Sunscreens have been shown to give the most effective protection for human skin from ultraviolet (UV) radiation. Chemicals from sunscreens (i.e., UV filters) accumulate in the sea and have toxic ...effects on marine organisms. In this report, we demonstrate that photoexcitation of inorganic UV filters (i.e., TiO2 and ZnO nanoparticles) under solar radiation produces significant amounts of hydrogen peroxide (H2O2), a strong oxidizing agent that generates high levels of stress on marine phytoplankton. Our results indicate that the inorganic oxide nanoparticle content in 1 g of commercial sunscreen produces rates of H2O2 in seawater of up to 463 nM/h, directly affecting the growth of phytoplankton. Conservative estimates for a Mediterranean beach reveal that tourism activities during a summer day may release on the order of 4 kg of TiO2 nanoparticles to the water and produce an increment in the concentration of H2O2 of 270 nM/day. Our results, together with the data provided by tourism records in the Mediterranean, point to TiO2 nanoparticles as the major oxidizing agent entering coastal waters, with direct ecological consequences on the ecosystem.
The world coastal-zone population and coastal tourism are expected to grow during this century. Associated with that, there will be an increase in the use of sunscreens and cosmetics with UV-filters ...in their formulation, which will make coastal regions worldwide susceptible to the impact of these cosmetics. Recent investigations indicate that organic and inorganic UV-filters, as well as many other components that are constituents of the sunscreens, reach the marine environment - directly as a consequence of water recreational activities and/or indirectly from wastewater treatment plants (WWTP) effluents. Toxicity of organic and inorganic UV filters has been demonstrated in aquatic organism. UV-filters inhibit growth in marine phytoplankton and tend to bioaccumulate in the food webs. These findings together with coastal tourism data records highlight the potential risk that the increasing use of these cosmetics would have in coastal marine areas. Nevertheless, future investigations into distribution, residence time, aging, partitioning and speciation of their main components and by-products in the water column, persistence, accumulation and toxicity in the trophic chain, are needed to understand the magnitude and real impact of these emerging pollutants in the marine system.
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•Sunscreen ingredients are detected in the marine environment.•Components of sunscreens have environmental consequences in coastal ecosystems.•Future investigations are needed to understand the environmental impact of sunscreens.
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The Mediterranean region is, by far, the leading tourism destination in the world, receiving more than 330 million tourists in 2016. This tourism is undertaken mostly for seaside ...holidays, and during the summer season concentrates between 46% and 69% of the total international arrivals; this is equivalent to a density of 2.9 tourists per meter of Mediterranean coast, or double this number taking into account the local/permanent population in addition. Previous studies have reported not only the presence of sunscreen in the various environmental compartments (water, sediments and biota) of the Mediterranean Sea (MS) and other regions, but also show that sunscreen products are toxic for marine biota and are accumulated and biomagnificated. Here, we highlight that the environmental risk of these chemicals is likely to be exacerbated in the MS due to the massive influx of tourists and its densely populated coasts, the basin's limited exchanges with the ocean, the high residence time of surface waters, and its oligotrophic waters.
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.
This study quantifies the concentration of trace metals in coastal marine macrophytes (seagrasses, Chlorophytae, Phaeophytae and Rhodophytae). We do so by compiling, from 155 peer review research ...articles, almost 23,000 estimates of trace metals (As, Cd, Co, Cr, Cu, Fe, Hg, Mn, Ni, Pb and Zn) contents in natural populations of marine macroalgae and seagrasses distributed worldwide. The objective was to explore the global distribution of concentrations of these metals in marine macrophytes, provide an estimate of their average and range in its tissues and to identify hotspots of coastal pollution. Our results reveal Phaeophytae as the group with the largest accumulation capacity and tolerance to elevated concentrations of metals regardless the species and the location. The mapping of geographic distribution of metal accumulation in marine macrophytes identifies some coastal areas as hotspots of trace metal contamination, where concentrations could reach levels up to 600 times higher than the mean.
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•A global dataset of trace metal concentration in marine macrophyte was compiled.•Phaeophytae can accumulate elevated concentrations of metals.•Hotspots of metal contamination have been identified in coastal areas worldwide.•Hotspots are mainly caused by anthropogenic activities.
Against the traditional vision, the relations between the Spanish Monarchy and the Republic of Venice improved significantly during the second half of the 17th century. Once again, the war against ...the Ottomans in Candia (1645-1669) forced the Serenissima to look for the support of the Catholic King. For this reason, the role played by their ambassadors in Madrid, with a view to achieve the necessary assistance of Philip IV, became essential for the Venetian interests. At the same time, they pursued to ensure a relevant and closer position to the principal nucleus of power in the Spanish court. Accordingly, the continuous disputes with the members of the Spanish institutions with regard to their lodging become an essential field of study to measure the degree of influence, supremacy or immunity of these legates during the reigns of the two last monarchs of the House of Austria.
Submarine groundwater discharge (SGD) and derived nutrient (NO2 –, NO3 –, NH4 +, PO4 3–, 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 DIN, 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.
After seventy years of peace, Venice was caught once again in a conflict against the Great Gateway for the kingdom of Candia (1645-1669). However, the Serenissima's appeals to the European powers for ...their support did not have the desired impact until the Ottoman attacks in Hungary and Transylvania in the late 1650s. These events allowed the Holy See to carry out a maneuver to recover the Catholic leadership through a common formula: The Holy League.
In the following pages we will analyze the role of the Papacy, the Empire, France, Spain and Venice in the congress that took place at the papal court between 1661 and 1662 to achieve the Catholic confederation. Negotiations that did not come to fruition in view of the conflicting goals of the different parties involved, and, especially, those of Philip IV and Louis XIV.
Tras setenta años de paz, Venecia se vio nuevamente atrapada en un conflicto con la Sublime Puerta por el reino de Candía (1645-1669). No obstante, el llamamiento de la Serenísima a las potencias europeas en pos de su apoyo no tuvo los efectos deseados hasta que, a finales de la década de los cincuenta, tuvieron lugar los ataques otomanos en Hungría y Transilvania. Estos hechos permitieron a la Santa Sede llevar a cabo una maniobra para recuperar el liderazgo del bando católico a través de una fórmula habitual: la Liga Santa.
En las siguientes páginas analizaremos el papel del Papado, el Imperio, Francia, España y Venecia en el congreso que tuvo lugar en la corte pontificia entre 1661 y 1662 para alcanzar la confederación católica. Unas negociaciones que no llegaron a buen puerto a tenor de los intereses contrapuestos de las distintas partes, y, muy especialmente, los de Felipe IV y Luis XIV.
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.