Keywords:Arsenic speciation Microwave-assisted extraction Edible algae Inductively coupled plasma atomic emission spectrometry High performance liquid chromatography Hydride generation-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 (xgg -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 (xgg -1 , whereas sulfonate and sulfate sugars were only detected in three of them (0.6-7.2 (xgg -1 ). Regarding arsenic toxic species, low concentration levels of dimethylarsinic acid (DMA) (<0.9 (xgg -1 ) and generally high arsenate (As(V)) concentrations (up to 77 (xgg -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.
Titania nanoparticles are intensely studied for photodegradation applications. Control of nanoscale morphology and microstructural properties of these materials is critical for photocatalytic performance. Uniform anatase-type TiO2 nanoparticles were prepared by the sol-gel process using titanium isopropoxide as precursor. Controlled annealing up to 400 °C established crystallization and particle size ranging between 20 and 30 nm. Detailed thermal examination reveals that anatase phase transformation into rutile is affected by the annealing temperature and by the initial particle size. The anatase to rutile phase transformation occurs in the nanoparticles at 550 °C. The Total Reflection X-ray Fluorescence (TXRF) study of the anatase nanoparticles shows a shift towards higher energy in the Ka Ti line of 10 eV, related to structural defects. These features were discussed in the photocatalytic behavior of several cement-based materials modified with the so-prepared anatase nanoparticles. The photocatalytic activity of the anatase-type TiO2/cement mortar system is evaluated from the degradation of Methylene Blue (MB) under UV irradiation, monitored through the absorbance at 665 nm. The results show that the photocatalytic composites exhibit up to 76.6% degradation efficiency. Mechanical testing of the nano-TiO2 modified cementitious composites evinces a moderate reinforcement of the strength properties at long ages.
Arsenic and heavy metal (specifically Cd, Cr, Cu, Ni, Pb, and Zn) uptake, translocation, and accumulation in ten native plant species spontaneously growing in soils polluted by mining activities were studied, with a focus on future phytoremediation work in polluted soils. Plant and soil samples were collected in the vicinity of the Mónica mine (NW Madrid, Spain). Soil analysis showed the ability of native plants for growing in soils with high concentration levels of Cd, Cu, Pb, Zn, and especially As. From these elements, the highest percentage of extractable elements was found for Cd and the lowest for Pb. A highly significant correlation was observed between total and extractable element concentrations in soils, except for Cu, indicating that total concentration is the most relevant factor for element mobility in these soils. Extractable elements in soils were better correlated with concentrations in plants than total elements in soils; thus, extraction methods applied are suitable to estimate the element phytoavailable fraction in soils, which depends on the plant species and not only on the element mobility in soils. High element concentrations were found in the aboveground parts of Corrigiola telephiifolia (As and Pb), Jasione montana (Cd and Zn), and Digitalis thapsi (As, Cd, Cu, Pb and Zn). However, considering the translocation and accumulation factors, together with the concentration levels found in roots and aboveground parts, only C. telephiifolia could be considered a Pb accumulator and an As hyperaccumulator plant, which could be used for future phytoremediation work in soils polluted with As.
So far, the relative importance of the plant and its microbiome in the development of early stages of plant seedling growth under arsenic stress has not been studied. To test the role of endophytic bacteria in increasing plant success under arsenic stress, gnotobiotic seeds of J. montana were inoculated with two endophytic bacteria: Pantoea conspicua MC-K1 (PGPB and As resistant bacteria) and Arthrobacter sp. MC-D3A (non-helper and non-As resistant bacteria) and an endobacteria mixture. In holobiotic seedlings (with seed-vectored microbes intact), neither the capacity of germination nor development of roots and lateral hairs was affected at 125 μM As(V). However, in gnotobiotic seedlings, the plants are negatively impacted by absence of a microbiome and presence of arsenic, resulting in reduced growth of roots and root hairs. The inoculation of a single PGPB (P. conspicua-MCK1) shows a tendency to the recovery of the plant, both in arsenic enriched and arsenic-free media, while the inoculation with Arthrobacter sp. does not help in the recovery of the plants. Inoculation with a bacterial mixture allows recovery of plants in arsenic free media; however, plants did not recover under arsenic stress, probably because of a bacterial interaction in the mixture.
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