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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 ∂ 15 N 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., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Authors. Published by Elsevier B.V. All rights reserved.)

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 CO 2 sinks in the form of organic carbon (C org ) 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, C org content and gran size distribution. The cores were dated by 210 Pb and 14 C-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, C org accumulation did not follow any general depth trend in our soil records, suggesting that temporal variation in C org 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 C org content, as well as the need for further studies on metal behavior, to understand their full potential as environmental records., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier B.V. All rights reserved.)

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., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier B.V. All rights reserved.)

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 NO 3 - was likely derived from atmosphere-aquifer interactions, while DOC:DON ratios reveal that NO 2 - and NH 4 + 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 m 3  s -1 for the entire investigated coastline, determined from simultaneous 224 Ra and 226 Ra mass balances. The contribution of groundwater PO 4 3- , 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., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier B.V. All rights reserved.)

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 ( 223 Ra, 224 Ra, 226 Ra and 228 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 2+ 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., (Copyright © 2019 Elsevier B.V. All rights reserved.)

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 ± 119 MPs·kg -1 DW, 2052 ± 746 MPs·kg -1 DW and 3.5 ± 1.4 MPs·m -3 , respectively. Fibers were found to be the largest class (70 ± 22%) of the three different environmental matrices investigated. We estimated that the Ebro surface water represents an input of 2.14 × 10 9 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., (Copyright © 2019 Elsevier B.V. All rights reserved.)

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 ( 223 Ra, 224 Ra, 226 Ra , 228 Ra) and radon ( 222 Rn) 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 222 Rn 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 223 Ra, 224 Ra, 226 Ra and 228 Ra, respectively), most importantly during rainfall events. In contrast, the 222 Rn 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 222 Rn concentrations in groundwater and when applying both tracers in dynamic microtidal coastal systems., (Copyright © 2017 Elsevier B.V. All rights reserved.)

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., (Copyright © 2016 Elsevier B.V. All rights reserved.)

The vertical distribution of (210)Pb is commonly used to date peat deposits accumulated over the last 100-150 years. However, several studies have questioned this method because of an apparent post-depositional mobility of (210)Pb within some peat profiles. In this study, we introduce the Initial Penetration–Constant Rate of Supply (IP-CRS) model for calculating ages derived from 210Pb profiles that are altered by an initial migration of the radionuclide. This new, two-phased, model describes the distribution of atmospheric-derived (210)Pb ((210)Pbxs) in peat taking into account both incorporation of (210)Pb into the accumulating peat matrix as well as an initial flushing of (210)Pb through the uppermost peat layers. The validity of the IP-CRS model is tested in four anomalous (210)Pb peat records that showed some deviations from the typical exponential decay profile not explained by variations in peat accumulation rates. Unlike the most commonly used (210)Pb-dating model (Constant Rate of Supply (CRS)), the IP-CRS model estimates peat accumulation rates consistent with typical growth rates for peatlands from the same areas. Confidence in the IP-CRS chronology is also provided by the good agreement with independent chronological markers (i.e. (241)Am and (137)Cs). Our results showed that the IP-CRS can provide chronologies from peat records where (210)Pb mobility is evident, being a valuable tool for studies reconstructing past environmental changes using peat archives during the Anthropocene.

The natural radionuclide (210)Pb is commonly used to establish accurate and precise chronologies for the recent (past 100-150 years) layers of peat deposits. The most widely used (210)Pb-dating model, Constant Rate of Supply (CRS), was applied using data from three peat cores from Chao de Lamoso, an ombrotrophic mire in Galicia (NW Spain). On the basis of the CRS-chronologies, maximum Pb concentrations and enrichment factors (EFs) occurred in the 1960s and late 1970s, consistent with the historical use of Pb. However, maximum Pb fluxes were dated in the 1940s and the late 1960s, 10 to 20 years earlier. Principal component analysis (PCA) showed that, although the (210)Pb distribution was mainly (74%) controlled by radioactive decay, about 20% of the (210)Pb flux variability was associated with atmospheric metal pollution, suggesting an extra (210)Pb supply source and thus invalidating the main assumption of the CRS model. When the CRS-ages were recalculated after correcting for the extra input from the (210)Pb inventory of the uppermost peat layers of each core, Pb flux variations were consistent with the historical atmospheric Pb deposition. Our results not only show the robustness of the CRS model to establish accurate chronologies of recent peat deposits but also provide evidence that there are confounding factors that might influence the calculation of reliable peat accumulation rates (and thus also element accumulation rates/fluxes). This study emphasizes the need to verify the hypotheses of (210)Pb-dating models and the usefulness of a full geochemical interpretation of peat bog records., (Copyright © 2012 Elsevier B.V. All rights reserved.)

In order to estimate atmospheric metal deposition in Southern Europe since the beginning of the Industrial Period (~1850 AD), concentration profiles of Pb, Zn and Cu were determined in four (210)Pb-dated peat cores from ombrotrophic bogs in Serra do Xistral (Galicia, NW Iberian Peninsula). Maximum metal concentrations varied by a factor of 1.8 for Pb and Zn (70 to 128μgg(-1) and 128 to 231μgg(-1), respectively) and 3.5 for Cu (11 to 37μgg(-1)). The cumulative metal inventories of each core varied by a factor of 3 for all analysed metals (132 to 329μgcm(-2) for Pb, 198 to 625μgcm(-2) for Zn and 22 to 69μgcm(-2) for Cu), suggesting differences in net accumulation rates among peatlands. Although results suggest that mean deposition rates vary within the studied area, the enhanced (210)Pb accumulation and the interpretation of the inventory ratios ((210)Pb/Pb, Zn/Pb and Cu/Pb) in two bogs indicated that either a record perturbation or post-depositional redistribution effects must be considered. After correction, Pb, Zn and Cu profiles showed increasing concentrations and atmospheric fluxes since the mid-XX(th) century to maximum values in the second half of the XX(th) century. For Pb, maximum fluxes were observed in 1955-1962 and ranged from 16 to 22mgm(-2)yr(-1) (mean of 18±1mgm(-2)yr(-1)), two orders of magnitude higher than in the pre-industrial period. Peaks in Pb fluxes in Serra do Xistral before the period of maximum consumption of leaded petrol in Europe (1970s-1980s) suggest the dominance of local pollutant sources in the area (i.e. coal mining and burning). More recent peaks were observed for Zn and Cu, with fluxes ranging from 32 to 52mgm(-2)yr(-1) in 1989-1996, and from 4 to 9mgm(-2)yr(-1) in 1994-2001, respectively. Our results underline the importance of multi-core studies to assess both the integrity and reliability of peat records, and the degree of homogeneity in bog accumulation. We show the usefulness of using the excess (210)Pb inventory to distinguish between differential metal deposition, accumulation or anomalous peat records., (Copyright © 2010 Elsevier B.V. All rights reserved.)