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- Determination of phthalic acid esters and di(2-ethylhexyl) adipate in fish and squid using the ammonium formate version of the QuEChERS method combined with gas chromatography mass spectrometryPublication . Sambolino, Annalisa; Ortega-Zamora, Cecilia; González-Sálamo, Javier; Dinis, Ana; Cordeiro, Nereida; Canning-Clode, João; Hernández-Borges, JavierIn the present study, the ammonium formate version of the QuEChERS method, considered highly advantageous in relation to instrument maintenance and other issues, was applied for the first time to extract a group of twelve phthalic acid esters (PAEs, i.e. dipropyl phthalate, DPP; diisobutyl phthalate, DIBP; dibutyl phthalate, DBP; diisopentyl phthalate, DIPP; di-n-pentyl phthalate, DNPP; dihexyl phthalate, DHP; butyl benzyl phthalate, BBP; dicyclohexyl phthalate, DCHP; di(2-ethylhexyl) phthalate, DEHP; di-n-octyl phthalate, DNOP; diisononyl phthalate, DINP; and diisodecyl phthalate, DIDP) and one adipate (di(2-ethylhexyl) adipate, DEHA) from two species of fish (Scomber colias and Katsuwonus pelamis) and one of squid (Loligo gahi). The method was validated in terms of linearity, trueness and matrix effects. Determination coefficients (R2 ) for matrix-matched calibration curves were higher than 0.99 in all cases, being the lowest calibration levels in the range 0.5–10 ng/g. Mean recovery values were between 70 and 117% with relative standard deviation values ≤20%. Matrix effects were soft (between − 20 and +20%) for most analytes and matrices, except in squid samples, which was mostly medium with a moderate ion suppression. The analysis of 10 samples of each type showed the presence of DIBP, DBP and DEHP at concentrations up to 44.2 ± 2.1 ng/g of wet weight in some of the samples and species, still not representing concerning values when considering the daily intake of such species of seafood in the human diet (tolerable daily intake -TDI- values were not exceeded). Results demonstrated that the ammonium formate version of the QuEChERS method can be applied with success for the extraction and determination of the selected PAEs and DEHA in fish and squid samples.
- The collapse of marine forests: drastic reduction in populations of the family Sargassaceae in Madeira Island (NE Atlantic)Publication . Bernal-Ibáñez, Alejandro; Gestoso, Ignacio; Wirtz, Peter; Kaufmann, Manfred; Serrão, Ester A.; Canning-Clode, João; Cacabelos, EvaSpecies of the genera Cystoseira, Ericaria, Gongolaria, and Sargassum (family Sargassaceae) are key components of the Mediterranean-Atlantic marine forests, essential for biodiversity and ecosystem functioning. Populations of these foundational species are particularly vulnerable to anthropogenic impacts, likely to be intensified under future scenarios of climate change. The decline and even disappearance of these species have been reported in different areas of the world. At Madeira Island (NE Atlantic), populations of Gongolaria abies-marina, Ericaria selaginoides, Sargassum vulgare, and Sargassum filipendula, the most ecologically relevant species in Macaronesian marine forests, have been suffering a drastic decline during the last decades, especially on the southern coast of the island, where anthropogenic pressure is higher than on the north coast. The lack of sufficient temporal coverage on qualitative and quantitative studies of Sargassaceae communities in Madeira poses a challenge to establish a specific period for this decline. Consulting qualitative studies and historical records, we have set for the first time a timeline that shows an evident decrease in Sargassaceae populations in the last 20 years on Madeira Island. Following this timeline, we pinpoint the start of this decline in the first decade of the 2000s. This can be particularly confirmed for places like Funchal and Reis Magos, with significantly higher historical records. Currently, most benthic communities on shallow subtidal rocky reefs along the south coast are dominated by sea urchins and crustose coralline algae, the so-called sea urchin barrens. However, in some cases, they are entirely covered by a layer of sediment. We discuss the possible factors contributing to these drastic changes, bringing Madeira’s marine forests to a dramatic decline. As many animal species rely on marine forests, the decline of Sargassaceae populations represents an invaluable ecological loss for the coastal ecosystem of the island.
- Seasonal variation in microplastics and zooplankton abundances and characteristics: the ecological vulnerability of an oceanic island systemPublication . Sambolino, Annalisa; Herrera, Inma; Álvarez, Soledad; Rosa, Alexandra; Alves, Filipe; Canning-Clode, João; Cordeiro, Nereida; Dinis, Ana; Kaufmann, ManfredThe ingestion of microplastics (MPs - plastic particles <5 mm) by planktivorous organisms represents a signif icant threat to marine food webs. To investigate how seasonality might affect plastic intake in oceanic islands' ecosystems, relative abundances and composition of MPs and mesozooplankton samples collected off Madeira Island (NE Atlantic) between February 2019 and January 2020 were analysed. MPs were found in all samples, with fibres accounting for 89 % of the particles. MPs and zooplankton mean abundance was 0.262 items/m3 and 18.137 individuals/m3 , respectively. Their monthly variations follow the seasonal fluctuation of environmental parameters, such as currents, chlorophyll-a concentration, sea surface temperature and precipitation intensity. A higher MPs/zooplankton ratio was recorded in the warm season (May-Oct), reaching 0.068 items/individual when considering large-sized particles (1000–5000 μm). This is the first study to assess the seasonal variability of MPs in an oceanic island system providing essential information respecting its ecological impact in pelagic environments.