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There is a current interest in the study of the geochemical behavior of the rare earth elements (REE) in aquatic systems since their identification as potential microcontaminants in natural waters. In this context, here we report the concentrations and patterns of dissolved REE (dREE) in the waters of the Gulf of Cádiz (GoC) and its major estuaries (Guadiana, Tinto-Odiel and Guadalquivir). Contamination in this area by metals has been extensively reported, linked to acid-mine inputs resulting from the mineralization of the Iberian Pyrite Belt, discharged mainly to the Tinto-Odiel river. However, the impact of these inputs on the concentrations and distribution of the dREE in the coastal waters of the GoC has not been addressed yet. Accordingly, elevated concentrations of dREE were obtained in the Tinto-Odiel estuary compared to the Guadiana and Guadalquivir, reflecting the impact of acid-mine drainage on this system. Only a significant fraction of anthropogenic gadolium (Gd) was observed in the Guadalquivir estuary, as a result of the input from major urban areas, where anthropogenic Gd fractions higher than 70% over the total dissolved pool were obtained for the freshwater end-member. Regarding the surface waters of the GoC, typical NE Atlantic distribution patterns of dREEs were obtained, but modified by two different end-members within this region. Accordingly, and despite the low water discharge of the Tinto-Odiel river, its elevated concentrations lead to an increase in the concentrations of dREEs in the nearshore waters of the GoC and producing a distinctive signature as observed for the MREE anomalies and HREE/LREE ratios. At the easternmost stations, close to the Strait of Gibraltar, these signals are also impacted by the inflow of Mediterranean waters and also by the discharge of the Guadalquivir river. [ABSTRACT FROM AUTHOR]

To investigate to what extent episodic physical processes regulate nutrient availability and phytoplankton assemblages of the Mahon estuary (Minorca Island), we carried out an intensive field study during 2010-2011. During the study period, environmental conditions spanned from intense stratification to a continuous mixing and from lack of riverine inflow to intense runoff. Our data reveals a sequence of biogeochemical states of the estuary that result from the interplay between runoff, other non-periodic forcings (winds, sea level oscillations), and variations in water renewal. Seasonal runoff was revealed as a major driver of winter circulation and of the influx of inorganic nutrients, in particular nitrate. However, because of the combination between runoff and flushing time, the effects of floodwater events on phytoplankton are short-lived (days). Conversely, during summer, when freshwater influx declines, water renewal relies on pulsed atmospheric forcing that may be of local or remote origin. As depicted from the low nitrate concentrations (<1 μM) and enhanced ammonium (>1 μM), this change in circulation and external loads carries nutrient assimilation within the estuary head and forces the use of remnant nutrients through regenerating pathways to sustain an enhanced phytoplankton biomass at the lower estuary. Episodic variability represented between 52 and 65% of the annual chlorophyll variance. Despite the fact that episodic pulses represented intense departures from base biogeochemical state of the estuary, at time scale larger than weeks, the phytoplankton community composition and dynamics was largely regulated by the integrated effect of these episodes and other environmental drivers associated with seasonality rather than by individual storm events only. Our results suggest that even though the system presents good recovery capacity to individual storm episodes, it may be more vulnerable to increased nutrient fluxes during summer, as well as to changes in episode timing and frequency. [ABSTRACT FROM AUTHOR]

Submarine groundwater discharge (SGD) and derived nutrient (NO2-, NO3-, NH4+, PO43-, and SiO2) and trace element (Cd, Co, Cu, Fe, Mo, Ni, Pb, V and Zn) loadings to the coastal sea were systematically assessed along the coast of Majorca Island, Spain, in a general survey around the island and in three representative coves during 2010. We estimated that brackish water discharges through the shoreline are important contributors to the DEN, SiO2 Fe, and Zn budgets of the nearshore waters. Furthermore, our results showed that SGD-derived elements are conditioned by the hydrogeological formations of the aquifer and discharge type. Thus, while rapid discharges through karstic conduits are enriched in SiO2 and Zn, the large detrital aquifers of the island typically present enhanced concentrations of Fe. The estimated total annual inputs of chemicals constituents discharged by SGD to the coastal waters were as follows: DIN: 610 × 103 kg yr-1, SiO2: 1400 × 103 kg yr-1, Fe: 3.2 × 103 kg yr-1, and Zn: 2.0 × 103 kg yr-1. Our results provide evidence that SGD is a major contributor to the dissolved pool of inorganic nutrients and trace metals in the nearshore waters of Majorca. [ABSTRACT FROM AUTHOR]

The article explores the relationship between the changes in microbial communities and submarine groundwater input. It presents a study concerning the response of a coastal microbial community to enriched groundwater coming from low-impacted and anthropogenically influenced localities of Cabrera harbour and Santa Ponça beach in Mallorca, Spain, respectively. Findings are said to confirm that groundwater input supports the growth of autotrophic plankton as well as causes short-term changes to the structure of the microbial food-web. The study suggests the possibility that new equilibrium states can be established in coastal communities as a result of continuous groundwater inputs that can also lead to alternative trophic interactions and diverse phytoplankton assemblages.

Microphytobenthos (MPB) contributes significantly to estuarine primary production, so that quantifying its biomass is crucial for assessing their ecosystem functioning. Conventional sampling methods are labour-intensive, logistically challenging, and cannot provide a comprehensive spatial distribution map of MPB biomass. Satellite imagery has offered a feasible alternative for mapping large areas at various temporal and spatial resolutions. However, no imaging device with a spatial resolution consistent with the few square centimetres sampled in-situ has been used in the field. This makes it challenging to accurately relate field biomass measurements with remotely sensed radiometric observations. In this study, two similar multispectral sensors were mounted on an unmanned aerial vehicle (UAV) at different altitudes, as well as on a custom-built device specifically designed to acquire images at ∼1 m altitude, in order to collect very-high spatial resolution reflectance data of MPB biofilms at the Guadalquivir Estuary (Spain) mudflats. In addition, a hyperspectral spectroradiometer acquiring in-situ field reflectance was used for validation. Simultaneously, MPB samples were collected using a 2 mm depth contact corer method, which were analysed through high-performance liquid chromatography (HPLC) to measure the concentrations of major MPB pigments. To assess the relationship between the MPB pigments and different reflectance-based spectral indices, generalised linear mixed effects models (GLMMs) were used, achieving a significant positive relationship between chlorophylls and all spectral indices tested. These models were used to map microphytobenthic biomass, yielding a mean biomass in the range of 30-50 mg Chl-a m -2 in the Guadalquivir estuary during late winter. This study demonstrates the potential of low-altitude/high spatial resolution radiometric imaging as an efficient, rapid, and non-destructive addition to in-situ measurements of MPB biomass, providing exciting perspectives for the monitoring of estuarine systems on a millimetric scale of variability., 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.)

The 2021 Tajogaite eruption in La Palma (Canary Islands, Spain) emitted vast volumes of lava during 85 days, which reached the ocean in several occasions at the western flank of the island. Most of these flows merged to create a primary lava delta, covering an area of 48 ha, with an additional 30 ha underwater. Here we characterize the effects of the lava-seawater interaction on the surrounding marine environment. The area was sampled during two multidisciplinary oceanographic cruises: the first one comprised the days before the lava reached the ocean and after the first contact; and the second took place a month later, when the lava delta was already formed but still receiving lava inputs. Physical-chemical anomalies were found in the whole water column at different depths up to 300 m in all measured parameters, such as turbidity (+9 NTU), dissolved oxygen concentration (-17.17 μmol kg -1 ), pH T25 (-0.1), and chlorophyll-a concentration (-0.33 mg m -3 ). Surface temperature increased up to +2.3 °C (28.5 °C) and surface salinity showed increases and decreases of -1.01 and +0.70, respectively, in a radius of 4 km around the lava delta. In the water column, the heated waters experimented a lava-induced upwelling, bringing deeper, nutrient-rich waters to shallower depths; however, this feature did not trigger any phytoplankton bloom. In fact, integrated chlorophyll-a showed an abrupt decrease of -41 % in just two days and -69 % a month later, compared to prior conditions. The chlorophyll-a depletion reached a distance larger than 2.5 km (not delimited)., 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.)

In this study, seawater quality was monitored with high-resolution satellite imagery during the 2021 volcanic eruption (September-December) on La Palma Island (Spain), the longest recorded in the history of the island, and the most destructive in the last century in Europe. The Sentinel-2A/B twin satellites and Landsat-8 satellite were jointly used as an optical constellation, which allowed us to successfully characterize the short- and medium-term evolution of the new lava delta and subsequent impact on the seawater. Robust atmospheric and sunglint correction approaches were applied to thoroughly quantify the environmental changes caused on the adjacent coastal waters. The cloud and volcanic ash coverage remained very high over the coast during the event, so restricted information with 14 images (45% of the total scenes) was retrieved from the multi-sensor approach. Nevertheless, the availability of pre-, syn-, and post-eruption satellite products allowed us to map and detect the main water quality variations in the marine environment. On the one hand, during the eruption, a change in the properties of the water quality was observed, with a markedly increased turbidity on the western side of the island near the new lava delta due to the deposition of volcanic ash and material. On the other hand, chlorophyll-a concentration did not significantly increase, algal blooms were not observed, and oligotrophic conditions were not swiftly altered towards eutrophic conditions. This information offered an excellent opportunity to characterize the emplacement of the new lava delta and its impact on the marine environment in La Palma. The present multi-sensor strategy is an excellent opportunity to highlight the potential of remote sensing technology as a relevant and powerful tool for future hazard monitoring and assessment during catastrophes and for a better interpretation of their impact on the marine environment., 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 © 2022 The Author(s). Published by Elsevier B.V. All rights reserved.)

The rupture of a mine dam in Aznalcóllar (SW Spain) in April 1998 entailed the contamination of Guadalquivir River and its estuary. To study the ability of bivalve shells to monitor the temporal changes on metal composition in the area, two year old Scrobicularia plana were obtained from two different locations of the estuary (Pantalan highly influenced and Pantoca less influenced) during the year 2000 and 2007. Co, Hg, Mo, Ni and Zn content was measured in shell and soft tissue of S. plana. Metal composition in shells sampled by micromilling and corresponding to the years 1999, 2000, 2006 and 2007 was higher in Pantalan (Co: 5.88 +/- 2.7 microg g(-1); Hg: 0.04 +/- 0.03 microg g(-1); Mo: 0.41 +/- 7.90 microg g(-1); Ni: 37.66 +/- 25.56 microg g(-1) and Zn: 9.19 +/- 8.88 microg g(-1)) than in Pantoca (Co: 3.64 +/- 0.50 microg g(-1); Hg: 0.02 +/- 0.02 microg g(-1); Mo: 4.70 +/- 1.20 microg g(-1); Ni: 7.21 +/- 13.60 microg g(-1) and Zn: 3.90 +/- 1.89 microg g(-1)). A marked temporal decrease was observed for all metals in Pantalan station with concentrations of Co, Hg, Mo, Ni and Zn varying respectively from 7.35 +/- 3.02, 0.05 +/- 0.03, 19.90 +/- 2.40, 70.58 +/- 21.94 and 18.04 +/- 0.98 microg g(-1), in 1999 to 3.07 +/- 1.08, 0.009 +/- 0.001, 2.40 +/- 1.43, 10.11 +/- 3.80 and 1.11 +/- 0.33 microg g(-1) in 2007, indicating that the effect of the mine accident had diminished significantly. Metal content in soft tissues did not follow the same decreasing trend indicating that soft tissues present a different capacity to accumulate metals from the environment. Our results confirm that micromilling shells are a suitable tool to assess bioaccumulation ofcontaminants during the entire life-span of bivalves.

A growing awareness of the risks associated with skin exposure to ultraviolet (UV) radiation over the past decades has led to increased use of sunscreen cosmetic products leading the introduction of new chemical compounds in the marine environment. Although coastal tourism and recreation are the largest and most rapidly growing activities in the world, the evaluation of sunscreen as source of chemicals to the coastal marine system has not been addressed. Concentrations of chemical UV filters included in the formulation of sunscreens, such as benzophehone 3 (BZ-3), 4-methylbenzylidene camphor (4-MBC), TiO₂ and ZnO, are detected in nearshore waters with variable concentrations along the day and mainly concentrated in the surface microlayer (i.e. 53.6-577.5 ng L⁻¹ BZ-3; 51.4-113.4 ng L⁻¹ 4-MBC; 6.9-37.6 µg L⁻¹ Ti; 1.0-3.3 µg L⁻¹ Zn). The presence of these compounds in seawater suggests relevant effects on phytoplankton. Indeed, we provide evidences of the negative effect of sunblocks on the growth of the commonly found marine diatom Chaetoceros gracilis (mean EC₅₀ = 125±71 mg L⁻¹). Dissolution of sunscreens in seawater also releases inorganic nutrients (N, P and Si forms) that can fuel algal growth. In particular, PO₄³⁻ is released by these products in notable amounts (up to 17 µmol PO₄³⁻g⁻¹). We conservatively estimate an increase of up to 100% background PO₄³⁻ concentrations (0.12 µmol L⁻¹ over a background level of 0.06 µmol L⁻¹) in nearshore waters during low water renewal conditions in a populated beach in Majorca island. Our results show that sunscreen products are a significant source of organic and inorganic chemicals that reach the sea with potential ecological consequences on the coastal marine ecosystem.