saturated during high seasons. Indeed, wastewater treatment plants (WWTP) can be located in coastal areas delivering high concentrations of nutrient effluents into the marine environment. Alternatively, WWTP effluents are introduced into coastal aquifers via injection wells, given that the geological matrix is used to filter naturally the transported effluent solutes. However, the injection of significant amounts of WWTP effluents can modify the hydrogeological dynamics and enrich substantially the solute concentrations in groundwaters. Zones with a hydraulic connection between the coastal aquifer and the sea, these contaminated groundwaters may be transferred to coastal environments via Submarine Groundwater Discharge (SGD). Thus, SGD may act as a pathway delivering part of the WWTP-derived nutrients and pollutants into the marine environment, which may lead to eutrophication or harmful algal blooms. More importantly, such process may become threatening for society when the discharge occurs into bathing waters, affecting the ecosystem and perception of stakeholders.In this study, we evaluate the role of SGD as a conveyor of nutrients from a karstic coastal aquifer affected by the injection of WWTP effluents to the Deià cove in Mallorca (Balearic Islands). Results show that the tourism seasonality changes the coastal aquifer natural dynamics during the dry season, delivering via SGD, nutrients concentrations above the maximum limits established by the Spanish and European water framework directives. Due to those enriched nutrient fluxes, the coastal water ecosystem has registered the highest values of ∂15N in Posidonia oceanica in the Balearic Islands and suffers periodic algal blooms, creating a conflict among stakeholders.

The assessment of the biogeochemical cycles in coastal environments often relies on riverine inputs as the main source of nutrients and other dissolved compounds from land to the ocean. However, the discharge of groundwater through continental margins, commonly known as Submarine Groundwater Discharge (SGD), is also recognized as relevant sources of nutrients to the coastal ocean, particularly in oligotrophic and semi-arid environments, such as the Mediterranean Sea. In this study, we use radioactive tracers (radium isotopes and radon) to i) quantify the magnitude of SGD-driven nutrient fluxes to a Mediterranean cove (Cala Pudent, Menorca, Balearic Islands) and ii) characterize the nutrient transformations occurring in the beach before groundwater discharges to the sea. Cala Pudent is a limestone coastal cove with a restricted connection to the open sea. In this system, groundwater from a permanent spring infiltrates through an organic substrate dominated by thick deposits of seagrass (Posidonia oceanica) leaf litter and flows into the sea. This substrate, together with the dynamic groundwater-seawater mixing, are chiefly influencing the nutrient enrichment and transformation occurring in the beach and thus modulating the SGD-derived nutrient input to the sea. The ecological implications of these inputs are also assessed, particularly for the Posidonia oceanica and Cymodocea nodosa meadows located near the study site.

Altres ajuts: acords transformatius de la UAB Unidad de excelencia María de Maeztu CEX2019-000940-M Submarine Groundwater Discharge (SGD) is recognized as a fundamental hydrological process that supports many coastal biogeochemical cycles and social-ecological systems. However, very little has been investigated about how SGD affects society and, specifically, human well-being. This study systematically examines the published scientific literature on the social implications of SGD by using an Ecosystem Service (ES) perspective. Coastal services provided by ecosystems dependent on SGD are analyzed and clustered in the four main categories of Ecosystem Services (i.e., Provisioning, Supporting, Regulating and Cultural), which are in turn divided into subcategories defined as outcomes. This allows identifying and discussing both benefits and threats to coastal societies resulting from SGD outcomes. From the 1532 articles initially reviewed, the most frequently mentioned category was the supporting services (835) due to the mainstream trend in scientific literature to focus on the role of SGD as a process influencing coastal biogeochemical cycles. Conversely, cultural ES were mentioned in only 49 cases, which should not necessarily be interpreted as a lack of research or interest in this topic, but that this type of references are often not found in the scientific literature but in the grey literature. A detailed publication review was additionally conducted, identifying 114 case studies from 96 different locations worldwide that reported cases in which SGD had social implications on the well-being. Our review also shows how the different types of Ecosystem Services can have multiple synergies and trade-offs between them, resulting in unequal impacts among stakeholder groups. Overall, this study identifies research gaps related to Ecosystem Services provided by SGD as well as opportunities for further studies, while developing an analytical framework that relies on the Ecosystem Services approach to guide future research on the social implications of SGD.

International audience; The Radium Delayed Coincidence Counter (RaDeCC) is one of the most extensively used equipment for measuring 223Ra and 224Ra activities in water and sediment samples. Samples are placed in a closed He-circulation system that carries the Rn produced by the decay of Ra to a scintillation cell. Each alpha decay recorded in the cell is routed to an electronic delayed coincidence system which enables the discrimination of 223Ra and 224Ra. In this study, the measurement and quantification methods using the RaDeCC system are assessed through analyses of registered data in different RaDeCC systems worldwide and a set of simulations. Results of this work indicate that the equations used to correct for 223Ra and 224Ra cross-talk interferences are only valid for a given range of activities and ratios between isotopes. Above certain limits that are specified in this study, these corrections may significantly overestimate the quantification of 223Ra and 224Ra activities (up to ~40% and 30%, respectively), as well as the quantification of their parents 227Ac and 228Th. High activities of 226Ra may also produce an overestimation of 224Ra activities due to the buildup of 222Rn, especially when long measurements with low activities of 224Ra are performed. An improved method to quantify 226Ra activities from the buildup of 222Rn with the RaDeCC system is also developed in this study. Wethus provide a new set of guidelines for the appropriate quantification of 223Ra, 224Ra, 227Ac, 228Th, and 226Ra with the RaDeCC system.

Coastal aquifers are affected by seawater intrusion (SWI), which causes their salinization, and yield submarine groundwater discharge (SGD), which feeds marine ecosystems. Characterizing groundwater dynamics in coastal aquifers is fundamental for understanding both processes and their interaction. In order to gain insights into SWI and SGD, we developed a 100 m-scale experimental field site located in a coastal alluvial aquifer at the mouth of an ephemeral stream on the Maresme coastline (Barcelona, Spain). Given the complexity of coastal aquifers and the dynamism of the processes occurring therein, understanding of the coupled processes can be achieved by combining methods and approaches across different hydrogeological disciplines. In this study, we conduct a detailed aquifer characterization based on the four pillars of hydrogeology: geology (lithological description and core samples analyses), geophysics (downhole and cross-hole measurements), hydraulics (pumping and tidal response tests) and hydrochemistry (major and minor elements, together with stable and Ra isotopes). Each discipline contributed to the characterization of the aquifer: (1) geological characterization revealed that the aquifer consists of fluvial sediments, organized in fining upwards sequences with alternating layers of gravel, sand and silt; (2) geophysics helped in identifying silt layers and their continuity, which play a segmenting role in the aquifer hydrodynamics; (3) hydraulics tests, specifically tidal response tests, evidenced that tidal loading, rather than hydraulic connection to the sea, drives the tidal response; and (4) hydrochemistry revealed a surprising high reactivity, as most ions reflect some reaction, beyond the expected cation exchange. The summary is that the aquifer, which initially looked like a homogeneous unconfined aquifer 22 m thick, effectively behaves as a multi-aquifer and reactive system with freshwater discharging beneath saltwater at several depths. The fact that thin silt layers caused such a significant impact opens new paths beyond this study both for coastal aquifer management (the possibility of transient pumping for freshwater resources) and marine ecology (expect diffuse groundwater discharge)., We acknowledge the contribution of all the members of the MEDISTRAES I, II and III project, from the Groundwater Hydrology Group of the Technical University of Catalonia (UPC) and the Spanish National Research Council (CSIC), the Autonomous University of Barcelona (UAB), the University of Barcelona (UB), the Geosciences Montpellier Laboratory, CNRS and the University of Rennes, for their support during experimental laboratory tests, the Argentona site creation, the setup of the electrodes during boreholes installation and for ensuring site maintenance. The final manuscript was significantly improved by critical, but constructive comments by two anonymous reviewers. This work was funded by the project PID2019-110212RB-C21, CGL2016-77122-C2-1-R/2-R and PID2019-110311RB-C22 of the Spanish Government and the project TerraMar (grant no. ACA210/18/00007) of the Catalan Water Agency. We would like to thank SIMMAR (Serveis Integrals de Manteniment del Maresme) and the Consell Comarcal del Maresme in the construction of the research site. This study contributes to the work carried out by the GHS (2017 SGR 1485) and MERS research group (2017 SGR 1588) for additional funding. M. Diego-Feliu acknowledges the economic support from the FI-2017 fellowships of the Generalitat de Catalunya autonomous government (2017FI_B_00365). V. Rodellas acknowledges financial support from the Beatriu de Pinós postdoctoral program of the Generalitat de Catalunya autonomous government (2019-BP-00241) The co-author Albert Folch is a Serra Húnter Fellow.

International audience; Porewater fluxes, including fresh groundwater discharge and circulation of surface waters through sediments, are increasingly documented to play an important role in hydrological and biogeochemical cycles of coastal water bodies. In most studies, the magnitude of porewater fluxes is inferred from geochemical tracers, but a detailed understanding of the underlying physical forces driving these fluxes remains limited. In this study, we evaluate the mechanisms driving porewater fluxes in the shallow coastal La Palme lagoon (France). We combined measurements of variations of salinity and temperature in the subsurface with 1-dimensional fluid, salt and heat transport models to evaluate the dynamics of porewater fluxes across the sediment-water interface in response to temporally variable forcings. Two main processes were identified as major drivers of porewater fluxes: i) temporal variations of lagoon water depths (forcing porewater fluxes up to 25 cm d−1) and ii) locally-generated wind waves (porewater fluxes of ~50 cm d−1). These processes operate over different spatial and temporal scales; Wind-driven waves force the shallow circulation of surface lagoon waters through sediments (mostly < 0.2 m), but are restricted to strong wind events (typically lasting for 1–3 days). In contrast, porewater fluxes driven by variations of lagoon water depths flush a much greater depth of sediment (>1 m). The spatial and temporal scales of driving forces will largely determine the significance of porewater fluxes, as well as their chemical composition. Thus, an appropriate evaluation of the magnitude of porewater-driven solute fluxes and their consequences for coastal ecosystems requires a solid and site-specific understanding of the underlying physical forces.

The characterization of saline water intrusion (SWI) and its hydrodynamics is a key issue to understand sub-marine groundwater discharge (SGD) and manage groundwater resources in coastal areas. To test and comparedifferent methods of characterization and monitoring, a new experimental site has been constructed in a coastalalluvial aquifer north of Barcelona city (Catalonia, Spain). The site is located between 30 and 90 m from theseashore and comprises 16 shallow piezometers organized in nests of three with depths ranging between 15 and25 m and 4 solitary piezometers. The objective of this paper is to combine different recently developed mon-itoring techniques to evaluate temporal variations in the aquifer hydrodynamics of the site at different spatialscales before and after the dry season of 2015. At the site scale,fibre optic distributed temperature sensing (FO-DTS), for thefirst time applied to study SWI, and cross-hole electrical resistivity tomography (CHERT) has beenapplied. At the meter/borehole scale, electrical conductivity of the formation has been applied not only in arepeated manner (¿time lapse¿), but also for thefirst time at relatively high frequency (1 sample every 10 min).CHERT has provided a better characterization of the seawater intrusion than electrical conductivity data ob-tained from piezometers. The combination of techniques has allowed improving the understanding of the systemby: 1) characterizing the extent and shape of SWI; 2) differentiating two different dynamics in the aquifer; and 3)identifying preferentialflow paths over different time and spatial intervals. Future challenges and the appli-cation of these techniques in other areas are also discussed., This work was funded by the projects CGL2013-48869-C2-1-R/2-R and CGL2016-77122-C2-1-R/2-R of the Spanish Government. We would like to thank SIMMAR (Serveis Integrals de Manteniment del Maresme) and the Consell Comarcal del Maresme in the construction of the research site. The authors want to thank the support of the Generalitat de Catalunya to MERS (2018 SGR-1588). This work is contributing to the ICTA ‘Unit of Excellence’ (MinECo, MDM2015-0552). Part of the funding was provided by the French network of hydrogeological observatories H+ (hplus/ore/fr/en) and the ANR project EQUIPEX CRITEX (grant ANR-11-EQPX-0011). V Rodellas acknowledges financial support from the Beatriu de Pinós postdoctoral program of the Generalitat de Catalunya (2017-BP-00334). M. Diego‐Feliu acknowledges the economic support from the FI‐2017 fellowships of the Generalitat de Catalunya autonomous government (2017FI_B_00365). This project also received funding from the European Union’s Horizon 2020 research and innovation programme under the Marie Sklodowska-Curie Grant Agreement No 722028.

Submarine groundwater discharge (SGD) is now recognized as an important process of the hydrological cycle worldwide and plays a major role as a conveyor of dissolved compounds to the ocean. Naturally occurring radium isotopes (223Ra, 224Ra, 226Ra and 228Ra) are widely employed geochemical tracers in marine environments. Whilst Ra isotopes were initially predominantly applied to study open ocean processes and fluxes across the continental margins, their most common application in the marine environment has undoubtedly become the identification and quantification of SGD. This review focuses on the application of Ra isotopes as tracers of SGD and associated inputs of water and solutes to the coastal ocean. In addition, we review i) the processes controlling Ra enrichment and depletion in coastal groundwater and seawater; ii) the systematics applied to estimate SGD using Ra isotopes and iii) we summarize additional applications of Ra isotopes in groundwater and marine studies. We also provide some considerations that will help refine SGD estimates and identify the critical knowledge gaps and research needs related to the current use of Ra isotopes as SGD tracers.

This study presents the results of the accumulation of (210)Po and (210)Pb in fish tissues and organs in a brackish-water marshland that is characterized by high concentrations of (222)Rn and (226)Ra supplied by submarine groundwater discharge (SGD). Tissues and organs from Cyprinus carpio, Chelon labrosus and Carassius auratus in the wetland were significantly enriched by both (210)Pb and (210)Po (up to 55 and 66 times, respectively) compared to blanks. The major input route of (210)Pb and (210)Po into the fish body seems to be through ingestion, due to the high levels of (210)Pb and (210)Po found in the gut content as well as in organs involved in digestion and metabolism (i.e. gut, kidney and hepatopancreas). Results showed that (210)Po was more accumulated in all fish tissues and organs except for the spine, which showed a higher affinity for (210)Pb, due to its capacity to replace Ca from apatite in bones. Over all the variables analyzed, fish tissues/organs and, secondarily, fish species were the most important factors explaining the concentration of radionuclides, whereas fish length and the sampling location played a minor role. The relationship of the two radionuclides varied markedly among tissues and their concentration levels were only correlated in gills, gut and, marginally, in spines. In general, the highest values of (210)Pb and (210)Po concentrations in tissues were found on C. labrosus tissues rather C. auratus and C. carpio. This study demonstrates that inputs of natural radionuclides supplied by SGD to coastal semi-enclosed areas (such as marshlands, lagoons or ponds) may significantly increase the contents of (210)Pb and (210)Po in fish tissues/organs. Thus, this study represents one of the first evidences of direct ecological effects derived from SGD.

The subterranean flow of water through sand barriers between coastal lagoons and the sea, driven by a positive hydraulic gradient, is a net new pathway for solute transfer to the sea. On the sea side of sand barriers, seawater circulation in the swash-zone generates a flux of recycled and new solutes. The significance and temporal variability of these vectors to the French Mediterranean Sea is unknown, despite lagoons constituting ~ 50% of the coastline. A one-dimensional Ra-224(ex)/Ra-223 reactive-transport model was used to quantify water flow between a coastal lagoon (La Palme) and the sea over a 6-month period. Horizontal flow between the lagoon and sea decreased from ~ 85 cm d(-1) during May 2017 (0.3 m(3) d(-1) m(-1) of shoreline) to ~ 20 cm d(-1) in July and was negligible in the summer months thereafter due to a decreasing hydraulic gradient. Seawater circulation in the swash-zone varied from 10 to 52 cm d(-1) (0.4-2.1 m(3) d(-1) m(-1)), driven by short-term changes in the prevailing wind and wave regimes. Both flow paths supply minor dissolved silica fluxes on the order of ~ 3-10 mmol Si d(-1) m(-1). Lagoon-sea water exchange supplies a net dissolved inorganic carbon (DIC) flux (320-1100 mmol C d(-1) m(-1)) two orders of magnitude greater than seawater circulation and may impact coastal ocean acidification. The subterranean flow of water through sand barriers represents a significant source of new DIC, and potentially other solutes, to the Mediterranean Sea during high lagoon water-level periods and should be considered in seasonal element budgets.

International audience; The role of groundwater and porewater fluxes as a source of nutrients to coastal ecosystems and their ecological implications are increasingly being recognized. In this study, the role of groundwater discharge and porewater fluxes in supporting primary production of coastal lagoons was evaluated by stable nitrogen and carbon isotope signature tracing of the transfer of nitrogen and carbon to primary producers. We determined the isotope signatures in macrophytes and phytoplankton (via particulate organic matter) and in the potential sources of inorganic nitrogen and carbon in two coastal lagoons on the French Mediterranean coastline. The δ15N of both macrophytes and phytoplankton reflect predominantly the nitrogen isotopic signatures of the karstic groundwater and porewater sources, indicating that they must have sourced the majority of their nitrogen from these sources, with punctual contributions from sewage input characterised by a significantly different isotopic signature. The δ13C signature of primary producers also shows the contribution of karstic groundwater discharge and porewater exchange as significant sources of dissolved inorganic carbon to primary production. This study links physical (nutrient delivery) and ecological (nutrient uptake) processes associated with primary production, thereby providing direct evidence for the ecological role groundwater discharge and porewater fluxes can play in coastal ecosystems.

The GEOTRACES Intermediate Data Product 2017 (IDP2017) is the second publicly available data product of the international GEOTRACES programme, and contains data measured and quality controlled before the end of 2016. The IDP2017 includes data from the Atlantic, Pacific, Arctic, Southern and Indian oceans, with about twice the data volume of the previous IDP2014. For the first time, the IDP2017 contains data for a large suite of biogeochemical parameters as well as aerosol and rain data characterising atmospheric trace element and isotope (TEI) sources. The TEI data in the IDP2017 are quality controlled by careful assessment of intercalibration results and multi-laboratory data comparisons at crossover stations. The IDP2017 consists of two parts: (1) a compilation of digital data for more than 450 TEIs as well as standard hydrographic parameters, and (2) the eGEOTRACES Electronic Atlas providing an on-line atlas that includes more than 590 section plots and 130 animated 3D scenes. The digital data are provided in several formats, including ASCII, Excel spreadsheet, netCDF, and Ocean Data View collection. Users can download the full data packages or make their own custom selections with a new on-line data extraction service. In addition to the actual data values, the IDP2017 also contains data quality flags and 1-σ data error values where available. Quality flags and error values are useful for data filtering and for statistical analysis. Metadata about data originators, analytical methods and original publications related to the data are linked in an easily accessible way. The eGEOTRACES Electronic Atlas is the visual representation of the IDP2017 as section plots and rotating 3D scenes. The basin-wide 3D scenes combine data from many cruises and provide quick overviews of large-scale tracer distributions. These 3D scenes provide geographical and bathymetric context that is crucial for the interpretation and assessment of tracer plumes near ocean margins or along ridges. The IDP2017 is the result of a truly international effort involving 326 researchers from 25 countries. This publication provides the critical reference for unpublished data, as well as for studies that make use of a large cross-section of data from the IDP2017. This article is part of a special issue entitled: Conway GEOTRACES - edited by Tim M. Conway, Tristan Horner, Yves Plancherel, and Aridane G. González., National Science Foundation (U.S.) (Grant OCE-0608600), National Science Foundation (U.S.) (Grant OCE0938349), National Science Foundation (U.S.) (Grant OCE-1243377), National Science Foundation (U.S.) (Grant OCE-1546580)

International audience; Understanding the transference of water resources within hydrogeological systems, particularly in coastal aquifers, in which groundwater discharge may occur through multiple pathways (through springs, into rivers and streams, towards the sea, etc.), is crucial for sustainable groundwater use. This research aims to demonstrate the usefulness of the application of conventional recharge assessment methods coupled to isotopic techniques for accurately quantifying the hydrogeological balance and submarine groundwater discharge (SGD) from coastal carbonate aquifers. Sierra Almijara (Southern Spain), a carbonate aquifer formed of Triassic marbles, is considered as representative of Mediterranean coastal karst formations. The use of a multi-method approach has permitted the computation of a wide range of groundwater infiltration rates (17-60%) by means of direct application of hydrometeorological methods (Thornthwaite and Kessler) and spatially distributed information (modified APLIS method). A spatially weighted recharge rate of 42% results from the most coherent information on physiographic and hydrogeological characteristics of the studied system. Natural aquifer discharge and groundwater abstraction have been volumetrically quantified, based on flow and water-level data, while the relevance of SGD was estimated from the spatial analysis of salinity, Rn-222 and the short-lived radium isotope Ra-224 in coastal seawater. The total mean aquifer discharge (44.9-45.9 hm(3) year(-1)) is in agreement with the average recharged groundwater (44.7 hm(3) year(-1)), given that the system is volumetrically equilibrated during the study period. Besides the groundwater resources assessment, the methodological aspects of this research may be interesting for groundwater management and protection strategies in coastal areas, particularly karst environments.

International audience; Evaluating the sources of nutrient inputs to coastal lagoons is required to understand the functioning of these ecosystems and their vulnerability to eutrophication. Whereas terrestrial groundwater processes are increasingly recognized as relevant sources of nutrients to coastal lagoons, there are still limited studies evaluating separately nutrient fluxes driven by terrestrial groundwater discharge and lagoon water recirculation through sediments. In this study, we assess the relative significance of these sources in conveying dissolved inorganic nutrients (NO3−, NH4+ and PO43−) to a coastal lagoon (La Palme lagoon; France, Mediterranean Sea) using concurrent water and radon mass balances. The recirculation of lagoon water through sediments represents a source of NH4+ (1900–5500 mol d−1) and PO43− (22–71 mol d−1), but acts as a sink of NO3−. Estimated karstic groundwater-driven inputs of NO3−, NH4+ and PO43− to the lagoon are on the order of 200–1200, 1–12 and 1.5–8.7 mol d−1, respectively. A comparison between the main nutrient sources to the lagoon (karstic groundwater, recirculation, diffusion from sediments, inputs from a sewage treatment plant and atmospheric deposition) reveals that the recirculation of lagoon water through sediments is the main source of both dissolved inorganic nitrogen (DIN) and phosphorous (DIP) to La Palme lagoon. These results are in contrast with several studies conducted in systems influenced by terrestrial groundwater inputs, where groundwater is often assumed to be the main pathway for dissolved inorganic nutrient loads. This work highlights the important role of lagoon water recirculation through permeable sediments as a major conveyor of dissolved nutrients to coastal lagoons and, thus, the need for a sound understanding of the recirculation-driven nutrient fluxes and their ecological implications to sustainably manage lagoonal ecosystems.

International audience; The circulation of seawater through permeable coastal sediments is increasingly recognized as an important source of nutrients, including dissolved silica (DSi), to the coastal ocean. Here, we utilized a Ra isotope (223 Ra, 224 Ra ex , 228 Ra) mass balance to quantify DSi fluxes driven by water circulation to a small shallow coastal lagoon (La Palme; French Mediter-ranean) during June 2016, as compared to karstic groundwater spring inputs. The DSi flux driven by lagoon water circulation (derived from 224 Ra ex) was approximately one order of magnitude greater (1900 ± 1700 mol d À1) than the DSi load of the karstic groundwater spring (250 ± 50 mol d À1) and greater than molecular diffusion (970 ± 750 mol d À1). Lagoon water circulation was a negligible source of 228 Ra, indicating that circulation-driven DSi inputs occur over a timescale of days. Offshore transects were studied to quantify fluxes of marine-derived submarine groundwater discharge (SGD) from the permeable sandy coastline adjacent to the lagoon, into the Mediterranean Sea. Surface water transects revealed near-shore enrichments of Ra and DSi, attributed to wave-setup and water exchange through the permeable beach between the lagoon and the sea. Upscaling over the 9.5 km stretch of sandy beaches results in a marine SGD-driven DSi flux of 2.3 ± 1.3 Â 10 4 mol d À1 , similar in magnitude to the Têt river during November 2016 (3.3 ± 2.4 Â 10 4 mol d À1), the largest river in the region. A positive relationship between DSi and 224 Ra ex in lagoon water and seawater, but not 228 Ra, suggests that 224 Ra ex and DSi enrichments are derived from a similar source, the sediment (i.e. lithogenic particle dissolution), operating on short timescales. A marine SGD-driven DSi flux to the Gulf of Lions (3.8 ± 2.2 Â 10 5 mol d À1) is likely continuous over time. The relatively constant DSi inputs from water circulation for the shallow lagoons and beaches along the French Mediterranean Sea

International audience; Tracer approaches to estimate both porewater exchange (the cycling of water between surface water and sediments, with zero net water flux) and groundwater inflow (the net flow of terrestrially derived groundwater into surface water) are commonly based on solute mass balances. However, this requires appropriate characterization of tracer end-member concentrations in exchanging or discharging water. Where either porewater exchange or groundwater inflow to surface water occur in isolation, then the water flux is easily estimated from the net tracer flux if the end-member is appropriately chosen. However, in most natural systems porewater exchange and groundwater inflow will occur concurrently. Our analysis shows that if groundwater inflow (Q g) and porewater exchange (Q p) mix completely before discharging to surface water, then the combined water flux (Q g 1 Q p) can be approximated by dividing the combined tracer flux by the difference between the porewater and surface water concentrations, (c p – c). If Q g and Q p do not mix prior to discharge, then (Q g 1 Q p) can only be constrained by minimum and maximum values. The minimum value is obtained by dividing the net tracer flux by the groundwater concentration, and the maximum is obtained by dividing by (c p – c). Dividing by the groundwater concentration gives a maximum value for Q g. If porewater exchange and groundwater outflow occur concurrently, then dividing the net tracer flux by (c p – c) will provide a minimum value for Q p. Use of multiple tracers, and spatial and temporal replication should provide a more complete picture of exchange processes and the extent of subsurface mixing.

© 2017 Elsevier. This manuscript version is made available under the CC-BY-NC-ND 4.0 license: http://creativecommons.org/licenses/by-nc-nd/4.0/ This author accepted manuscript is made available following 24 month embargo from date of publication (Jan 2018) in accordance with the publisher’s archiving policy, Water recirculation through permeable sediments induced by wave action, tidal pumping and currents enhances the exchange of solutes and fine particles between sediments and overlying waters, and can be an important hydro-biogeochemical process. In shallow water, most of the recirculation is likely to be driven by the interaction of wave-driven oscillatory flows with bottom topography which can induce pressure fluctuations at the sediment-water interface on very short timescales. Tracer-based methods provide the most reliable means for characterizing this short-timescale exchange. However, the commonly applied approaches only provide a direct measure of the tracer flux. Estimating water fluxes requires characterizing the tracer concentration in discharging porewater; this implies collecting porewater samples at shallow depths (usually a few mm, depending on the hydrodynamic dispersivity), which is very difficult with commonly used techniques. In this study, we simulate observed vertical profiles of radon concentration beneath shallow coastal lagoons using a simple water recirculation model that allows us to estimate water exchange fluxes as a function of depth below the sediment-water interface. Estimated water fluxes at the sediment water interface at our site were 0.18–0.25 m/day, with fluxes decreasing exponentially with depth. Uncertainty in dispersivity is the greatest source of error in exchange flux, and results in an uncertainty of approximately a factor-of-five.

International audience; Groundwater discharge in coastal karst aquifers worldwide represents a substantial part of the water budget and is a main pathway for nutrient transport to the sea. Groundwater discharge to the sea manifests under different forths, making its assessment very challenging particularly in highly heterogeneous coastal systems karst systems. In this study, we present a methodology approach to identify and quantify four forms of groundwater discharge in a mixed lithology system in southern Spain (Maro-Cerro Gordo) that includes an ecologically protected coastal area comprised of karstic marble. We found that groundwater discharge to the sea occurs via: (1) groundwater-fed creeks, (2) coastal springs, (3) diffuse groundwater seepage through seabed sediments, and (4) submarine springs. We used a multi-method approach combining tracer techniques (salinity, Ra-224, and Rn-222) and direct measurements (seepage meters and flowmeters) to evaluate the discharge. Groundwater discharge via submarine springs was the most difficult to assess due to their depth (up to 15 m) and extensive development of the springs conduits. We determined that the total groundwater discharge over the 16 km of shoreline of the study area was at least 11 +/- 3 x 10(3) m(3) d(-1) for the four types of discharge assessed. Groundwater-derived nitrate (NO3-) fluxes to coastal waters over similar to 3 km (or 20%) in a highly populated and farmed section of Maro-Cerro Gordo was 641 +/- 166 mol d(-1), or similar to 75% of the total NO3- loading in the study area. We demonstrate in this study that a multi-method approach must be applied to assess all forms of SGD and derived nutrient fluxes to the sea in highly heterogeneous karst aquifer systems.

Altres ajuts: the government of Spain and the Fulbright Commission for a post-doctoral fellowship to J.G-O. (ref 2007-0516) The approach to quantify submarine groundwater discharge using Ra isotopes generally involves developing a Ra mass balance in an estuary, bay or lagoon. In this work we present a 224Ra mass balance used to evaluate the importance of the submarine groundwater discharge (SGD) in Long Island Sound (NY, US), the third most important estuary in US, located between Long Island and Connecticut that is usually affected by summertime hypoxia in the western basin. Three surveys were conducted between April 2009 and August 2010 where 25 water stations were sampled for Ra isotopes, oxygen and Mn. Stations were oriented along 4 transects: one axial extending from the western to the eastern Sound and three longitudinal transects in the western, central and eastern Sound. The inventory of 224Ra in the water column in summer was circa 2 times greater than in winter, suggesting an increased 224Ra flux to the Sound in summer. A mass balance for 224Ra was constructed considering tidal exchange, inputs from rivers, desorption from resuspended particles, diffusive fluxes (including bioirrigation) from bottom sediments and radioactive decay in the water column. Fluxes of 224Ra from bottom sediments were measured by incubating cores under oxic conditions in a continuous flow mode such that the overlying water was circulated through a Mn-oxide fiber to maintain a constant activity of 224Ra. Fluxes from muddy sediments (comprising ~67% of the Sound bottom) ranged from 127 to 312dpmm-2d-1 and were ~60dpmm-2d-1 in sandy sediments (33% of the Sound). Incubations under hypoxic conditions showed variable fluxes depending on reduction and mobilization of Mn. The 224Ra mass balance shows a net input of Ra to the Sound of 106±50×1012dpmy-1 in spring and 244±112×1012dpmy-1 in the summer that is attributed to SGD. Elevated 224Ra values were observed near shore and in the pore fluids of the coarse beach sands along the Long Island and Connecticut coasts, suggesting that SGD driven by tidal recirculation through the beach face is a major source of 224Ra to the Sound. Seasonal variation in this source seems unlikely, and the calculated 224Ra SGD fluxes for spring and summer overlap within the uncertainties. Nevertheless we conclude that variations in the 224Ra water column inventories could be produced by seasonal changes in bioirrigation and/or redox cycling of Mn as well as sediment resuspension and desorption of 224Ra from resuspended particles, and that our mass balance underestimates these terms, particularly in the summer. 224Ra fluxes from sediments in estuaries, especially those with significant areas of muddy sediments and seasonal hypoxia, are important and should be well constrained in future uses of this isotope as a tracer for SGD.

We present a new method to determine 226Ra in aqueous environmental samples, based on the rate of ingrowth of 222Rn from 226Ra, using the radium delayed coincidence counter (RaDeCC). We use the same instrument setup that is used for the determination of 223Ra and 224Ra. In contrast to methods published earlier, the approach does not require a modification of the counting equipment, counting separately for 226Ra, or waiting for radioactive equilibrium. We show that the calibration works from as low as 10 dpm (0.166 Bq) per sample, up to more than 1000 dpm (16.7 Bq). Although uncertainties are larger (typically around 10%) than reported uncertainties for γ counting, liquid scintillation, or mass spectrometry at comparable activities, the simple setup, low cost, and robustness of the method make it a useful approach for underway measurements, combinations with short-lived radium isotopes, or monitoring purposes when limited funding or infrastructure is available.

Coastal groundwater discharge (CGD) plays an important role in coastal hydrogeological systems as they are a water resource that needs to be managed, particularly in wetland areas. Despite its importance, identifying and monitoring CGD often presents physical and logistical constraints, restraining the application of more traditional submarine groundwater discharge surveying techniques. Here we investigate the capability of electrical resistivity imaging (ERI) in the Peniscola wetland (Mediterranean coast, Spain). ERI surveying made it possible to identify and delineate an ascending regional groundwater flow of thermal and Ra-enriched groundwater converging with local flows and seawater intrusion. The continuous inputs of Ra-rich groundwater have induced high activities of Ra isotopes and 222Rn into the marsh area, becoming among the highest previously reported in wetlands and coastal lagoons. Geoelectrical imaging enabled inferring focused upward discharging areas, leaking from the aquifer roof through a confining unit and culminating as spring pools nourishing the wetland system. Forward modelling over idealized subsurface configurations, borehole datasets, potentiometric records from standpipe piezometers, petrophysical analysis, and four natural and independent tracers (224Ra, 222Rn, temperature and salinity) permitted assessing the geoelectrical model and a derived hydrogeological pattern. The research highlights the potential of ERI to improve hydrogeological characterization of subsurface processes in complex contexts, with different converging flows. Additionally, a hydrogeological conceptual model for a groundwater-fed coastal wetland was proposed, based on the integration of surveying datasets. Copyright © 2013 John Wiley & Sons, Ltd.

International audience; Submarine groundwater discharge (SGD) has been identified as an important source of Sr to the ocean and the SGD-driven Sr flux to the global ocean has been recently re-evaluated (Beck et al., 2013). However, the uncertainty of this value is still high because of the uncertainties related to the determination of SGD flow rates and the paucity of (Sr/Sr)-Sr-87-Sr-86 data in SGD end-members. As carbonates have high Sr concentrations and are subjected to intense heightened weathering, they might significantly influence the SGD input of Sr to the ocean. Here we present data on Sr concentrations and Sr-87/Sr-86 ratios in three carbonate dominated sites of the western area of the Mediterranean Sea, a semi-enclosed basin characterized by abundant coastal carbonates. The Sr-87/(86) Sr ratios in groundwater were lower compared to modern seawater (similar to 0.70916), as expected for areas dominated by carbonate lithologies. Concentrations of Sr and Sr-87/Sr-86 ratios in groundwater showed conservative mixing in the studied subterranean estuaries. By using SGD flow rates reported in the literature for the study areas, a flow-weighted fresh SGD end-member characterized by a Sr concentration of 27-30 mu M and a Sr-87/Sr-86 ratio of 0.707834-0.708020 was calculated for the eastern coast of the Iberian Peninsula. Integrating these Sr data with literature data (i.e. values of Sr concentration and Sr-87/Sr-86 ratio from other lithologies as well as SGD flow rates), we also calculated the fresh SGD-driven Sr flux to the entire Mediterranean Sea, obtaining a value of (0.34-0.83) . 10(9) mol y(-1), with a Sr-87/Sr-86 of 0.7081-0.7086. Thus, for the entire Mediterranean basin, SGD is globally a source of Sr less radiogenic compared to seawater. The SGD Sr flux to the Mediterranean Sea represents 5-6% of the SGD Sr flux to the global ocean and the Mediterranean SGD end-member has higher Sr concentration (5-12 mu M) than the global SGD end-member (2.9 mu M). This confirms the significant role of carbonate lithologies on SGD-driven Sr fluxes to seawater. The fresh SGD-driven Sr flux to the Mediterranean Sea is about 20-50% of the riverine Sr input and significantly higher than the input through atmospheric dust deposition. Therefore SGD should be considered as an important continental source of Sr to the basin. (C) 2016 Elsevier Ltd. All rights reserved.