Pilot monitoring study of ibuprofen in surface waters of north of Portugal

Ibuprofen is amongst the most worldwide consumed pharmaceuticals. The present work presents the first data in the occurrence of ibuprofen in Portuguese surface waters, focusing in the north area of the country, which is one of the most densely populated areas of Portugal. Analysis of ibuprofen is based on pre-concentration of the analyte with solid phase extraction and subsequent determination with liquid chromatography coupled to fluorescence detection. A total of 42 water samples, including surface waters, landfill leachates,Wastewater Treatment Plant (WWTP), and hospital effluents, were analyzed in order to evaluate the occurrence of ibuprofen in the north of Portugal. In general, the highest concentrations were found in the river mouths and in the estuarine zone. The maximum concentrations found were 48,720 ngL−1 in the landfill leachate, 3,868 ngL−1 in hospital effluent, 616 ngL−1 in WWTP effluent, and 723 ngL−1 in surface waters (Lima river). Environmental risk assessment was evaluated and at the measured concentrations only landfill leachates reveal potential ecotoxicological risk for aquatic organisms. Owing to a high consumption rate of ibuprofen among Portuguese population, as prescribed and nonprescribed medicine, the importance of hospitals, WWTPs, and landfills as sources of entrance of pharmaceuticals in the environment was pointed out. Landfill leachates showed the highest contribution for ibuprofen mass loading into surface waters. On the basis of our findings, more studies are needed as an attempt to assess more vulnerable areas.

Construção de um robô trepador com locomoção através de rodas e adesão através de meios magnéticos

Mestrado em Engenharia Electrotécnica e de Computadores

Static and hydrodynamic monitoring of citalopram based on its electro-oxidation behavior at a glassy-carbon surface

The electrooxidative behavior of citalopram (CTL) in aqueous media was studied by cyclic voltammetry (CV) and square-wave voltammetry (SWV) at a glassy-carbon electrode. The electrochemical behaviour of CTL involves two electrons and two protons in the irreversible and diffusion controlled oxidation of the tertiary amine group. The maximum analytical signal was obtained in a phosphate buffer (pH ¼ 8.2). For analytical purposes, an SWV method and a flow-injection analysis (FIA) system with amperometric detection were developed. The optimised SWV method showed a linear range between 1.10 10 5–1.20 10 4 molL 1, with a limit of detection (LOD) of 9.5 10 6 molL 1. Using the FIA method, a linear range between 2.00 10 6–9.00 10 5 molL 1 and an LODof 1.9 10 6 molL 1 were obtained. The validation of both methods revealed good performance characteristics confirming applicability for the quantification of CTL in several pharmaceutical products.

Agar extraction from integrated multitrophic aquacultured Gracilaria vermiculophylla: Evaluation of a microwave-assisted process using response surface methodology

Microwave-assisted extraction (MAE) of agar from Gracilaria vermiculophylla, produced in an integrated multitrophic aquaculture (IMTA) system, from Ria de Aveiro (northwestern Portugal), was tested and optimized using response surface methodology. The influence of the MAE operational parameters (extraction time, temperature, solvent volume and stirring speed) on the physical and chemical properties of agar (yield, gel strength, gelling and melting temperatures, as well as, sulphate and 3,6-anhydro-Lgalactose contents) was evaluated in a 2^4 orthogonal composite design. The quality of the extracted agar compared favorably with the attained using traditional extraction (2 h at 85ºC) while reducing drastically extraction time, solvent consumption and waste disposal requirements. Agar MAE optimum results were: an yield of 14.4 ± 0.4%, a gel strength of 1331 ± 51 g/cm2, 40.7 ± 0.2 _C gelling temperature, 93.1 ± 0.5ºC melting temperature, 1.73 ± 0.13% sulfate content and 39.4 ± 0.3% 3,6-anhydro-L-galactose content. Furthermore, this study suggests the feasibility of the exploitation of G. vermiculophylla grew in IMTA systems for agar production.

Determination of ochratoxin A in bread: evaluation of microwave-assisted extraction using an orthogonal composite design coupled with response surface methodology

An analytical method using microwave-assisted extraction (MAE) and liquid chromatography (LC) with fluorescence detection (FD) for the determination of ochratoxin A (OTA) in bread samples is described. A 24 orthogonal composite design coupled with response surface methodology was used to study the influence of MAE parameters (extraction time, temperature, solvent volume, and stirring speed) in order to maximize OTA recovery. The optimized MAE conditions were the following: 25 mL of acetonitrile, 10 min of extraction, at 80 °C, and maximum stirring speed. Validation of the overall methodology was performed by spiking assays at five levels (0.1–3.00 ng/g). The quantification limit was 0.005 ng/g. The established method was then applied to 64 bread samples (wheat, maize, and wheat/maize bread) collected in Oporto region (Northern Portugal). OTAwas detected in 84 % of the samples with a maximum value of 2.87 ng/g below the European maximum limit established for OTA in cereal products of 3 ng/g.

Response surface methodology applied to SPE for the determination of ibuprofen in various types of water samples

Over the last few years, there has been a growing concern about the presence of pharmaceuticals in the environment. The main objective of this study was to develop and validate an SPE method using surface response methodology for the determination of ibuprofen in different types of water samples. The influence of sample pH and sample volume on the ibuprofen recovery was studied. The effect of each studied independent variable is pronounced on the dependent variable (ibuprofen recovery). Good selectivity, extraction efficiency, and precision were achieved using 600 mL of sample volume with the pH adjusted to 2.2. LC with fluorescence detection was employed. The optimized method was applied to 20 water samples from the North and South of Portugal.

Analysis of the nano-surface of a modified glassy carbon electrode by pseudo phase plane method

This paper presents the Pseudo phase plane (PPP) method for detecting the existence of a nanofilm on the nitroazobenzene-modified glassy carbon electrode (NAB-GC) system. This modified electrode systems and nitroazobenze-nanofilm were prepared by the electrochemical reduction of diazonium salt of NAB at the glassy carbon electrodes (GCE) in nonaqueous media. The IR spectra of the bare glassy carbon electrodes (GCE), the NAB-GC electrode system and the organic NAB film were recorded. The IR data of the bare GC, NAB-GC and NAB film were categorized into five series consisting of FILM1, GC-NAB1, GC1; FILM2, GC-NAB2, GC2; FILM3, GC-NAB3, GC3 and FILM4, GC-NAB4, GC4 respectively. The PPP approach was applied to each group of the data of unmodified and modified electrode systems with nanofilm. The results provided by PPP method show the existence of the NAB film on the modified GC electrode.

Shear strength of adhesively bonded polyolefins with minimal surface preparation

Interest in polyethylene and polypropylene bonding has increased in the last years. However, adhesive joints with adherends which are of low surface energy and which are chemically inert present several difficulties. Generally, their high degree of chemical resistance to solvents and dissimilar solubility parameters limit the usefulness of solvent bonding as a viable assembly technique. One successful approach to adhesive bonding of these materials involves proper selection of surface pre-treatment prior to bonding. With the correct pre-treatment it is possible to glue these materials with one or more of several adhesives required by the applications involved. A second approach is the use of adhesives without surface pre-treatment, such as hot melts, high tack pressure-sensitive adhesives, solvent-based specialty adhesives and, more recently, structural acrylic adhesives as such 3M DP-8005® and Loctite 3030®. In this paper, the shear strengths of two acrylic adhesives were evaluated using the lap shear test method ASTM D3163 and the block shear test method ASTM D4501. Two different industrial polyolefins (polyethylene and polypropylene) were used for adherends. However, the focus of this study was to measure the shear strength of polyethylene joints with acrylic adhesives. The effect of abrasion was also studied. Some test specimens were manually abraded using 180 and 320 grade abrasive paper. An additional goal of this work was to examine the effect of temperature and moisture on mechanical strength of adhesive joints.

A survey of technologies and applications for climbing robots locomotion and adhesion

The interest in the development of climbing robots has grown rapidly in the last years. Climbing robots are useful devices that can be adopted in a variety of applications, such as maintenance and inspection in the process and construction industries. These systems are mainly adopted in places where direct access by a human operator is very expensive, because of the need for scaffolding, or very dangerous, due to the presence of an hostile environment. The main motivations are to increase the operation efficiency, by eliminating the costly assembly of scaffolding, or to protect human health and safety in hazardous tasks. Several climbing robots have already been developed, and other are under development, for applications ranging from cleaning to inspection of difficult to reach constructions. A wall climbing robot should not only be light, but also have large payload, so that it may reduce excessive adhesion forces and carry instrumentations during navigation. These machines should be capable of travelling over different types of surfaces, with different inclinations, such as floors, walls, or ceilings, and to walk between such surfaces (Elliot et al. (2006); Sattar et al. (2002)). Furthermore, they should be able of adapting and reconfiguring for various environment conditions and to be self-contained. Up to now, considerable research was devoted to these machines and various types of experimental models were already proposed (according to Chen et al. (2006), over 200 prototypes aimed at such applications had been developed in the world by the year 2006). However, we have to notice that the application of climbing robots is still limited. Apart from a couple successful industrialized products, most are only prototypes and few of them can be found in common use due to unsatisfactory performance in on-site tests (regarding aspects such as their speed, cost and reliability). Chen et al. (2006) present the main design problems affecting the system performance of climbing robots and also suggest solutions to these problems. The major two issues in the design of wall climbing robots are their locomotion and adhesion methods. With respect to the locomotion type, four types are often considered: the crawler, the wheeled, the legged and the propulsion robots. Although the crawler type is able to move relatively faster, it is not adequate to be applied in rough environments. On the other hand, the legged type easily copes with obstacles found in the environment, whereas generally its speed is lower and requires complex control systems. Regarding the adhesion to the surface, the robots should be able to produce a secure gripping force using a light-weight mechanism. The adhesion method is generally classified into four groups: suction force, magnetic, gripping to the surface and thrust force type. Nevertheless, recently new methods for assuring the adhesion, based in biological findings, were proposed. The vacuum type principle is light and easy to control though it presents the problem of supplying compressed air. An alternative, with costs in terms of weight, is the adoption of a vacuum pump. The magnetic type principle implies heavy actuators and is used only for ferromagnetic surfaces. The thrust force type robots make use of the forces developed by thrusters to adhere to the surfaces, but are used in very restricted and specific applications. Bearing these facts in mind, this chapter presents a survey of different applications and technologies adopted for the implementation of climbing robots locomotion and adhesion to surfaces, focusing on the new technologies that are recently being developed to fulfill these objectives. The chapter is organized as follows. Section two presents several applications of climbing robots. Sections three and four present the main locomotion principles, and the main "conventional" technologies for adhering to surfaces, respectively. Section five describes recent biological inspired technologies for robot adhesion to surfaces. Section six introduces several new architectures for climbing robots. Finally, section seven outlines the main conclusions.

Using remote experimentation in a large undergraduate course: initial findings

The use of remote labs in undergraduate courses has been reported in literature several times since the mid 90's. Nevertheless, very few articles present results about the correspondent learning gains obtained by students, and in what conditions those systems can be more efficient, thus suggesting a lack of data concerning their pedagogical effectiveness. This paper addresses such a gap by presenting some initial findings concerning the use of a remote lab (VISIR), in a large undergraduate course on Physics, with over 550 students enrolled.

Insignificant impact of prescribed fire on surface soil in a Pinus pinaster plantation, northern Portugal

Following a prescribed fire in a Pinus pinaster forest site located in the north-west Portugal, monitoring of any changes in selected soil characteristics and soil hydrology was undertaken to assess the effects of burning on the following: pH, electrical conductivity, water content, organic carbon and porosity. Thirty plots were established on a regular grid. At each sample plot before and after the fire, samples were collected (disturbed samples from depths of 0-1cm and 1-5cm; undisturbed core samples from 0-5cm). The results indicate that there was no measurable impact on the properties of the soil following this carefully conducted prescribed fire. The fire only affected the litter layer, as intended. Confirmation of this minimal impact on the soil was provided by regrowth of grasses and herbs already occurring two months after the fire. The implication is, therefore, that provided this wildfire-risk reduction strategy is carried out under existing strict guidelines, any impact on soil quality will be minimal.

Effects of prescribed fire on surface soil in a Pinus pinaster plantation, northern Portugal

In order to decrease the risk of severe wildfire, prescribed fire has recently been adopted in Portugal and elsewhere in the Mediterranean as a major tool for reducing the fuel load instead of manual or mechanical removal of vegetation. There has been some research into its impact on soils in shrublands and grasslands, but to date little research has been conducted in forested areas in the region. As a result, the impact of prescribed fire on the physico-chemical soil characteristics of forest soils has been assumed to be minimal, but this has not been demonstrated. In this study, we present the results of a monitoring campaign of a detailed pre- and post-prescribed fire assessment of soil properties in a long-unburnt P. pinaster plantation, NW Portugal. The soil characteristics examined were pH, total porosity, bulk density, moisture content, organic matter content and litter/ash quantity. The results show that there was no significant impact on the measured soil properties, the only effect being confined to minor changes in the upper 1 cm of soil. We conclude that provided the fire is carried out according to strict guidelines in P. pinaster forest, a minimal impact on soil properties can be expected.

An uncertainty and sensitivity analysis applied to the prioritisation of pharmaceuticals as surface water contaminants from wastewater treatment plant direct emissions

In this study, the concentration probability distributions of 82 pharmaceutical compounds detected in the effluents of 179 European wastewater treatment plants were computed and inserted into a multimedia fate model. The comparative ecotoxicological impact of the direct emission of these compounds from wastewater treatment plants on freshwater ecosystems, based on a potentially affected fraction (PAF) of species approach, was assessed to rank compounds based on priority. As many pharmaceuticals are acids or bases, the multimedia fate model accounts for regressions to estimate pH-dependent fate parameters. An uncertainty analysis was performed by means of Monte Carlo analysis, which included the uncertainty of fate and ecotoxicity model input variables, as well as the spatial variability of landscape characteristics on the European continental scale. Several pharmaceutical compounds were identified as being of greatest concern, including 7 analgesics/anti-inflammatories, 3 β-blockers, 3 psychiatric drugs, and 1 each of 6 other therapeutic classes. The fate and impact modelling relied extensively on estimated data, given that most of these compounds have little or no experimental fate or ecotoxicity data available, as well as a limited reported occurrence in effluents. The contribution of estimated model input variables to the variance of freshwater ecotoxicity impact, as well as the lack of experimental abiotic degradation data for most compounds, helped in establishing priorities for further testing. Generally, the effluent concentration and the ecotoxicity effect factor were the model input variables with the most significant effect on the uncertainty of output results.

New findings on the dynamics of HIV and TB coinfection models

In this paper we study a model for HIV and TB coinfection. We consider the integer order and the fractional order versions of the model. Let α∈[0.78,1.0] be the order of the fractional derivative, then the integer order model is obtained for α=1.0. The model includes vertical transmission for HIV and treatment for both diseases. We compute the reproduction number of the integer order model and HIV and TB submodels, and the stability of the disease free equilibrium. We sketch the bifurcation diagrams of the integer order model, for variation of the average number of sexual partners per person and per unit time, and the tuberculosis transmission rate. We analyze numerical results of the fractional order model for different values of α, including α=1. The results show distinct types of transients, for variation of α. Moreover, we speculate, from observation of the numerical results, that the order of the fractional derivative may behave as a bifurcation parameter for the model. We conclude that the dynamics of the integer and the fractional order versions of the model are very rich and that together these versions may provide a better understanding of the dynamics of HIV and TB coinfection.

P53 and Cancer-Associated Sialylated Glycans Are Surrogate Markers of Cancerization of the Bladder Associated with Schistosoma haematobium Infection

BACKGROUND: Bladder cancer is a significant health problem in rural areas of Africa and the Middle East where Schistosoma haematobium is prevalent, supporting an association between malignant transformation and infection by this blood fluke. Nevertheless, the molecular mechanisms linking these events are poorly understood. Bladder cancers in infected populations are generally diagnosed at a late stage since there is a lack of non-invasive diagnostic tools, hence enforcing the need for early carcinogenesis markers. METHODOLOGY/PRINCIPAL FINDINGS: Forty-three formalin-fixed paraffin-embedded bladder biopsies of S. haematobium-infected patients, consisting of bladder tumours, tumour adjacent mucosa and pre-malignant/malignant urothelial lesions, were screened for bladder cancer biomarkers. These included the oncoprotein p53, the tumour proliferation rate (Ki-67>17%), cell-surface cancer-associated glycan sialyl-Tn (sTn) and sialyl-Lewisa/x (sLea/sLex), involved in immune escape and metastasis. Bladder tumours of non-S. haematobium etiology and normal urothelium were used as controls. S. haematobium-associated benign/pre-malignant lesions present alterations in p53 and sLex that were also found in bladder tumors. Similar results were observed in non-S. haematobium associated tumours, irrespectively of their histological nature, denoting some common molecular pathways. In addition, most benign/pre-malignant lesions also expressed sLea. However, proliferative phenotypes were more prevalent in lesions adjacent to bladder tumors while sLea was characteristic of sole benign/pre-malignant lesions, suggesting it may be a biomarker of early carcionogenesis associated with the parasite. A correlation was observed between the frequency of the biomarkers in the tumor and adjacent mucosa, with the exception of Ki-67. Most S. haematobium eggs embedded in the urothelium were also positive for sLea and sLex. Reinforcing the pathologic nature of the studied biomarkers, none was observed in the healthy urothelium. CONCLUSION/SIGNIFICANCE: This preliminary study suggests that p53 and sialylated glycans are surrogate biomarkers of bladder cancerization associated with S. haematobium, highlighting a missing link between infection and cancer development. Eggs of S. haematobium express sLea and sLex antigens in mimicry of human leukocytes glycosylation, which may play a role in the colonization and disease dissemination. These observations may help the early identification of infected patients at a higher risk of developing bladder cancer and guide the future development of non-invasive diagnostic tests.