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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]

Sunscreens have been shown to give the most effective protection for human skin from ultraviolet (UV) radiation. Chemicals from sunscreens (Le., 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 (H202), 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 H202 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 T i0 2 nanoparticles to the water and produce an increment in the concentration of H202 of 270 nM/day. Our results, together with the data provided by tourism records in the Mediterranean, point to Ti02 nanoparticles as the major oxidizing agent entering coastal waters, with direct ecological consequences on the ecosystem. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]