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.

Remoção de ibuprofeno de águas por oxidação catalítica

A ocorrência e destino de fármacos no ambiente aquático tem vindo a ser reconhecido como um problema emergente em química ambiental. Alguns compostos são resistentes à degradação nas estações de tratamento de águas residuais, ETARs, enquanto que outros, ainda que sofram degradação parcial, continuam a ser lançados nos meios aquáticos em quantidades apreciáveis. O Ibuprofeno, IB, um dos anti­ inflamatórios mais consumidos por todo o mundo, é um dos fármacos mais detectados no meio hídrico. Apesar dos sistemas de tratamento convencionais utilizados nas ETARs removerem até 90% do IB das águas residuais, é frequente o efluente descarregado conter ainda quantidades significativas deste poluente. A presença destes compostos no ambiente deve ser avaliada dado que possuem actividade biológica, mesmo a baixas concentrações. Os processos avançados de oxidação com peróxido de hidrogénio, na presença de catalisadores heterogéneos, permitem melhorar significativamente a remoção deste tipo de compostos em águas. Assim, foi objectivo deste trabalho o estudo da utilização de peróxido de hidrogénio como agente oxidante na remoção de IB em soluções aquosas, na presença de complexo de acetilacetonato de Ni (II) disperso em PDMS ou encapsulado em zeólitos NaY. Para o doseamento do fármaco em solução foi necessário desenvolver um método analítico consistindo de separação cromatográfica por HPLC e detecção e quantificação por UV-Vis. Não houve necessidade de recorrer a um passo de pré­ concentração de amostras por extracção em fase sólida (SPE) devido ao facto das concentrações de IB medidas ao longo do trabalho se terem sempre encontrado acima do LOQ (811 g L-1) do método analítico por injecção directa. Deste estudo pode concluir-se que o catalisador que apresentou melhor actividade catalítica e consequentemente maior remoção do IB em solução, foi o complexo de acetilacetonato de Ni (II), disperso em PDMS. Foi avaliada a influência, na conversão do IB, de diferentes parâmetros como a concentração inicial de peróxido de hidrogénio adicionada, quantidade de catalisador utilizada na mistura reaccional e temperatura. Os resultados permitiram concluir que os aumentos destes parâmetros conduzem a um aumento da actividade catalítica da reacção. A estabilidade catalítica do acetilacetonato de Ni (II)/PDMS, foi avaliada em ensaios consecutivos com a mesma amostra e nas mesmas condições, tendo-se observado que, após 8 utilizações, o catalisador perde ligeiramente a actividade (cerca de 11% do seu valor inicial). ABSTRACT: The presence and fate of pharmaceuticals in the aquatic environment is an emergent issue in environmental chemistry. Some compounds are poorly removed in wastewater treatment plants (WWTPs) while others, in spite of being partially removed, are still present in the WWTPs effluents and discharged in the receiving water bodies. Ibuprofen, IB, a non-steroid anti-inflammatory drug, is one of the most used and also one of the most frequently detected pharmaceutical contaminants in aquifers worldwide. Its removal by conventional wastewater treatment processes used in most WWTPs is usually high (up to 90% of incoming IB may be removed), but duet the high loads present in the influents, still significant amounts of IB usually leave the WWTPs in the treated effluents. The presence of these compounds in the environment must be evaluated considering that they may have some biological activity even at low concentrations. Advanced oxidation processes using hydrogen peroxide, in the presence of heterogeneous catalysts, provide a significantly improved removal of this type of substances from waters. Therefore, it was the aim of this work to study the use of hydrogen peroxide as an oxidizing agent in the removal of IB from aqueous solutions, in the presence of the catalyst nickel (II) acetylacetonate dispersed in PDMS or encapsulated in the NaY zeolite. For the quantification of the pharmaceutical in aqueous solution it was necessary to develop an analytical methodology based in chromatographic separation by HPLC and with UV-Vis detection and quantification. There was no need for a pre­concentration step of the samples by solid phase extraction (SPE) as the IB concentrations measured were always above the limit of quantification (811 bL1 of) the analytical method. The results from this study have shown that the catalyst which presented the best catalytic activity and the highest IB removal in solution was nickel (II) acetylacetonate dispersed in PDMS.

"Portuguese Observatory of Taeniasis and Cysticercosis": A "One Health" example for epidemiological surveillance of one neglected disease in a European country

Cysticercosis results from the ingestion Taenia solium eggs directly by faecal-oral route or contaminated food or water. Human tapeworm carriers who have become infected after ingesting pork meat contaminated with cysticerci release these eggs. Cysticercosis occurs after tapeworm eggs are ingested by an intermediate host (pig or human) and then hatch, migrate, and lodge in the host's tissues, where they develop onto larval cysticerci. When they lodged in the central nervous system of humans, results in the disease condition called Neurocysticercosis (NCC), with a heterogeneous manifestations depending of the locations of cysts, number, size and their stage of evolution (1). Consequently the prognostic ranges from asymptomatic to situations leading to death in 2% to 9.8%. of cases (7) In swine’s there are few studies, but recent works have proved that animals, for the same reasons, also have neurological abnormalities, expressed by seizures, stereotypic walk in circles, chewing motions with foamy salivation included tonic muscle contractions followed by a sudden diminution in all muscle tone leading to collapse (2). Conventional domestic wastewater treatment processes may not be totally effective in inactivating parasites eggs from Taenia solium, allowing some contamination of soils and agricultural products (11). In Portugal there are some evidence of aggregation of human cysticercosis cases in specific regions, bases in ecological design studies (6). There are few information about human tapeworm carriers and social and economic factors associated with them. Success in knowledge and consequently in lowering transmission is limited by the complex network of biological and social factors that maintain the spread. Effective control of mostly zoonosis require One Health approach, after a real knowledge and transparency in the information provided by the institutions responsible for both animal and human health, allowing sustained interventions targeted at the transmission cycle's crucial nodes. In general, the model used to control, reflects a rural reality, where pigs are raised freely, poor sanitation conditions and incipient sanitary inspection. In cysticercosis, pigs are obligate intermediate hosts and so considered as first targets for control and used as sentinels to monitor environmental T. solium contamination (3). Usually environmental contamination with Taenia spp. eggs is a key issue in most of studies with landscape factors influencing presence of Taenia spp. antigens in both pigs and humans (5). Soil-related factors as well as socio-economic and behavioural factors are associated with the emergence of significant clustering human cysticercosis (4,5). However scarce studies has been produced in urban environmental and in developed countries with the finality to characterize the spatial pattern. There are still few data available regarding its prevalence and spatial distribution; Transmission patterns are likely to exhibit correlations as housing conditions, water supply, basic sanitation, schooling and birthplace of the individual or relatives, more than pigs rearing free, soil conditions (9). As a matter of fact, tapeworm carriers from endemic zones can auto-infect or transmit infection to other people or arrive already suffering NCC (as a result of travelling to or being a citizen from an endemic cysticercosis country) to a free cysticercosis country. Transmission is fecal-oral; this includes transmission through person-to-person contact, through autoinfection, or through contaminated food This has been happening in different continents as North America (5.4–18% been autochthonous), Europe and Australia (7). Recently, case reports of NCC have also emerged from Muslim countries. (10). Actually, different papers relate an epidemic situation in Spain and Portugal (7, 8). However the kind of study done does not authorize such conclusion. There are no evidence that infections were acquired in Portugal and there are not characterized the mode of transmission. Papers with these kind of information will be allow to have economic consequences resulted from artificial trade barriers with serious consequences for pig producers and pig meat trade. We need transparency in information’s that allow provide the basis to support the development and targeting of future effective control programmes (and prove we need that). So, to have a real picture of the disease, it is necessary integrate data from human, animal and environmental factors surrounding human and pig cases to characterize the pattern of the transmission. The design needs to be able to capture unexpected, and not common outcomes (routine data). We need to think “One Health” to get a genuine image of the situation.