Nanofiltration of surface water for the removal of endocrine disruptors

The assessment of surface water nanofiltration (NF) for the removal of endocrine disruptors (EDs) Nonylphenol Ethoxylate (IGEPAL), 4-Nonylphenol (NP) and 4-Octylphenol (OP) was carried out with three commercial NF membranes - NF90, NF200, NF270. The permeation experiments were conducted in laboratory flat-cell units of 13.2 x 10(-4) m(2) of surface area and in a DSS Lab-unit M20 with a membrane surface area of 0.036 m2. The membranes hydraulic permeabilities ranged from 3.7 to 15.6 kg/h/m(2)/bar and the rejection coefficients to NaCl, Na2SO4 and Glucose are for NF90: 97%, 99% and 97%, respectively; for NF200: 66%, 98% and 90%, respectively and for NF270: 48%, 94% and 84%, respectively. Three sets of nanofiltration experiments were carried out: i) NF of aqueous model solutions of NP, IGEPAL and OP running in total recirculation mode; ii) NF of surface water from Rio Sado (Settibal, Portugal) running in concentration mode; iii) NF of surface water from Rio Sado inoculated with NP, IGEPAL and OP running in concentration mode. The results of model solutions experiments showed that the EDs rejection coefficients are approximately 100% for all the membranes. The results obtained for the surface water showed that the rejection coefficients to natural organic Matter (NOM) are 94%, 82% and 78% for NF90, NF200 and NF 270 membranes respectively, with and without inoculation of EDs. The rejection coefficients to EDs in surface water with and without inoculation of EDs are 100%, showing that there is a fraction of NOM of high molecular weight that retains the EDs in the concentrate and that there is a fraction of NOM of low molecular weight that permeates through the NF membranes free of EDs.

Otimização de dose em mamografia

Mestrado em Radiações Aplicadas às Tecnologias da Saúde. Área de especialização: Imagem Digital com Radiação X.

Proteção radiológica em mamografia

Mestrado em Radiações Aplicadas às Tecnologias da Saúde. Área de especialização: Proteção contra Radiações.

Dosimetric effect by shallow air cavities in high energy electron beams

This study evaluates the dosimetric impact caused by an air cavity located at 2 mm depth from the top surface in a PMMA phantom irradiated by electron beams produced by a Siemens Primus linear accelerator. A systematic evaluation of the effect related to the cavity area and thickness as well as to the electron beam energy was performed by using Monte Carlo simulations (EGSnrc code), Pencil Beam algorithm and Gafchromic EBT2 films. A home-PMMA phantom with the same geometry as the simulated one was specifically constructed for the measurements. Our results indicate that the presence of the cavity causes an increase (up to 70%) of the dose maximum value as well as a shift forward of the position of the depthedose curve, compared to the homogeneous one. Pronounced dose discontinuities in the regions close to the lateral cavity edges are observed. The shape and magnitude of these discontinuities change with the dimension of the cavity. It is also found that the cavity effect is more pronounced (6%) for the 12 MeV electron beam and the presence of cavities with large thickness and small area introduces more significant variations (up to 70%) on the depthedose curves. Overall, the Gafchromic EBT2 film measurements were found in agreement within 3% with Monte Carlo calculations and predict well the fine details of the dosimetric change near the cavity interface. The Pencil Beam calculations underestimate the dose up to 40% compared to Monte Carlo simulations; in particular for the largest cavity thickness (2.8 cm).

Diffuse liver disease classification from ultrasound surface characterization, clinical and laboratorial data

In this work liver contour is semi-automatically segmented and quantified in order to help the identification and diagnosis of diffuse liver disease. The features extracted from the liver contour are jointly used with clinical and laboratorial data in the staging process. The classification results of a support vector machine, a Bayesian and a k-nearest neighbor classifier are compared. A population of 88 patients at five different stages of diffuse liver disease and a leave-one-out cross-validation strategy are used in the classification process. The best results are obtained using the k-nearest neighbor classifier, with an overall accuracy of 80.68%. The good performance of the proposed method shows a reliable indicator that can improve the information in the staging of diffuse liver disease.

Monitorization of alveolar deposited surface area of nanoparticles and ultrafine particles in different environments

Nanotechnology is an important emerging industry with a projected annual market of around one trillion dollars by 2015. It involves the control of atoms and molecules to create new materials with a variety of useful functions. Although there are advantages on the utilization of these nano-scale materials, questions related with its impact over the environment and human health must be addressed too, so that potential risks can be limited at early stages of development. At this time, occupational health risks associated with manufacturing and use of nanoparticles are not yet clearly understood. However, workers may be exposed to nanoparticles through inhalation at levels that can greatly exceed ambient concentrations. Current workplace exposure limits are based on particle mass, but this criteria could not be adequate in this case as nanoparticles are characterized by very large surface area, which has been pointed out as the distinctive characteristic that could even turn out an inert substance into another substance exhibiting very different interactions with biological fluids and cells. Therefore, it seems that, when assessing human exposure based on the mass concentration of particles, which is widely adopted for particles over 1 μm, would not work in this particular case. In fact, nanoparticles have far more surface area for the equivalent mass of larger particles, which increases the chance they may react with body tissues. Thus, it has been claimed that surface area should be used for nanoparticle exposure and dosing. As a result, assessing exposure based on the measurement of particle surface area is of increasing interest. It is well known that lung deposition is the most efficient way for airborne particles to enter the body and cause adverse health effects. If nanoparticles can deposit in the lung and remain there, have an active surface chemistry and interact with the body, then, there is potential for exposure. It was showed that surface area plays an important role in the toxicity of nanoparticles and this is the metric that best correlates with particle-induced adverse health effects. The potential for adverse health effects seems to be directly proportional to particle surface area. The objective of the study is to identify and validate methods and tools for measuring nanoparticles during production, manipulation and use of nanomaterials.

10 kVp rule – An anthropomorphic pelvis phantom imaging study using a CR system: impact on image quality and effective dose using AEC and manual mode

Purpose - This study aims to investigate the influence of tube potential (kVp) variation in relation to perceptual image quality and effective dose (E) for pelvis using automatic exposure control (AEC) and non-AEC in a Computed Radiography (CR) system. Methods and materials - To determine the effects of using AEC and non-AEC by applying the 10 kVp rule in two experiments using an anthropomorphic pelvis phantom. Images were acquired using 10 kVp increments (60–120 kVp) for both experiments. The first experiment, based on seven AEC combinations, produced 49 images. The mean mAs from each kVp increment were used as a baseline for the second experiment producing 35 images. A total of 84 images were produced and a panel of 5 experienced observers participated for the image scoring using the two alternative forced choice (2AFC) visual grading software. PCXMC software was used to estimate E. Results - A decrease in perceptual image quality as the kVp increases was observed both in non-AEC and AEC experiments, however no significant statistical differences (p > 0.05) were found. Image quality scores from all observers at 10 kVp increments for all mAs values using non-AEC mode demonstrates a better score up to 90 kVp. E results show a statistically significant decrease (p = 0.000) on the 75th quartile from 0.37 mSv at 60 kVp to 0.13 mSv at 120 kVp when applying the 10 kVp rule in non-AEC mode. Conclusion - Using the 10 kVp rule, no significant reduction in perceptual image quality is observed when increasing kVp whilst a marked and significant E reduction is observed.

Increasing source to image distance for AP pelvis imaging: impact on radiation dose and image quality

Aim - A quantative primary study to determine whether increasing source to image distance (SID), with and without the use of automatic exposure control (AEC) for antero-posterior (AP) pelvis imaging, reduces dose whilst still producing an image of diagnostic quality. Methods - Using a computed radiography (CR) system, an anthropomorphic pelvic phantom was positioned for an AP examination using the table bucky. SID was initially set at 110 cm, with tube potential set at a constant 75 kVp, with two outer chambers selected and a fine focal spot of 0.6 mm. SID was then varied from 90 cm to 140 cm with two exposures made at each 5 cm interval, one using the AEC and another with a constant 16 mAs derived from the initial exposure. Effective dose (E) and entrance surface dose (ESD) were calculated for each acquisition. Seven experienced observers blindly graded image quality using a 5-point Likert scale and 2 Alternative Forced Choice software. Signal-to-Noise Ratio (SNR) was calculated for comparison. For each acquisition, femoral head diameter was also measured for magnification indication. Results - Results demonstrated that when increasing SID from 110 cm to 140 cm, both E and ESD reduced by 3.7% and 17.3% respectively when using AEC and 50.13% and 41.79% respectively, when the constant mAs was used. No significant statistical (T-test) difference (p = 0.967) between image quality was detected when increasing SID, with an intra-observer correlation of 0.77 (95% confidence level). SNR reduced slightly for both AEC (38%) and no AEC (36%) with increasing SID. Conclusion - For CR, increasing SID significantly reduces both E and ESD for AP pelvis imaging without adversely affecting image quality.

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.

10 kVp rule – An anthropomorphic pelvis phantom imaging study using a CR system: impact on image quality and effective dose using AEC and manual mode

Background - Pelvis and hip radiography are consistently found to be amongst the highest contributors to the collective effective dose (E) in all ten DOSE DATAMED countries in Europe, representing 2.8 to 9.4% of total collective dose (S) in the TOP 20 exams list. The level of image quality should provide all the diagnostic information in order not to jeopardise the diagnosis, but being able to provide the needed clinical information with the minimum dose. A recent study suggests further research to determine whether the “10 kVp rule” would have value for a range of examinations using Computed Radiography (CR) systems. As a “rule of thumb” increasing the kVp by 10 whilst halving the mAs is suggested to give a similar perceptual image quality when compared to the original exposure factors. Aims - In light of the 10kVp rule, this study aims to investigate the influence of tube potential (kVp) variation in relation to perceptual image quality and E for pelvis imaging using automatic exposure control (AEC) and non-AEC in a Computed Radiography (CR) system. Research questions - Does the 10kVp rule works for the pelvis in relation to image quality in a CR system? Does the image quality differs when the AEC is used instead of manual mode using the 10kVp rule and how this impacts on E?

Reproducibility of simulated myocardial lesions simulated on a virtual phantom

Human virtual phantoms are being widely used to simulate and characterize the behavior of different organs, either in diagnosis stages but also to enable foreseeing the therapeutic effects obtained on a certain patient. In the present work a typical patient’s heart was simulated using XCAT2©, considering the possibility of a lesion and/or anatomical alteration being affecting the myocardium. These simulated images, were then used to carry out a set of parametric studies using Matlab©. Although performed in controlled sceneries, these studies are very important to understand and characterize the performance of the methodologies used, as well as to determine to what extent the relations between the perturbation introduced at the myocardium and the resulting simulated images can be considered conclusive.

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.

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.