Arsenic speciation in edible alga samples by microwave-assisted extraction and high performance liquid chromatography coupled to atomic fluorescence spectrometry

Twelve commercially available edible marine algae from France, Japan and Spain and the certified reference material (CRM) NIES No. 9 Sargassum fulvellum were analyzed for total arsenic and arsenic species. Total arsenic concentrations were determined by inductively coupled plasma atomic emission spectrometry (ICP-AES) after microwave digestion and ranged from 23 to 126 μg g−1. Arsenic species in alga samples were extracted with deionized water by microwave-assisted extraction and showed extraction efficiencies from 49 to 98%, in terms of total arsenic. The presence of eleven arsenic species was studied by high performance liquid chromatography–ultraviolet photo-oxidation–hydride generation atomic–fluorescence spectrometry (HPLC–(UV)–HG–AFS) developed methods, using both anion and cation exchange chromatography. Glycerol and phosphate sugars were found in all alga samples analyzed, at concentrations between 0.11 and 22 μg g−1, whereas sulfonate and sulfate sugars were only detected in three of them (0.6-7.2 μg g−1). Regarding arsenic toxic species, low concentration levels of dimethylarsinic acid (DMA) (<0.9 μg g−1) and generally high arsenate (As(V)) concentrations (up to 77 μg g−1) were found in most of the algae studied. The results obtained are of interest to highlight the need to perform speciation analysis and to introduce appropriate legislation to limit toxic arsenic species content in these food products.

Validación de HP UV-LED para la detección en continuo de contaminantes en aguas continentales mediante fluorescencia

La preservación del medio ambiente, el avance en las técnicas para que el impacto de la actividad humana sobre la fauna y flora sea lo menor posible, hacen que se deban monitorizar los diversos indicadores de calidad. El presente estudio viene motivado debido a que actualmente existen sistemas de medida y control en continuo de la calidad de las aguas, al margen de los estudios de laboratorio por toma de muestras, a través de los cuales se obtienen indicadores de calidad. El desarrollo tecnológico en analizadores en continuo para la medida de fósforo, amonio, DBO y otros, hacen que cada vez se consiga un control más exhaustivo de la calidad en tiempo real. Sin embargo, la detección temprana de contaminantes que no deben encontrarse presentes en el agua, hacen que el desarrollo de sensores de detección de estos contaminantes sea de gran utilidad. A este respecto, las técnicas mediante fluorescencia presentan enormes ventajas, ya que no existe contacto directo con la muestra, reduciéndose el desgaste y alargando el tiempo entre mantenimientos, como se ha comprobado en numerosos desarrollos con tecnología láser. Para la producir fluorescencia, tradicionalmente se vienen utilizando en el laboratorio principalmente lámparas de gas y monocromadores. Los nuevos LED de alta potencia en el espectro ultravioleta son una alternativa muy interesante que además puede ser aplicada en los mencionados sistemas de medición en continuo. En este trabajo se realiza un estudio de viabilidad de estos dispositivos como fuentes de excitación para la producción de fluorescencia tomando como contaminantes los hidrocarburos. El funcionamiento en estaciones en continuo hace que se tenga que realizar además ensayos de vida acelerados, así como estudios de modos de trabajo. Al respecto de la fluorescencia producida, se estudia la influencia de factores que pueden afectar a las medidas, tales como la temperatura. El estudio del espectro y su análisis para la identificación del contaminante es otro de los puntos desarrollados en este trabajo. Por último, y dado que la monitorización se realiza en modo continuo, es necesario un sistema de comunicaciones compacto y fiable: en este apartado se analizan los metamateriales como solución tecnológica, ya que se adapta perfectamente a la filosofía de estas estaciones de medición. ABSTRACT Currently the monitoring of quality indicators is a need to preserve the environment and minimize the impact of human activity on the fauna and flora. Currently there are measuring systems and continuous monitoring of water quality, regardless of sampling laboratory studies, through which quality indicators are obtained. Technological development in continuous analyzers for the measurement of phosphorus, ammonia, BOD and others increasingly make a more comprehensive real-time quality control is achieved. However, early detection of contaminants that should not be present in the water, make the development of sensors for detecting these contaminants is very useful. In this regard, fluorescence techniques have huge advantages, since there is no direct contact with the sample, reducing wear and extending the time between maintenance, as has been demonstrated in numerous developments in laser technology. To produce fluoresce, traditionally are being used mainly gas lamps and monochromators at the laboratory. The new high-power LEDs in the ultraviolet spectrum are a very interesting alternative that can also be applied in the above continuous measurement systems. In this paper a viability study of these devices as excitation sources to produce fluorescence using hydrocarbon as contaminants is performed. The stations in continuous operation makes it necessary to also perform accelerated life tests and studies operating modes. In regard to the fluorescence produced, the influence of factors that may affect the measurements, such as temperature is studied. The study of the spectrum and analysis to identify the contaminant is another of the points developed in this work. Finally, since the monitoring is carried out in continuous mode, a compact and reliable communication is necessary: in this section metamaterials as a technological solution is analyzed since it fits perfectly with the philosophy of these measuring stations.