The connection between Submarine Groundwater Discharge and seawater quality: The threat of treated wastewater injected into coastal aquifers.

Submarine Groundwater Discharge (SGD) delivers nutrients to the coastal sea triggering phytoplankton blooms, eutrophication, and can also serve as a pathway for contaminants. Wastewater treatment plants (WWTP) including injection wells in coastal areas influence coastal aquifers and might impact the composition and magnitude of SGD fluxes. In tourist areas, wastewater treatment may be less efficient and larger in volume during high seasons, potentially impacting nutrient fluxes from SGD and exacerbating environmental impacts. This study analyzes the nutrient transfer from treated wastewater injection in karstic aquifers to the coastal sea via SGD, considering the impacts of tourism seasonality. This study is conducted in Cala Deià, a small cove in the Balearic Islands, a Mediterranean tourist destination. The findings suggest that the seasonality of tourism, leading to variations in the volume of wastewater treated in the WWTP, influences the dynamics of the coastal aquifer. This leads to increased SGD water and nutrient fluxes to the sea in summer, i.e. the peak tourist season. The measured DIN, DIP, and DSi inventories in the cove are much larger in August than in April (3, 10, and 1.5 times higher, respectively) due to higher input of nutrients in summer due to SGD impacted by the WWTP. These elevated nutrient flows can support algal blooms in the cove, compromising water quality for local swimmers and tourists. Indeed, in August, shoreline stations exhibited eutrophic Chl-a concentrations, with peaks reaching approximately 4 mg Chl-a L-1. These elevated levels suggest the presence of an algal bloom during the survey. The anthropogenic origin of SGD-driven nutrients is traced in seawater and seagrass meadows, as evidenced by high ∂15N signatures indicative of polluted areas. Thus, the high pressure exerted on coastal areas by tourism activities increased the magnitude of SGD nutrient fluxes, thereby threatening coastal ecosystems and the services they provide.

Concentrations and distribution of 210Pb in bird feathers and its potential for tracing age and flight times.

Bird feathers have been widely used as environmental indicators, providing key information on environmental pollution. However, there is little available information on the adsorption of natural radioactivity in bird feathers and consequently, its impact on the field of movement ecology is not yet known. This study investigates the concentration and distribution of 210Pb in wing- and tail-feathers of different bird species with contrasting migratory strategies, and discusses its potential use as a tracer of age and flight times. Adsorption of 210Pb in bird feathers is directly related to the interaction of feathers with air, therefore it is hypothesised that the presence of this radionuclide is proportional to the length of flight times, and is asymmetrically distributed in flight feathers. Consequently, a significant difference is expected between 210Pb concentrations in feathers of long-distance migrants when compared to sedentary species. For this purpose, a total of 45 samples from eight individuals of three bird species with distinct migratory strategies were analysed: a highly aerial and long-distance migratory species (Common swift Apus apus), and two largely sedentary species widely distributed across Europe (Great tit Parus major and Tawny owl Strix aluco). Novel findings show that the content of 210Pb in bird feathers of adult migratory birds is much higher than in sedentary birds or juvenile individuals, demonstrating this naturally occurring radionuclide can provide information about the contact time between feathers and air. Additionally, 210Pb adsorption was not evenly distributed in bird feathers. The findings provide a new method to trace age and flight time of birds using 210Pb in feathers, complementing conventional techniques in bird migration studies.

Drivers of variability in Blue Carbon stocks and burial rates across European estuarine habitats.

The implementation of climate change mitigation strategies based on the conservation and restoration of Blue Carbon ecosystems requires a deep understanding of the magnitude and variability in organic carbon (Corg) storage across and within these ecosystems. This study explored the variability in soil Corg stocks and burial rates across and within intertidal estuarine habitats of the Atlantic European coast and its relation to biotic and abiotic drivers. A total of 136 soil cores were collected across saltmarshes located at different tidal zones (high marsh, N = 45; low marsh, N = 30), seagrass meadows (N = 17) and tidal flats (N = 44), and from the inner to the outer sections of five estuaries characterized by different basin land uses. Soil Corg stocks were higher in high-marsh communities (65 ± 3 Mg ha-1) than in low-marsh communities (38 ± 3 Mg ha-1), seagrass meadows (40 ± 5 Mg ha-1) and unvegetated tidal flats (46 ± 3 Mg ha-1) whereas Corg burial rates also tended to be higher in high marshes (62 ± 13 g m-2 y-1) compared to low marshes (43 ± 15 g m-2 y-1) and tidal flats (35 ± 9 g m-2 y-1). Soil Corg stocks and burial rates decreased from inner to outer estuarine sections in most estuaries reflecting the decrease in the river influence towards the estuary mouth. Higher soil Corg stocks were related to higher content of silt and clay and higher proportion of forest and natural land within the river basin, pointing at new opportunities for protecting coastal natural carbon sinks based on the conservation and restoration of upland ecosystems. Our study contributes to the global inventory of Blue Carbon by adding data from unexplored regions and habitats in Europe, and by identifying drivers of variability across and within estuaries.

Can a Sediment Core Reveal the Plastic Age? Microplastic Preservation in a Coastal Sedimentary Record.

The seafloor is the major sink for microplastic (MP) pollutants. However, there is a lack of robust data on the historical evolution of MP pollution in the sediment compartment, particularly the sequestration and burial rate of small MPs. By combining a palaeoceanographic approach and state-of-the-art analytical methods for MP identification down to 11 µm in size, we present the first high-resolution reconstruction of MP pollution from an undisturbed sediment core collected in the NW Mediterranean Sea. Furthermore, we investigate the fate of MPs once buried in the sediments by evaluating the changes in the size distribution of the MPs and the weathering status of the polyolefins, polyethylene, and polypropylene. Our results indicate that the MP mass sequestered in the sediment compartment mimics the global plastic production from 1965 to 2016. We observed an increase in the weathering status of the polyolefins as the size decreased. However, the variability in the size and weathering status of the MPs throughout the sedimentary record indicated that these pollutants, once incorporated into sediments, remain preserved with no further degradation under conditions lacking remobilization.

Coastal engineering infrastructure impacts Blue Carbon habitats distribution and ecosystem functions.

Intertidal estuarine habitats (e.g., saltmarshes and tidal flats) provide important ecosystem services to society, including coastal protection, food provision and Corg sequestration. Yet, estuaries and estuarine habitats have been subjected to intense human pressure, such as land-use change and artificialization of the shoreline to support economic activities and uses. Construction of engineering infrastructures (e.g., piers, bridges) in these areas alters estuary-wide hydromorphological conditions and thus sedimentation patterns at the estuarine scale, which are key drivers of habitats distribution and ecosystem structure, processes and functions. Most of the research on the impact of civil engineering structures on coastal habitats has focused on the biological communities that colonize them or the bottoms where they are placed, whereas their indirect impacts on adjacent habitats has been largely unexplored. Understanding the influence of man-made infrastructures on the distribution of estuarine habitats and functions is critical, particularly considering that shoreline armoring is expected to increase as a way to protect coastal areas from hazards derived from climate change. Shifts in habitat distribution and functions occur in several years or decades and relating them with the occurrence of past historical events is challenging when no monitoring data is available. By examining historical aerial photographs and different biogeochemical properties along a saltmarsh soil record, this study demonstrates that the construction of an infrastructure (i.e. bridge) caused a rapid transformation (~ 30 years) of a bare sandflat into a high marsh community and to significant changes in sediment biogeochemical properties, including the decrease in sediment accretion rate and Corg burial rates since then. This study contributes to increase the knowledge on the impact that the construction in coastal areas of civil engineering infrastructures can cause in intertidal habitats distribution and the ecological functions they provide for climate change adaption and mitigation.

High spatial heterogeneity and low connectivity of bacterial communities along a Mediterranean subterranean estuary.

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.

Groundwater discharge as a driver of methane emissions from Arctic lakes.

Lateral CH4 inputs to Arctic lakes through groundwater discharge could be substantial and constitute an important pathway that links CH4 production in thawing permafrost to atmospheric emissions via lakes. Yet, groundwater CH4 inputs and associated drivers are hitherto poorly constrained because their dynamics and spatial variability are largely unknown. Here, we unravel the important role and drivers of groundwater discharge for CH4 emissions from Arctic lakes. Spatial patterns across lakes suggest groundwater inflows are primarily related to lake depth and wetland cover. Groundwater CH4 inputs to lakes are higher in summer than in autumn and are influenced by hydrological (groundwater recharge) and biological drivers (CH4 production). This information on the spatial and temporal patterns on groundwater discharge at high northern latitudes is critical for predicting lake CH4 emissions in the warming Arctic, as rising temperatures, increasing precipitation, and permafrost thawing may further exacerbate groundwater CH4 inputs to lakes.

Seagrass (Halophila stipulacea) invasion enhances carbon sequestration in the Mediterranean Sea.

The introduction and establishment of exotic species often result in significant changes in recipient communities and their associated ecosystem services. However, usually the magnitude and direction of the changes are difficult to quantify because there is no pre-introduction data. Specifically, little is known about the effect of marine exotic macrophytes on organic carbon sequestration and storage. Here, we combine dating sediment cores (210 Pb) with sediment eDNA fingerprinting to reconstruct the chronology of pre- and post-arrival of the Red Sea seagrass Halophila stipulacea spreading into the Eastern Mediterranean native seagrass meadows. We then compare sediment organic carbon storage and burial rates before and after the arrival of H. stipulacea and between exotic (H. stipulacea) and native (C. nodosa and P. oceanica) meadows since the time of arrival following a Before-After-Control-Impact (BACI) approach. This analysis revealed that H. stipulacea arrived at the areas of study in Limassol (Cyprus) and West Crete (Greece) in the 1930s and 1970s, respectively. Average sediment organic carbon after the arrival of H. stipulacea to the sites increased in the exotic meadows twofold, from 8.4 ± 2.5 g Corg  m-2  year-1 to 14.7 ± 3.6 g Corg  m-2  year-1 , and, since then, burial rates in the exotic seagrass meadows were higher than in native ones of Cymodocea nodosa and Posidonia oceanica. Carbon isotopic data indicated a 50% increase of the seagrass contribution to the total sediment Corg pool since the arrival of H. stipulacea. Our results demonstrate that the invasion of H. stipulacea may play an important role in maintaining the blue carbon sink capacity in the future warmer Mediterranean Sea, by developing new carbon sinks in bare sediments and colonizing areas previously occupied by the colder thermal affinity P. oceanica.

The microbial dimension of submarine groundwater discharge: current challenges and future directions.

Despite the relevance of submarine groundwater discharge (SGD) for ocean biogeochemistry, the microbial dimension of SGD remains poorly understood. SGD can influence marine microbial communities through supplying chemical compounds and microorganisms, and in turn, microbes at the land-ocean transition zone determine the chemistry of the groundwater reaching the ocean. However, compared with inland groundwater, little is known about microbial communities in coastal aquifers. Here, we review the state of the art of the microbial dimension of SGD, with emphasis on prokaryotes, and identify current challenges and future directions. Main challenges include improving the diversity description of groundwater microbiota, characterized by ultrasmall, inactive and novel taxa, and by high ratios of sediment-attached versus free-living cells. Studies should explore microbial dynamics and their role in chemical cycles in coastal aquifers, the bidirectional dispersal of groundwater and seawater microorganisms, and marine bacterioplankton responses to SGD. This will require not only combining sequencing methods, visualization and linking taxonomy to activity but also considering the entire groundwater-marine continuum. Interactions between traditionally independent disciplines (e.g. hydrogeology, microbial ecology) are needed to frame the study of terrestrial and aquatic microorganisms beyond the limits of their presumed habitats, and to foster our understanding of SGD processes and their influence in coastal biogeochemical cycles.

Processes driving seagrass soils composition along the western Mediterranean: The case of the southeast Iberian Peninsula.

Seagrasses are distributed all along the coast of the Mediterranean Sea being Posidonia oceanica and Cymodocea nodosa the most common species. They promote sedimentation, leading to the formation of well-structured soils. Over the last decade, a growing attention has been paid to their role as CO2 sinks in the form of organic carbon (Corg) and to their use as environmental archives. However, most of the knowledge about pedogenetic processes in these soils refer to the rhizosphere. This study aims to understand seagrass soils biogeochemistry in the rhizosphere and below, which in turn can help to understand their long term formation processes. Fifteen cores were strategically sampled along a 350 km stretch of the Southeast Iberian coast, and analyzed for elemental composition (XRF core-scanning), magnetic susceptibility, Corg content and gran size distribution. The cores were dated by 210Pb and 14C-AMS techniques to estimate soil accretion. Principal component analysis was used to explore the main geochemical processes linked to soil formation. The results showed that terrestrial runoff plays a key role in meadow soil composition. Furthermore, Corg accumulation did not follow any general depth trend in our soil records, suggesting that temporal variation in Corg inputs is an important factor in determining carbon depth distribution within the soil. We obtained evidence that the establishment of well-developed, stable C. nodosa meadows in the Mediterranean Sea may be promoted by adverse environmental conditions to P. oceanica settlement. Metal's behavior within the meadow deposit and their interaction with organic matter and carbonates is unclear. The results presented in this paper highlight the importance of the influence of land-based inputs in the characteristics of seagrass meadow deposits, highly determining their Corg content, as well as the need for further studies on metal behavior, to understand their full potential as environmental records.

Long-term dynamics of production in western Mediterranean seagrass meadows: Trade-offs and legacies of past disturbances.

Seagrasses are marine angiosperms that can form highly productive, and valuable underwater meadows, which are currently in regression. A reliable assessment of their status and future evolution requires studies encompassing long-term temporal scales. With the aim of understanding seagrass ecosystem dynamics over the last centuries and millennia, twelve sediment cores were studied from seagrass meadows located along the Andalusian coast and at the Cabrera Island (western Mediterranean). This study is pioneer in using Fourier Transform Infrared (FTIR) spectroscopy as a tool to study environmental change in seagrass sediments. FTIR is a form of vibrational spectroscopy that provides information about the sediment chemical composition. Principal Component Analysis (PCA) was used to summarise spatio-temporal data of the FTIR vibratory peaks in combination with climate and geochemical proxy data. Several PCA signals were identified: (1) one likely related to the relative changes of the main primary producers and the sedimentary environment (carbonate or siliciclastic sediments, with aromatic or aliphatic organic matter); (2) the marine community production (polysaccharides, total organic matter content and biogenic silica); and (3) the seagrass production (aromatics, carbohydrates, phenols, proteins and lipids). A decrease of seagrass production along the mainland coast was evident since AD ~1850, which may be due to combined negative impacts of seawater warming, local anthropogenic impacts, and extreme setting conditions. The legacy of these combined stressors might have influenced the current poor state of seagrass meadows in the Alboran Sea. Our results also revealed a significant long-term trade-off between the level of seagrass production and its temporal stability (calculated as the inverse of the coefficient of variation). This study provides a reliable baseline data, helping to assess the magnitude of seagrass regression and its drivers. This paleoecological information can help design more targeted management plans and identify meadows where local management could be more efficient.

Submarine karstic springs as a source of nutrients and bioactive trace metals for the oligotrophic Northwest Mediterranean Sea.

Groundwater springs in karstified carbonate aquifers are known to transport carbon, nutrients and trace elements to the coastal ocean. The biogeochemical significance of submarine karstic springs and their impact on coastal primary production are often difficult to quantify. We investigated several karstic springs, including the first-order Port-Miou spring, in an urbanized watershed that is also severely impacted by sewage effluent (Calanques of Marseille-Cassis, France). Karstic springs were elevated in major nutrients and bioactive trace metals over Mediterranean seawater, with relatively low concentration ranges. Groundwater NO3- was likely derived from atmosphere-aquifer interactions, while DOC:DON ratios reveal that NO2- and NH4+ was autochthonously produced during mixing between karst groundwater and seawater. Submarine groundwater discharge (SGD) during March 2018 (wet season, baseflow conditions) was 6.7 ± 2.0 m3 s-1 for the entire investigated coastline, determined from simultaneous 224Ra and 226Ra mass balances. The contribution of groundwater PO43-, the major limiting nutrient of the Mediterranean Sea, sustained only 1% of primary production adjacent to sewage outfall, but between 7 and 100% of the local primary production in areas that were not impacted by sewage. Groundwater and seawater Fe:DIN and Fe:DIP ratios suggest that Fe was not a limiting micro-nutrient during the period of study, where bioactive trace metal fluxes were dominated by sewage and atmospheric deposition, although excess Fe from groundwater may locally enhance N fixation. Groundwater solute fluxes may easily vary by a factor of two or more over time because karst aquifers are sensitive to precipitation, as is the case of the regional carbonate karstified aquifer of Port-Miou, highlighting the critical importance of properly characterizing nutrient and trace metal inputs in these coastal environments.

Historical reconstruction of Small-scale gold mining activities in tropical wetland sediments in Bajo Cauca-Antioquia, Colombia.

Global mining activities in Latin America have increased exponentially over the last decade. The present study aims to assess the historical impact of Artisanal and Small-scale Gold Mining activities (ASGM) in the Department of Antioquia, Colombia, a region characterized by increased mining development over the past century. Historical trends of heavy metals (i.e., Ag, Cr, Cu, Hg, Ni, Pb, and Zn) were reconstructed for the past century in a tropical wetland near the mining district. Results indicate that local mining operations did not have a significant influence in the area until the mid-20th century when metal concentrations began to increase and exceeded background values. The significant increase in both sediment accumulation rates and total organic carbon (TOC) content during the 1920s reflects the deforestation of the area due to the diversification of the economy (e.g. coffee cultivation, mining or animal husbandry). Both concentrations and accumulation rates of metals increased exponentially after the 1980s as a consequence of the reactivation of alluvial gold exploitation, reaching values that exceeded up to 2-5 times the background levels. The historical metal trends in sediments from Las Palmas wetland reflected the historical socio-economic development in Antioquia and can be used as a good proxy for evaluating anthropogenic impacts in this region.

Remobilization of dissolved metals from a coastal mine tailing deposit driven by groundwater discharge and porewater exchange.

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 (223Ra, 224Ra, 226Ra and 228Ra) 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 Fe2+ 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.

River Deltas as hotspots of microplastic accumulation: The case study of the Ebro River (NW Mediterranean).

Microplastics (MPs) are considered pollutants that are ubiquitously distributed in aquatic environments. One of the key hotspot areas to understand fluxes of MPs entering into the oceans are transitional systems, between fresh and marine waters, where river estuaries in particular play an important role. In this study we analyzed MPs occurrence in the Ebro River Delta, Northeastern Iberian Peninsula, one of the largest wetland areas in the NW Mediterranean Basin. Microplastic profile, abundance, distribution, and characteristics were screened across different environmental matrices. MPs were collected in sandy beaches on the northern edge of the delta, in estuarine benthic sediments, and in surface waters of the Ebro River, with a mean abundance of 422 ±â€¯119 MPs·kg-1 DW, 2052 ±â€¯746 MPs·kg-1 DW and 3.5 ±â€¯1.4 MPs·m-3, respectively. Fibers were found to be the largest class (70 ±â€¯22%) of the three different environmental matrices investigated. We estimated that the Ebro surface water represents an input of 2.14 × 109 MPs·yr-1 to the Mediterranean Sea. The main contribution of this study is a new insight on the distribution of MPs across different environmental matrices in river estuaries, where estuarine benthic sediments were identified as a potential important sink for MPs.

Radium tracing nutrient inputs through submarine groundwater discharge in the global ocean.

Riverine and atmospheric inputs are often considered as the main terrestrial sources of dissolved inorganic nitrogen (DIN), phosphorus (DIP), and silicon (DSi) in the ocean. However, the fluxes of nutrients via submarine groundwater discharge (SGD) often exceed riverine inputs in different local and regional scale settings. In this study, we provide a first approximation of global nutrient fluxes to the ocean via total SGD, including pore water fluxes, by combining a global compilation of nutrient concentrations in groundwater and the SGD-derived 228Ra fluxes. In order to avoid overestimations in calculating SGD-derived nutrient fluxes, the endmember value of nutrients in global groundwater was chosen from saline groundwater samples (salinity >10) which showed relatively lower values over all regions. The results show that the total SGD-derived fluxes of DIN, DIP, and DSi could be approximately 1.4-, 1.6-, and 0.7-fold of the river fluxes to the global ocean (Indo-Pacific and Atlantic Oceans), respectively. Although significant portions of these SGD-derived nutrient fluxes are thought to be recycled within sediment-aquifer systems over various timescales, SGD-derived nutrient fluxes should be included in the global ocean budget in order to better understand dynamic interactions at the land-ocean interface.

Historical anthropogenic mercury in two lakes of Central Chile: comparison between an urban and rural lake.

Mercury concentrations in the environment tend to decrease in recent years due to environmental restrictions. Lakes store mercury in their sediments, making them potential secondary contamination sources. In South America, the occurrence of mercury in lake systems has been associated mainly with volcanic emissions and only few records anthropogenic contamination in the pre-Hispanic period. The objective of this research was to study historical anthropogenic mercury concentration in two lakes in Central Chile (La Señoraza and Pillo), in order to establish background mercury levels and their variations from preindustrial to modern periods. Different background levels and mercury concentrations were found in each lake, with significantly higher concentrations in Lake La Señoraza during the last 150 years. Mining-related activities during the nineteenth century could have a negligible influence on mercury concentrations. Later on, the use of coal railroads and subsequent employment of mercury in the cellulose industry were associated with three- and fourfold increases in mercury concentration over the nineteenth century background levels, which decrease once these activities ceased. However, in the case of Lake Pillo, an important increase in mercury concentration can be observed between 1990 and the early twenty-first century, which could be related to a higher watershed/lake area ratio, extensive agriculture, and volcanic emission, being the latter that could have contributed with mercury to both systems. Nevertheless, sedimentological characteristics in Lake Pillo can be favorable to retain mercury in this aquatic system up to the present day.

Constraining the temporal variations of Ra isotopes and Rn in the groundwater end-member: Implications for derived SGD estimates.

Submarine groundwater discharge (SGD) has been recognized as an important supplier of chemical compounds to the ocean that may influence coastal geochemical cycles. Radium isotopes (223Ra, 224Ra, 226Ra,228Ra) and radon (222Rn) have been widely applied as tracers of SGD. Their application requires the appropriate characterization of both the concentrations of tracers in the discharging groundwater and their distribution in the coastal water column. This study evaluates the temporal evolution of Ra isotopes and 222Rn concentrations in a dynamic subterranean estuary of a microtidal Mediterranean coastal aquifer that experiences large displacements of the fresh-saltwater interface as a necessary initial step in evaluating the influence of SGD in coastal waters. We show that changes in groundwater salinities due to the seaward displacement of the fresh-saltwater interface produced large variations in Ra activities in groundwater (by a factor of ~19, ~14, ~6, and ~11 for 223Ra, 224Ra, 226Ra and 228Ra, respectively), most importantly during rainfall events. In contrast, the 222Rn activities in groundwater oscillated only by a factor of 3 during these rainy periods. The large temporal variability in Ra activities hampers the characterization of the SGD end-member when using Ra isotopes as tracers, and thus presents a challenge for obtaining accurate SGD estimates. This study emphasizes the need to understand the hydrodynamics of coastal aquifers to appropriately constrain the Ra isotopes and 222Rn concentrations in groundwater and when applying both tracers in dynamic microtidal coastal systems.

Seasonal variation and sources of dissolved trace metals in Maó Harbour, Minorca Island.

The environmental conditions of semi-enclosed coastal water-bodies are directly related to the catchment, human activities, and oceanographic setting in which they are located. As a result of low tidal forcing, and generally weak currents, waters in Mediterranean harbours are poorly renewed, leading to quality deterioration. Here, we characterise the seasonal variation of trace metals (i.e. Co, Cd, Cu, Fe, Mo, Ni, Pb, and Zn) in surface waters, and trace metal content in sediments from Maó Harbour, a semi-enclosed coastal ecosystem in the NW Mediterranean Sea. Our results show that most of the dissolved trace metals in the waters of Maó Harbour exhibit a marked inner-outer concentration gradient, suggesting a permanent input into the inner part of the harbour. In general, metal concentrations in the waters of Maó Harbour are higher than those in offshore waters. Concentration of Cu (21±8nM), Fe (9.2±3.2nM) and Pb (1.3±0.4nM) are particularly high when compared with other coastal areas of the Mediterranean Sea. The concentration of some metals such as Cu and Zn increases during summertime, when the human population and boat traffic increase during the tourism season, and when resuspension from the metal enriched sediments is higher. The evaluation of the metal sources in the harbour reveals that, compared with other putative sources such as runoff, aerosol deposition and fresh groundwater discharges, contaminated sediments are the main source of the metals found in the water column, most likely through vessel-driven resuspension events. This study contributes to the understanding of the processes that control the occurrence and distribution of trace metals in Maó Harbour, thus aiding in the effective management of the harbour, and enhancing the overall quality of the seawater ecosystem.

Coastal ocean and shelf-sea biogeochemical cycling of trace elements and isotopes: lessons learned from GEOTRACES.

Continental shelves and shelf seas play a central role in the global carbon cycle. However, their importance with respect to trace element and isotope (TEI) inputs to ocean basins is less well understood. Here, we present major findings on shelf TEI biogeochemistry from the GEOTRACES programme as well as a proof of concept for a new method to estimate shelf TEI fluxes. The case studies focus on advances in our understanding of TEI cycling in the Arctic, transformations within a major river estuary (Amazon), shelf sediment micronutrient fluxes and basin-scale estimates of submarine groundwater discharge. The proposed shelf flux tracer is 228-radium (T1/2 = 5.75 yr), which is continuously supplied to the shelf from coastal aquifers, sediment porewater exchange and rivers. Model-derived shelf 228Ra fluxes are combined with TEI/ 228Ra ratios to quantify ocean TEI fluxes from the western North Atlantic margin. The results from this new approach agree well with previous estimates for shelf Co, Fe, Mn and Zn inputs and exceed published estimates of atmospheric deposition by factors of approximately 3-23. Lastly, recommendations are made for additional GEOTRACES process studies and coastal margin-focused section cruises that will help refine the model and provide better insight on the mechanisms driving shelf-derived TEI fluxes to the ocean.This article is part of the themed issue 'Biological and climatic impacts of ocean trace element chemistry'.