Avaliação da eficiência de remoção do contaminante de origem farmacêutica atenolol pela planta phragmites australis em leitos construídos de macrófitas

O atenolol é um fármaco β-bloqueador normalmente encontrado em águas residuais devido à incapacidade que os processos convencionais de tratamento destas águas têm em removê-lo. Neste trabalho foram utilizados microcosmos de leitos construídos de macrófitas de fluxo sub-superficial utilizando uma matriz de argila expandida (LECA) e plantados com Phragmites australis para avaliar a sua capacidade em remover atenolol das águas residuais. Para a detecção e quantificação do atenolol em soluções aquosas (águas e efluentes) desenvolveu-se e optimizou-se uma metodologia analítica usando separação cromatográfica por HPLC e detecção espectrofotométrica por diode array (HPLC-DAD) ou por ultravioleta visível (HPLC-UV-Vis). Desenvolveu-se também um procedimento de limpeza e concentração de amostra por extracção em fase sólida (SPE), o qual foi utilizado sempre que as concentrações do analito se encontraram abaixo dos limites de quantificação do equipamento. A utilização desta metodologia de HPLC, combinada com uma eficaz pré-concentração por SPE, resultou num método analítico com um limite de quantificação muito reduzido (9 ngmL-1) e elevada reprodutibilidade (RSD<4%). A eficiência de remoção de atenolol pelos sistemas de macrófitas estudados foi de 93% após um tempo de retenção de 4 dias. Foram testados leitos só com LECA e com LECA e plantas para remoção do atenolol. Nos leitos só com LECA, a cinética de remoção foi caracterizada por um rápido passo inicial (uma remoção de aproximadamente 75% após apenas 24 h), o qual é frequentemente atribuído à adsorção na matriz de LECA. A remoção de atenolol nos leitos de LECA continuou a aumentar de forma constante até ao final do ensaio (8 dias), sendo, contudo cerca de 5-10% mais baixo do que o valor observado nos leitos das plantas após os 4 primeiros dias. Para o tempo de retenção de 4 dias a maioria do atenolol é removido pela matriz de LECA, porém um acréscimo de cerca de 12-14% relativamente à eficiência de remoção global pode ser atribuído às plantas (Phragmites australis), o que está de acordo com trabalhos anteriormente publicados. Apesar de ser necessário realizar mais testes utilizando sistemas em larga escala, de modo a conseguir avaliar totalmente o comportamento do atenolol num sistema de leitos construídos de macrófitas, o presente estudo apresenta a possibilidade de aplicar este tipo de sistemas, relativamente baratos, no tratamento de águas residuais contaminadas com atenolol. ABSTRACT: Atenolol is a β-blocker drug commonly found in wastewaters due to the inability of the conventional wastewater treatment processes to remove it. ln this study, subsurface flow constructed wetland microscosm systems have been established with a matrix of light expanded clay aggregates (LECA) and planted with Phragmites australis in order to evaluate their ability to remove atenolol from wastewater. For the detection and quantification of atenolol in aqueous solutions (water and wastewater), an adequate analytical methodology was developed and optimized using chromatographic separation by HPLC and diode array (DAD) or UV-Vis spectrophotometric detection. A sample clean-up and preconcentration procedure by solid phase extraction (SPE) was also developed for use whenever the concentration levels of the analyte were below the instrument's limit of quantification. Combined with an efficient SPE concentration step, the use of HPLC yielded an analytical method for atenolol quantification with very low LOQ (9 ngmL-1) and high reproducibility (RSD< 4%). Overall atenolol removal efficiency of 93% was achieved after a retention time of only 4 days with the microcosm systems planted with Phragmites australis. The removal kinetics was characterized by an initial fast step (removal of about 75% after just 24h) which is mainly attributable to adsorption on the LECA matrix. Atenolol removal in LECA beds continues to increase in a steady pace up to the end of the assay (8 days) being nevertheless about 5-l 0% lower than those observed in the planted beds after the first 4 days. For the retention time of 4 days most of the atenolol is removed by the LECA matrix but an additional 12-14% to the overall removal efficiency can be attributed to the Phragmites plants, which comes in agreement with other published reports. Despite the fact that further tests using larger­ scale systems are required to fully evaluate the atenolol behavior in a constructed wetland system, this study points out to the possible application of these low-cost wastewater systems to treat atenolol contaminated wastewater.

Geomorphological constraining of tsunami (?) run-up in the Alcantarilha coastal lowland (Central Algarve, Portugal)

The Alcantarilha lowland, partly barred by a well developed barrier, including foredunes covering Pleistocene-Holocene beachrock and aeolianite, develops across the Alcantarilha infilled estuary, the beach-dune extending further SE until the Salgados lagoon. A topographic and coring survey revealed a peculiar feature at the leeward toe of the dune ridge close to the inlet area: a sandy fan with location, shape and morphology suggesting emplacement by single or multiple overwash of the barrier tip rather than tidal forcing. Its storm or tsunami origin and age are under investigation, and the only time-constrain available at present is that it should post-date ca. 6600 cal BP, the most recent in situ aeolianite (Moura et al., 2007) dated so far. METHODS, DATA SET AND RESULTS The fan boundaries are distinctive in aerial photos and satellite images: it is roughly ellipsoidal, ~200 m wide and ~300 m elongated paralleling the shoreline, rising ~ 0.9-1.2 m above the surrounding floodplain surface. Detailed topography shows that its short axis aligns with SW-NE elongated (though irregular) depressions in the dune crest, which link the beach with the fan. This could have favoured funnelling of, or erosion by, water overtopping the barrier but, in either case, the fan should correspond to extreme and abrupt event(s) of coastal flooding. 18 trenches and cores were performed in the exposed area of the fan and nearby flood plain to obtain samples and data on its sedimentology, lithostratigraphy and geometry. The fan consists of well sorted and rounded sand (Fig. 2). It thins away and wedges out landwards of the apex (located near Alc29T) where it is partly covered by dune sand. Its lower boundary is undulating and marked by textural contrast between sand (fan) and underlying mud (alluvial/lagoonal); an accumulation of marine-sourced perforated pebbles showing limited lateral continuity may pinpoint this boundary near the foredune (core Alc 25, ca. 80 m westward of profile in Fig.1); mud-balls were also observed immediately above this surface in cores and trenches. As the washover was probably emplaced in a barred lagoonal/estuarine floodplain setting, the fan’s northern outer belt is enclosed by low-energy sediments (not shown in Fig. 2).