Rethinking Rice Preparation for Highly Efficient Removal of Inorganic Arsenic Using Percolating Cooking Water

A novel way of cooking rice to maximize the removal of the carcinogen inorganic arsenic (Asi) is presented here. In conventional rice cooking water and grain are in continuous contact, and it is known that the larger the water:rice cooking ratio, the more Asi removed by cooking, suggesting that the Asi in the grain is mobile in water. Experiments were designed where rice is cooked in a continual stream of percolating near boiling water, either low in Asi, or Asi free. This has the advantage of not only exposing grain to large volumes of cooking water, but also physically removes any Asi leached from the grain into the water receiving vessel. The relationship between cooking water volume and Asi removal in conventional rice cooking was demonstrated for the rice types under study. At a water-to-rice cooking ratio of 12:1, 57±5% of Asi could be removed, average of 6 wholegrain and 6 polished rice samples. Two types of percolating technology were tested, one where the cooking water was recycled through condensing boiling water steam and passing the freshly distilled hot water through the grain in a laboratory setting, and one where tap water was used to cook the rice held in an off-the-shelf coffee percolator in a domestic setting. Both approaches proved highly effective in removing Asi from the cooking rice, with up to 85% of Asi removed from individual rice types. For the recycled water experiment 59±8% and 69±10% of Asi was removed, on average, compared to uncooked rice for polished (n=27) and wholegrain (n=13) rice, respectively. For coffee percolation there was no difference between wholegrain and polished rice, and the effectiveness of Asi removal was 49±7% across 6 wholegrain and 6 polished rice samples. The manuscript explores the potential applications and further optimization of this percolating cooking water, high Asi removal, discovery.

Data Cleaning and Outlier Removal: Application in Human Skin Detection

An outlier removal based data cleaning technique is proposed to
clean manually pre-segmented human skin data in colour images.
The 3-dimensional colour data is projected onto three 2-dimensional
planes, from which outliers are removed. The cleaned 2 dimensional
data projections are merged to yield a 3D clean RGB data. This data
is finally used to build a look up table and a single Gaussian classifier
for the purpose of human skin detection in colour images.

Biological phosphorus removal during high-rate, low-temperature, anaerobic digestion of wastewater.

We report, for the first time, extensive biologically-mediated phosphate removal from wastewater during high-rate anaerobic digestion (AD). A hybrid sludge bed/fixed-film (packed pumice stone) reactor was employed for low-temperature (12°C) anaerobic treatment of synthetic sewage wastewater. Successful phosphate removal from the wastewater (up to 78% of influent phosphate) was observed, mediated by biofilms in the reactor. Scanning electron microscopy and energy dispersive X-ray analysis revealed the accumulation of elemental phosphorus (~2%) within the sludge bed and fixed-film biofilms. 4’, 6-diamidino-2-phenylindole (DAPI) staining indicated phosphorus accumulation was biological in nature and mediated through the formation of intracellular inorganic polyphosphate (polyP) granules within these biofilms. DAPI staining further indicated that polyP accumulation was rarely associated with free cells. Efficient and consistent chemical oxygen demand (COD) removal was recorded, throughout the 732-day trial, at applied organic loading rates between 0.4-1.5 kg COD m-3 d-1 and hydraulic retention times of 8-24 hours, while phosphate removal efficiency ranged from 28-78% on average per phase. Analysis of protein hydrolysis kinetics and the methanogenic activity profiles of the biomass revealed the development, at 12˚C, of active hydrolytic and methanogenic populations. Temporal microbial changes were monitored using Illumina Miseq analysis of bacterial and archaeal 16S rRNA gene sequences. The dominant bacterial phyla present in the biomass at the conclusion of the trial were the Proteobacteria and Firmicutes and the dominant archaeal genus was Methanosaeta. Trichococcus and Flavobacterium populations, previously associated with low temperature protein degradation, developed in the reactor biomass. The presence of previously characterised polyphosphate accumulating organisms (PAOs) such as Rhodocyclus, Chromatiales, Actinobacter and Acinetobacter was recorded at low numbers. However, it is unknown as yet if these were responsible for the luxury polyP uptake observed in this system. The possibility of efficient phosphate removal and recovery from wastewater during AD would represent a major advance in the scope for widespread application of anaerobic wastewater treatment technologies.

Design, production and characterisation of granular adsorbent material for arsenic removal from contaminated wastewater

The objective of this research was to design granulated iron oxide for the adsorption of heavy metals from wastewater. Polyvinyl acetate (PVAc) was chosen as a suitable binder; as it is water insoluble. Initial experiments on selection of suitable solvent of the polymer were carried out using three solvents namely; methanol, acetone and toluene. Based on the initial tests on product yield and mechanical strength, acetone was selected as the solvent for the polyvinyl acetate binder. Design of experiment was then used to investigate the influence of granulation process variables; impeller speed, binder concentration and liquid to solid ratio on the properties of the granular materials. The response variables in the study were granules mean size, stability in water and granule strength. The results showed that the combination of high impeller speed and high binder concentration favour the formation of strong and stable granules. Results also showed that leaching of the binder into the simulated was water was negligible. Trial adsorption experiments carried out using the strongest and most stable iron oxide granules produced in this work showed removal efficiency of around 70% of synthetic arsenic solutions with initial concentration of 1000 ppb.

Mercury (II) removal from aqueous solutions by microporous materials

O Mercúrio é um dos metais pesados mais tóxicos existentes no meio ambiente, é persistente e caracteriza-se por bioamplificar e bioacumular ao longo da cadeia trófica. A poluição com mercúrio é um problema à escala global devido à combinação de emissões naturais e emissões antropogénicas, o que obriga a políticas ambientais mais restritivas sobre a descarga de metais pesados. Consequentemente o desenvolvimento de novos e eficientes materiais e de novas tecnologias para remover mercúrio de efluentes é necessário e urgente. Neste contexto, alguns materiais microporosos provenientes de duas famílias, titanossilicatos e zirconossilicatos, foram investigados com o objectivo de avaliar a sua capacidade para remover iões Hg2+ de soluções aquosas. De um modo geral, quase todos os materiais estudados apresentaram elevadas percentagens de remoção, confirmando que são bons permutadores iónicos e que têm capacidade para serem utilizados como agentes descontaminantes. O titanossilicato ETS-4 foi o material mais estudado devido à sua elevada eficiência de remoção (>98%), aliada à pequena quantidade de massa necessária para atingir essa elevada percentagem de remoção. Com apenas 4 mg⋅dm-3 de ETS-4 foi possível tratar uma solução com uma concentração igual ao valor máximo admissível para descargas de efluentes em cursos de água (50 μg⋅dm-3) e obter água com qualidade para consumo humano (<1.0 μg⋅dm-3), de acordo com a legislação Portuguesa (DL 236/98). Tal como para outros adsorbentes, a capacidade de remoção de Hg2+ do ETS- 4 depende de várias condições experimentais, tais como o tempo de contacto, a massa, a concentração inicial de mercúrio, o pH e a temperatura. Do ponto de vista industrial as condições óptimas para a aplicação do ETS-4 são bastante atractivas, uma vez que não requerem grandes quantidades de material e o tratamento da solução pode ser feito à temperatura ambiente. A aplicação do ETS-4 torna-se ainda mais interessante no caso de efluentes hospitalares, de processos de electro-deposição com níquel, metalúrgica, extracção de minérios, especialmente ouro, e indústrias de fabrico de cloro e soda cáustica, uma vez que estes efluentes apresentam valores de pH semelhantes ao valor de pH óptimo para a aplicação do ETS-4. A cinética do processo de troca iónica é bem descrita pelo modelo Nernst-Planck, enquanto que os dados de equilíbrio são bem ajustados pelas isotérmicas de Langmuir e de Freundlich. Os parâmetros termodinâmicos, ΔG° and ΔH° indicam que a remoção de Hg2+ pelo ETS-4 é um processo espontâneo e exotérmico. A elevada eficiência do ETS-4 é confirmada pelos valores da capacidade de remoção de outros materiais para os iões Hg2+, descritos na literatura. A utilização de coluna de ETS-4 preparada no nosso laboratório, para a remoção em contínuo de Hg2+ confirma que este material apresenta um grande potencial para ser utilizado no tratamento de águas. ABSTRACT: Mercury is one of the most toxic heavy metals, exhibiting a persistent character in the environment and biota as well as bioamplification and bioaccumulation along the food chain. Natural inputs combined with the global anthropogenic sources make mercury pollution a planetary-scale problem, and strict environmental policies on metal discharges have been enforced. The development of efficient new materials and clean-up technologies for removing mercury from effluents is, thus, timely. In this context, in my study, several microporous materials from two families, titanosilicates and zirconosilicates were investigated in order to assess their Hg2+ sorption capacity and removal efficiency, under different operating conditions. In general, almost all microporous materials studied exhibited high removal efficiencies, confirming that they are good ion exchangers and have potential to be used as Hg2+ decontaminant agents. Titanosilicate ETS-4 was the material most studied here, by its highest removal efficiency (>98%) and lowest mass necessary to attain it. Moreover, according with the Portuguese legislation (DL 236/98) it is possible to attain drinking water quality (i.e. [Hg2+]< 1.0 μg⋅dm-3) by treating a solution with a Hg2+ concentration equal to the maximum value admissible for effluents discharges into water bodies (50 μg⋅dm-3), using only 4 mg⋅dm-3 of ETS-4. Even in the presence of major freshwater cations, ETS-4 removal efficiency remains high. Like for other adsorbents, the sorption capacity of ETS-4 for Hg2+ ions is strongly dependent on the operating conditions, such as contact time, mass, initial Hg2+ concentration and solution pH and, to a lesser extent, temperature. The optimum operating conditions found for ETS-4 are very attractive from the industrial point of view because the application of ETS-4 for the treatment of wastewater and/or industrial effluents will not require larges amounts of adsorbent, neither energy supply for temperature adjustments becoming the removal process economically competitive. These conditions become even more interesting in the case of medical institutions liquid, nickel electroplating process, copper smelter, gold ore tailings and chlor-alkali effluents, since no significant pH adjustments to the effluent are necessary. The ion exchange kinetics of Hg2+ uptake is successfully described by the Nernst-Planck based model, while the ion exchange equilibrium is well fitted by both Langmuir and Freundlich isotherms. Moreover, the feasibility of the removal process was confirmed by the thermodynamic parameters (ΔG° and ΔH°) which indicate that the Hg2+ sorption by ETS-4 is spontaneous and exothermic. The higher efficiency of ETS-4 for Hg2+ ions is corroborate by the values reported in literature for the sorption capacity of other adsorbents for Hg2+ ions. The use of an ETS-4 fixed-bed ion exchange column, manufactured in our laboratory, in the continuous removal of Hg2+ ions from solutions confirms that this titanosilicate has potential to be used in industrial water treatment.

Genotoxicity in humans and indicator species exposed to uranium wastes

Os riscos dos resíduos provenientes da extração do urânio estão associados ao seu conteúdo em metais e radionuclídeos, o que levanta preocupações às autoridades governamentais e à população em geral. As populações humanas e outras espécies animais que vivem em zonas de exploração de urânio poderão estar expostas à radiação através de resíduos e poeiras radioactivase também através de água e alimentos contaminados. A determinação dos riscos deste tipo de contaminantes é feita, principalmente, através da análise química de amostras ambientais, dando-se menos importância à determinação de efeitos biológicos. A determinação de efeitos biológicos causados pela exposição a poluentes, tem-se revelado muito importante para uma avaliação da qualidade ambiental, de modo a providenciar indicações acerca dos efeitos negativos nos seres vivos e também para complementar a informação dada pelas análises químicas de amostras ambientais. Este facto levou ao estabelecimento de biomarcadores, que consistem em respostas biológicas adversas que são específicas de uma exposição a toxinas ambientais, para serem usadas como ferramentas de avaliação da qualidade ambiental. Neste trabalho foram analisadas respostas a nível molecular e celular, em minhocas, ratinhos do campo e humanos, a fim de determinar o risco químico e radiológico dos resíduos provenientes da mina de urânio da Cunha Baixa. Este trabalho teve também como objectivo a clarificação das respostas subjacentes à exposição a metais e radionuclídeos, a fim de permitir o desenvolvimento de potenciais novos biomarcadores moleculares. Durante este trabalho foram efectuados ensaios com minhocas, em que estas foram expostas durante 56 dias a solo contaminado proveniente da mina de urânio da Cunha Baixa, em laboratório e in situ. Durante a exposição foram analisados vários parâmetros, como o crescimento, reprodução, bioacumulação de metais e radionuclídeos, histopatologia, danos no DNA, citotoxicidade e perfil de expressão genética. Para além disso, foram amostrados ratinhos do campo na mina de urânio da Cunha Baixa e numa área de referência para determinação de danos no DNA, níveis de expressão e mutações em genes supressores de tumores e também bioacumulação de metais. Por fim, foram recolhidas amostras de sangue em voluntários saudáveis pertencentes à população da aldeia da Cunha Baixa, para determinação de danos no DNA, imunofenotipagem e quantificação de metais no sangue. Os resultados revelaram que as minhocas assim como os ratinhos do campo foram negativamente afetados pela exposição aos resíduos mineiros em todos os níveis de organização biológica aqui analisados, o que faz destes organismos bons indicadores para a determinação do risco destas áreas contaminadas, evidenciando o potencial risco da exposição a estes contaminantes. Para além disso, o estudo feito à população da Cunha Baixa revelou danos no ADN e diminuição de populações importantes de células imunitárias (nomeadamente linfócitos T e NK), o que poderá resultar da exposição aos resíduos da mina, tornando as pessoas mais susceptíveis ao desenvolvimento de processos de carcinogénese. O presente estudo contribuiu significativamente para a caracterização dos riscos da exposição a resíduos provenientes de minas de urânio abandonadas, evidenciando os seus efeitos negativos a nível molecular e celular, que potencialmente poderão causar instabilidade genómica e aumentar o risco de desenvolvimento de doenças genéticas.

Removal of cyanobacteria and cyanotoxins from drinking water by powdered activated carbon adsorption/ultrafiltration

Tese dout., Ciências e Tecnologias do Ambiente, Universidade do Algarve, 2009

Development of new technologies for the selective removal of volatile compounds with applications in forensic science and natural aromas

Tese de doutoramento, Farmácia (Química Farmacêutica e Terapêutica), Universidade de Lisboa, Faculdade de Farmácia, 2015

Nanoporous carbons from sisal residues and their application in hybrid TiO2/carbon photocatalysts for the removal and degradation of phenol in solution

Tese de doutoramento, Química (Química Tecnológica), Universidade de Lisboa, Faculdade de Ciências, 2016

Copper and lead removal by peanut hulls: equilibrium and kinetic studies

This research work aims to study the use of peanut hulls, an agricultural and food industry waste, for copper and lead removal through equilibrium and kinetic parameters evaluation. Equilibrium batch studies were performed in a batch adsorber. The influence of initial pH was evaluated (3–5) and it was selected between 4.0 and 4.5. The maximum sorption capacities obtained for the Langmuir model were 0.21 ± 0.03 and 0.18 ± 0.02 mmol/g, respectively for copper and lead. In bi-component systems, competitive sorption of copper and lead was verified, the total amount adsorbed being around 0.21 mmol of metal per gram of material in both mono and bi-component systems. In the kinetic studies equilibrium was reached after 200 min contact time using a 400 rpm stirring rate, achieving 78% and 58% removal, in mono-component system, for copper and lead respectively. Their removal follows a pseudo-second-order kinetics. These studies show that most of the metals removal occurred in the first 20 min of contact, which shows a good uptake rate in all systems.

Numerical solution of a PDE system with non-linear steady state conditions that translates the air stripping pollutants removal

This work deals with the numerical simulation of air stripping process for the pre-treatment of groundwater used in human consumption. The model established in steady state presents an exponential solution that is used, together with the Tau Method, to get a spectral approach of the solution of the system of partial differential equations associated to the model in transient state.