Caracterização da matéria orgânica natural em águas para consumo humano

O tratamento de água para consumo humano tem por objectivos não só a sua qualidade em termos de parâmetros químicos e físicos, como também microbiológicos. Considerando que a MON pode afectar os sistemas de tratamento, a sua redução minimiza a formação de subprodutos de desinfecção, como por exemplo os trihalometanos e diminui o crescimento de microrganismos ao longo do sistema de distribuição. Nesse sentido tem havido recentemente uma grande evolução na investigação relativamente à remoção de matéria orgânica natural. O principal objectivo deste trabalho foi o de caracterizar a matéria orgânica presente na água bruta e ao longo do processo de tratamento, assim como a sua evolução sazonal. Os dados obtidos a partir desta caracterização poderão contribuir para uma futura optimização no processo de tratamento de águas de consumo. O processo utilizado baseou-se na sorção da matéria orgânica dissolvida em diferentes tipos de resinas de permuta iónica, DAX-8, DAX-4 e IRA-958, permitindo a sua separação em várias fracções: ácidos muito hidrofóbicos (VHA), ácidos ligeiramente hidrofóbicos (SHA), compostos hidrofílicos carregados (CHA) e hidrofílicos neutros (NEU). De acordo com os resultados obtidos apenas a fracção NEU demonstrou ter uma tendência sazonal, apresentando valores máximos no Verão, nos pontos de amostragem referentes à água bruta superficial (PA802) e água bruta superficial após pré-tratamento por filtração (PA800). Os valores de COD não mostraram uma variação sazonal para as amostras de água bruta superficial que rondaram os 2 mg C/L ao longo do período de amostragem (Julho a Outubro), durante o qual se verificou uma baixa pluviosidade e temperaturas médias muito semelhantes. Os compostos NEU predominam em todos os pontos de amostragem não apresentando uma tendência definida ao longo do tratamento. Observou-se uma diminuição das fracções SHA e CHA ao longo do tratamento. Não se pode indicar uma tendência definida relativamente à fracção VHA. Verifica-se globalmente uma diminuição do teor de MON ao longo do tratamento. Este trabalho demonstrou que na água bruta superficial existe uma predominância dos compostos NEU, seguidos dos SHA, dos VHA e finalmente dos compostos CHA. Na água bruta captada no sub-leito do rio, verifica-se apenas a existência dos compostos NEU, sendo as restantes fracções praticamente nulas. Os valores mais elevados de TSUVA254nm foram obtidos para as amostras que não sofreram qualquer tratamento, água bruta do sub-leito (PA903) e superficial (PA802), e água bruta após pré-filtração (PA800). Nos restantes pontos de amostragem, apesar de se verificarem valores inferiores, não se observa uma diminuição deste parâmetro ao longo do tratamento, nem uma variação sazonal. Os valores de TSUVA254nm obtidos são geralmente inferiores a 3 L.mgC-1.m-1, correspondendo a materiais não húmicos, que são considerados biodegradáveis. Para as amostras de água tratada os valores oscilam entre os 1,23 e 1,58 L.mgC-1.m-1, valores inferiores a 2 L.mgC-1.m-1, o que é considerado um valor de referência ao nível do tratamento, segundo a USEPA.

Sistema de modelização tridimensional para ambientes não estruturados

A navegação de veículos autónomos em ambientes não estruturados continua a ser um problema em aberto. A complexidade do mundo real ainda é um desafio. A difícil caracterização do relevo irregular, dos objectos dinâmicos e pouco distintos(e a inexistência de referências de localização) tem sido alvo de estudo e do desenvolvimento de vários métodos que permitam de uma forma eficiente, e em tempo real, modelizar o espaço tridimensional. O trabalho realizado ao longo desta dissertação insere-se na estratégia do Laboratório de Sistemas Autónomos (LSA) na pesquisa e desenvolvimento de sistemas sensoriais que possibilitem o aumento da capacidade de percepção das plataformas robóticas. O desenvolvimento de um sistema de modelização tridimensional visa acrescentar aos projectos LINCE (Land INtelligent Cooperative Explorer) e TIGRE (Terrestrial Intelligent General proposed Robot Explorer) maior autonomia e capacidade de exploração e mapeamento. Apresentamos alguns sensores utilizados para a aquisição de modelos tridimensionais, bem como alguns dos métodos mais utilizados para o processo de mapeamento, e a sua aplicação em plataformas robóticas. Ao longo desta dissertação são apresentadas e validadas técnicas que permitem a obtenção de modelos tridimensionais. É abordado o problema de analisar a cor e geometria dos objectos, e da criação de modelos realistas que os representam. Desenvolvemos um sistema que nos permite a obtenção de dados volumétricos tridimensionais, a partir de múltiplas leituras de um Laser Range Finder bidimensional de médio alcance. Aos conjuntos de dados resultantes associamos numa nuvem de pontos coerente e referenciada. Foram desenvolvidas e implementadas técnicas de segmentação que permitem inspeccionar uma nuvem de pontos e classifica-la quanto às suas características geométricas, bem como ao tipo de estruturas que representem. São apresentadas algumas técnicas para a criação de Mapas de Elevação Digital, tendo sido desenvolvida um novo método que tira partido da segmentação efectuada

Plataforma remota de gestão de um parque de GateBoxes

A monitorização de redes é um aspeto de elevada importância, principalmente em redes de média ou grande dimensão. A necessidade de utilização de uma ferramenta para realização dessa gestão facilita o trabalho e proporciona de uma forma mais rápida e eficaz a identificação de problemas na rede e nos seus sistemas. Neste sentido, o presente trabalho tem como objetivo o desenvolvimento de uma solução para a monitorização de GateBoxes, um dos produtos desenvolvidos e comercializados pela empresa NextToYou. A necessidade de monitorização das GateBoxes, por parte da NextToYou, é essencial para que possa detetar falhas no seu funcionamento ou realizar notificações aquando da deteção de problemas para uma rápida resolução. Neste contexto a empresa decidiu implementar uma ferramenta para a referida monitorização e propôs, no âmbito da tese, o desenvolvimento de uma aplicação que satisfizesse esses propósitos. Disponibilizou então, para o desenvolvimento uma plataforma, a WebForge, e definiu alguns requisitos funcionais dessa ferramenta, tais como, a monitorização remota de informação, gestão de alarmes, geração de avisos e notificações. Para a elaboração deste trabalho foram realizados estudos teóricos sobre o tema da gestão e monitorização remotas, realizando-se posteriormente o desenvolvimento de uma aplicação para a monitorização de GateBoxes. Após a implementação efetuou-se a validação do trabalho realizado através da execução de testes e demonstrações, de forma a poder validar e verificar o desempenho do sistema.

Gold electrode modified by self-assembled monolayers of thiols to determine DNA sequences hybridization

The process of immobilization of biological molecules is one of the most important steps in the construction of a biosensor. In the case of DNA, the way it exposes its bases can result in electrochemical signals to acceptable levels. The use of self-assembled monolayer that allows a connection to the gold thiol group and DNA binding to an aldehydic ligand resulted in the possibility of determining DNA hybridization. Immobilized single strand of DNA (ssDNA) from calf thymus pre-formed from alkanethiol film was formed by incubating a solution of 2-aminoethanothiol (Cys) followed by glutaraldehyde (Glu). Cyclic voltammetry (CV) was used to characterize the self-assembled monolayer on the gold electrode and, also, to study the immobilization of ssDNA probe and hybridization with the complementary sequence (target ssDNA). The ssDNA probe presents a well-defined oxidation peak at +0.158 V. When the hybridization occurs, this peak disappears which confirms the efficacy of the annealing and the DNA double helix performing without the presence of electroactive indicators. The use of SAM resulted in a stable immobilization of the ssDNA probe, enabling the hybridization detection without labels. This study represents a promising approach for molecular biosensor with sensible and reproducible results.

A waste management school approach towards sustainability

Education towards sustainability in Chemical Engineering (CEng) gave birth to awaste management program (WMP) at Instituto Superior de Engenharia do Porto, in Portugal. It involves students, teachers, and laboratory technicians. It aims to enhance the conscientiousness of the decision-maker next generation for saving resources, managing wastes, and at same time to develop applied chemistry understanding. This program was implemented in 1999 and is responsible for management and fate of all inorganic wastewater providing from training experimental activities of the CEng degree. An immediate reduction of wastes at their source was first defined. Wastes were collected separately and were reused, recycled or chemically treated, and after analytically controlled as legally imposed. Solids formed after this program were recycled, purified or followed suitable elimination. Global results point out environmental, pedagogical, and social benefits. Active participants are aware, in agreement, and publicly committed to the WMP.

Heterogeneous kinetics of the reduction of chromium (VI) by elemental iron

Zero valent iron (ZVI) has been extensively used as a reactive medium for the reduction of Cr(VI) to Cr(III) in reactive permeable barriers. The kinetic rate depends strongly on the superficial oxidation of the iron particles used and the preliminary washing of ZVI increases the rate. The reaction has been primarily modelled using a pseudo-first-order kinetics which is inappropriate for a heterogeneous reaction. We assumed a shrinking particle type model where the kinetic rate is proportional to the available iron surface area, to the initial volume of solution and to the chromium concentration raised to a power ˛ which is the order of the chemical reaction occurring at surface. We assumed α= 2/3 based on the likeness to the shrinking particle models with spherical symmetry. Kinetics studies were performed in order to evaluate the suitability of this approach. The influence of the following parameters was experimentally studied: initial available surface area, chromium concentration, temperature and pH. The assumed order for the reaction was confirmed. In addition, the rate constant was calculated from data obtained in different operating conditions. Digital pictures of iron balls were periodically taken and the image treatment allowed for establishing the time evolution of their size distribution.

Short- and medium-term effects of manual therapy on cervical active range of motion and pressure pain sensitivity in latent myofascial pain of the upper trapezius muscle: a randomized controlled trial

Objective: The purpose of this study was to investigate effects of different manual techniques on cervical ranges of 17 motion and pressure pain sensitivity in subjects with latent trigger point of the upper trapezius muscle. 18 Methods: One hundred seventeen volunteers, with a unilateral latent trigger point on upper trapezius due to computer 19 work, were randomly divided into 5 groups: ischemic compression (IC) group (n = 24); passive stretching group (n = 20 23); muscle energy technique group (n = 23); and 2 control groups, wait-and-see group (n = 25) and placebo group 21 (n = 22). Cervical spine range of movement was measured using a cervical range of motion instrument as well as 22 pressure pain sensitivity by means of an algometer and a visual analog scale. Outcomes were assessed pretreatment, 23 immediately, and 24 hours after the intervention and 1 week later by a blind researcher. A 4 × 5 mixed repeated- 24 measures analysis of variance was used to examine the effects of the intervention and Cohen d coefficient was used. 25 Results: A group-by-time interaction was detected in all variables (P b .01), except contralateral rotation. The 26 immediate effect sizes of the contralateral flexion, ipsilateral rotation, and pressure pain threshold were large for 3 27 experimental groups. Nevertheless, after 24 hours and 1 week, only IC group maintained the effect size. 28 Conclusions: Manual techniques on upper trapezius with latent trigger point seemed to improve the cervical range of 29 motion and the pressure pain sensitivity. These effects persist after 1 week in the IC group. (J Manipulative Physiol 301 Ther 2013;xx:1-10)

Bisphenol A migration from plastic materials: direct insight of ecotoxicity in Daphnia magna

Bisphenol A (BPA) is an endocrine disrupting chemical (EDC) whose migration from food packaging is recognized worldwide. However, the real overall food contamination and related consequences are yet largely unknown. Among humans, children’s exposure to BPA has been emphasized because of the immaturity of their biological systems. The main aim of this study was to assess the reproductive impact of BPA leached from commercially available plastic containers used or related to child nutrition, performing ecotoxicological tests using the biomonitoring species Daphnia magna. Acute and chronic tests, as well as single and multigenerational tests were done. Migration of BPA from several baby bottles and other plastic containers evaluated by GC-MS indicated that a broader range of foodstuff may be contaminated when packed in plastics. Ecotoxicological test results performed using defined concentrations of BPA were in agreement with literature, although a precocious maturity of daphnids was detected at 3.0 mg/L. Curiously, an increased reproductive output (neonates per female) was observed when daphnids were bred in the polycarbonate (PC) containers (145.1±4.3 % to 264.7±3.8 %), both in single as in multigenerational tests, in comparison with the negative control group (100.3±1.6 %). A strong correlated dose-dependent ecotoxicological effect was observed, providing evidence that BPA leached from plastic food packaging materials act as functional estrogen in vivo at very low concentrations. In contrast, neonate production by daphnids cultured in polypropylene and non-PC bottles was slightly but not significantly enhanced (92.5±2.0 % to 118.8±1.8 %). Multigenerational tests also revealed magnification of the adverse effects, not only on fecundity but also on mortality, which represents a worrying trend for organisms that are chronically exposed to xenoestrogens for many generations. Two plausible explanations for the observed results could be given: a non-monotonic dose–response relationship or a mixture toxicity effect.

Wine and grape polyphenols — a chemical perspective

Phenolic compounds constitute a diverse group of secondary metabolites which are present in both grapes and wine. The phenolic content and composition of grape processed products (wine) are greatly influenced by the technological practice to which grapes are exposed. During the handling and maturation of the grapes several chemical changes may occur with the appearance of new compounds and/or disappearance of others, and consequent modification of the characteristic ratios of the total phenolic content as well as of their qualitative and quantitative profile. The non-volatile phenolic qualitative composition of grapes and wines, the biosynthetic relationships between these compounds, and the most relevant chemical changes occurring during processing and storage will be highlighted in this review.

β-Lactams: chemical structure, mode of action and mechanisms of resistance

This synopsis summarizes the key chemical and bacteriological characteristics of β-lactams, penicillins, cephalosporins, carbanpenems, monobactams and others. Particular notice is given to first-generation to fifth-generation cephalosporins. This reviewalso summarizes the main resistancemechanism to antibiotics, focusing particular attention to those conferring resistance to broad-spectrum cephalosporins by means of production of emerging cephalosporinases (extended-spectrum β-lactamases and AmpC β-lactamases), target alteration (penicillin-binding proteins from methicillin-resistant Staphylococcus aureus) and membrane transporters that pump β-lactams out of the bacterial cell.

Using a prioritized medium access control protocol for incrementally obtaining an interpolation of sensor readings

This paper addresses sensor network applications which need to obtain an accurate image of physical phenomena and do so with a high sampling rate in both time and space. We present a fast and scalable approach for obtaining an approximate representation of all sensor readings at high sampling rate for quickly reacting to critical events in a physical environment. This approach is an improvement on previous work in that after the new approach has undergone a startup phase then the new approach can use a very small sampling period.

A pseudo-medium-wide 8-competitive interface for two-level compositional real-time scheduling of constrained- deadline sporadic tasks on a uniprocessor

Compositional real-time scheduling clearly requires that ”normal” real-time scheduling challenges are addressed but challenges intrinsic to compositionality must be addressed as well, in particular: (i) how should interfaces be described? and (ii) how should numerical values be assigned to parameters constituting the interfaces? The real-time systems community has traditionally used narrow interfaces for describing a component (for example, a utilization/bandwidthlike metric and the distribution of this bandwidth in time). In this paper, we introduce the concept of competitive ratio of an interface and show that typical narrow interfaces cause poor performance for scheduling constrained-deadline sporadic tasks (competitive ratio is infinite). Therefore, we explore more expressive interfaces; in particular a class called medium-wide interfaces. For this class, we propose an interface type and show how the parameters of the interface should be selected. We also prove that this interface is 8-competitive.

WiDom: a dominance protocol for wireless medium access

In this paper, we address the problem of sharing a wireless channel among a set of sporadic message streams where a message stream issues transmission requests with real-time deadlines. We propose a collision-free wireless medium access control (MAC) protocol which implements static-priority scheduling, supports a large number of priority levels and is fully distributed. It is an adaptation to a wireless channel of the dominance protocol used in the CAN bus. But, unlike that protocol, our protocol does not require a node having the ability to receive an incoming bit from the channel while transmitting to the channel. The evaluation of the protocol with real embedded computing platforms is presented to show that the proposed protocol is in fact collision-free and prioritized. We measure the response times of our implementation and show that the response-time analysis developed for the protocol offers an upper bound on the response times.

Delay-bounded medium access for unidirectional wireless links

Consider a wireless network where links may be unidirectional, that is, a computer node A can broadcast a message and computer node B will receive this message but if B broadcasts then A will not receive it. Assume that messages have deadlines. We propose a medium access control (MAC) protocol which replicates a message in time with carefully selected pauses between replicas, and in this way it guarantees that for every message at least one replica of that message is transmitted without collision. The protocol ensures this with no knowledge of the network topology and it requires neither synchronized clocks nor carrier sensing capabilities. We believe this result is significant because it is the only MAC protocol that offers an upper bound on the message queuing delay for unidirectional links without relying on synchronized clocks.

Preliminary discussion on globally prioritized medium access for multi-channel wireless systems

We discuss the development of a simple globally prioritized multi-channel medium access control (MAC) protocol for wireless networks. This protocol provides “hard” pre-run-time real-time guarantees to sporadic message streams, exploits a very large fraction of the capacity of all channels for “hard” real-time traffic and also makes it possible to fully utilize the channels with non real-time traffic when hard real-time messages do not request to be transmitted. The potential of such protocols for real-time applications is discussed and a schedulability analysis is also presented.