Analysis of polycyclic aromatic hydrocarbons in atmospheric particulate samples by microwaveassisted extraction and liquid chromatography

A methodology based on microwave-assisted extraction (MAE) and LC with fluorescence detection (FLD) was investigated for the efficient determination of 15 polycyclic aromatic hydrocarbons (PAHs) regarded as priority pollutants by the US Environmental Protection Agency and dibenzo(a,l)pyrene in atmospheric particulate samples. PAHs were successfully extracted from real outdoor particulate matter (PM) samples with recoveries ranging from 81.4±8.8 to 112.0±1.1%, for all the compounds except for naphthalene (62.3±18.0%) and anthracene (67.3±5.7%), under the optimum MAE conditions (30.0 mL of ACN for 20 min at 110ºC). No clean-up steps were necessary prior to LC analysis. LOQs ranging from 0.0054 ng/m3 for benzo( a)anthracene to 0.089 ng/m3 for naphthalene were reached. The validated MAE methodology was applied to the determination of PAHs from a set of real world PM samples collected in Oporto (north of Portugal). The sum of particulate-bound PAHs in outdoor PM ranged from 2.5 and 28 ng/m3.

A multiresidue method for the analysis of carbamate and urea pesticides from soils by microwave-assisted extraction and liquid chromatography with photodiode array detection

A multiresidue approach using microwave-assisted extraction and liquid chromatography with photodiode array detection was investigated for the determination of butylate, carbaryl, carbofuran, chlorpropham, ethiofencarb, linuron,metobromuron, and monolinuron in soils. The critical parameters of the developed methodology were studied. Method validation was performed by analyzing freshly and aged spiked soil samples. The recoveries and relative standard deviations reached using the optimized conditions were between 77.0 ± 0.46% and 120 ± 2.9% except for ethiofencarb (46.4 ± 4.4% to 105 ± 1.6%) and butylate (22.1 ± 7.6% to 49.2 ± 11%). Soil samples from five locations of Portugal were analysed.

The wedding of Prince Charles and Camilla Parker-Bowles: royal mediation and press mediatization

Bearing in mind the relationship between discourse and society at large, this article addresses the way the British monarchy represented Charles’s second marriage and the way the media constructed their accounts in the period from 10 February (announcement) until 9 April 2005 (wedding) in relation to wider issues such as power relations, newspaper economic structures and popular culture. Particular attention is paid to the multifunctional features of discourse (i.e. its ideational, interpersonal and textual functions), which requires a contextualized reading of a dual process of mediation: on the one hand, the staging of the ceremony by St. James’s Palace and its strategy for attaining monologic closure and, on the other hand, discursive representations by the British press open to a polyphony of voices and discursive frames

Occurrence of bisphenol A, estrone, 17b-estradiol and 17a-ethinylestradiol in Portuguese rivers

This study focused on the occurrence of several EDCs including bisphenol A, estrone (E1), the 17b-estradiol (E2) and 17a- thinylestradiol (EE2) in fourteen rivers of Portugal. Samples analysis revealed a widespread contamination of BPA especially in Ave, Cávado, Douro, Ferro, Sousa and Vizela Rivers. Achieving 98.4 ng/L for the highest concentration. The estrogens achieved above the method quantification limit (MQL) were E1 in Águeda River and E2 in Ave, Lima and Tâmega Rivers. The maximum concentration detected for E1 was 26.9 ng/L. EE2 was detected only below MQL.

Development of a simple analytical method for the simultaneousdetermination of paracetamol, paracetamol-glucuronide andp-aminophenol in river water

Paracetamol is among the most worldwide consumed pharmaceuticals. Although its occurrence in the environment is well documented, data about the presence of its metabolites and transformation products is very scarce. The present work describes the development of an analytical method for the simultaneous determination of paracetamol, its principal metabolite (paracetamol-glucuronide) and its main transformation product (p-aminophenol) based on solid phase extraction (SPE) and high performance liquid chromatography coupled to diode array detection (HPLC-DAD). The method was applied to analysis of river waters, showing to be suitable to be used in routine analysis. Different SPE sorbents were compared and the use of two Oasis WAX cartridges in tandem proved to be the most adequate approach for sample clean up and pre-concentration. Under optimized conditions, limits of detection in the range 40–67 ng/L were obtained, as well as mean recoveries between 60 and 110% with relative standard deviations (RSD) below 6%. Finally, the developed SPE-HPLC/DAD method was successfully applied to the analysis of the selected compounds in samples from seven rivers located in the north of Portugal. Nevertheless all the compounds were detected, it was the first time that paracetamol-glucuronide was found in river water at concentrations up to 3.57 μg/L.

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.

A sensitivity study of the WRF model in wind simulation for an area of high wind energy

The performance of the Weather Research and Forecast (WRF) model in wind simulation was evaluated under different numerical and physical options for an area of Portugal, located in complex terrain and characterized by its significant wind energy resource. The grid nudging and integration time of the simulations were the tested numerical options. Since the goal is to simulate the near-surface wind, the physical parameterization schemes regarding the boundary layer were the ones under evaluation. Also, the influences of the local terrain complexity and simulation domain resolution on the model results were also studied. Data from three wind measuring stations located within the chosen area were compared with the model results, in terms of Root Mean Square Error, Standard Deviation Error and Bias. Wind speed histograms, occurrences and energy wind roses were also used for model evaluation. Globally, the model accurately reproduced the local wind regime, despite a significant underestimation of the wind speed. The wind direction is reasonably simulated by the model especially in wind regimes where there is a clear dominant sector, but in the presence of low wind speeds the characterization of the wind direction (observed and simulated) is very subjective and led to higher deviations between simulations and observations. Within the tested options, results show that the use of grid nudging in simulations that should not exceed an integration time of 2 days is the best numerical configuration, and the parameterization set composed by the physical schemes MM5–Yonsei University–Noah are the most suitable for this site. Results were poorer in sites with higher terrain complexity, mainly due to limitations of the terrain data supplied to the model. The increase of the simulation domain resolution alone is not enough to significantly improve the model performance. Results suggest that error minimization in the wind simulation can be achieved by testing and choosing a suitable numerical and physical configuration for the region of interest together with the use of high resolution terrain data, if available.

Geography of the Information Society

All every day activities take place in space. And it is upon this that all information and knowledge revolve. The latter are the key elements in the organisation of territories. Their creation, use and distribution should therefore occur in a balanced way throughout the whole territory in order to allow all individuals to participate in an egalitarian society, in which the flow of knowledge can take precedence over the flow of interests. The information society depends, to a large extent, on the technological capacity to disseminate information and, consequently, the knowledge throughout territory, thereby creating conditions which allow a more balanced development, from the both the social and economic points of view thus avoiding the existence of info-exclusion territories. Internet should therefore be considered more than a mere technology, given that its importance goes well beyond the frontiers of culture and society. It is already a part of daily life and of the new forms of thinking and transmitting information, thus making it a basic necessity essential, for a full socio-economic development. Its role as a platform of creation and distribution of content is regarded as an indispensable element for education in today’s society, since it makes information a much more easily acquired benefit.”…in the same way that the new technologies of generation and distribution of energy allowed factories and large companies to establish themselves as the organisational bases of industrial society, so the internet today constitutes the technological base of the organisational form that characterises the Information Era: the network” (CASTELLS, 2004:15). The changes taking place today in regional and urban structures are increasingly more evident due to a combination of factors such as faster means of transport, more efficient telecommunications and other cheaper and more advanced technologies of information and knowledge. Although their impact on society is obvious, society itself also has a strong influence on the evolution of these technologies. And although physical distance has lost much of the responsibility it had towards explaining particular phenomena of the economy and of society, other aspects such as telecommunications, new forms of mobility, the networks of innovation, the internet, cyberspace, etc., have become more important, and are the subject of study and profound analysis. The science of geographical information, allows, in a much more rigorous way, the analysis of problems thus integrating in a much more balanced way, the concepts of place, of space and of time. Among the traditional disciplines that have already found their place in this process of research and analysis, we can give special attention to a geography of new spaces, which, while not being a geography of ‘innovation’, nor of the ‘Internet’, nor even ‘virtual’, which can be defined as one of the ‘Information Society’, encompassing not only the technological aspects but also including a socio-economic approach. According to the last European statistical data, Portugal shows a deficit in terms of information and knowledge dissemination among its European partners. Some of the causes are very well identified - low levels of scholarship, weak investments on innovation and R&D (both private and public sector) - but others seem to be hidden behind socio-economical and technological factors. So, the justification of Portugal as the case study appeared naturally, on a difficult quest to find the major causes to territorial asymmetries. The substantial amount of data needed for this work was very difficult to obtain and for the islands of Madeira and Azores was insufficient, so only Continental Portugal was considered for this study. In an effort to understand the various aspects of the Geography of the Information Society and bearing in mind the increasing generalised use of information technologies together with the range of technologies available for the dissemination of information, it is important to: (i) Reflect on the geography of the new socio-technological spaces. (ii) Evaluate the potential for the dissemination of information and knowledge through the selection of variables that allow us to determine the dynamic of a given territory or region; (iii) Define a Geography of the Information Society in Continental Portugal.

Assessment of ultrafine particles in Portuguese preschools: levels and exposure doses

The aim of this work was to assess ultrafine particles (UFP) number concentrations in different microenvironments of Portuguese preschools and to estimate the respective exposure doses of UFP for 3–5-year-old children (in comparison with adults). UFP were sampled both indoors and outdoors in two urban (US1, US2) and one rural (RS1) preschool located in north of Portugal for 31 days. Total levels of indoor UFP were significantly higher at the urban preschools (mean of 1.82x104 and 1.32x104 particles/cm3 at US1 an US2, respectively) than at the rural one (1.15x104 particles/cm3). Canteens were the indoor microenvironment with the highest UFP (mean of 5.17x104, 3.28x104, and 4.09x104 particles/cm3 at US1, US2, and RS1), whereas the lowest concentrations were observed in classrooms (9.31x103, 11.3x103, and 7.14x103 particles/cm3 at US1, US2, and RS1). Mean indoor/outdoor ratios (I/O) of UFP at three preschools were lower than 1 (0.54–0.93), indicating that outdoor emissions significantly contributed to UFP indoors. Significant correlations were obtained between temperature, wind speed, relative humidity, solar radiation, and ambient UFP number concentrations. The estimated exposure doses were higher in children attending urban preschools; 3–5-year-old children were exposed to 4–6 times higher UFP doses than adults with similar daily schedules.

Age-period-cohort effects in the incidence of hip fractures: political and economic events are coincident with changes in risk

Introduction: Healthcare improvements have allowed prevention but have also increased life expectancy, resulting in more people being at risk. Our aim was to analyse the separate effects of age, period and cohort on incidence rates by sex in Portugal, 2000–2008. Methods: From the National Hospital Discharge Register, we selected admissions (aged ≥49 years) with hip fractures (ICD9-CM, codes 820.x) caused by low/moderate trauma (falls from standing height or less), readmissions and bone cancer cases. We calculated person-years at risk using population data from Statistics Portugal. To identify period and cohort effects for all ages, we used an age–period–cohort model (1-year intervals) followed by generalised additive models with a negative binomial distribution of the observed incidence rates of hip fractures. Results: There were 77,083 hospital admissions (77.4 % women). Incidence rates increased exponentially with age for both sexes (age effect). Incidence rates fell after 2004 for women and were random for men (period effect). There was a general cohort effect similar in both sexes; risk of hip fracture altered from an increasing trend for those born before 1930 to a decreasing trend following that year. Risk alterations (not statistically significant) coincident with major political and economic change in the history of Portugal were observed around birth cohorts 1920 (stable–increasing), 1940 (decreasing–increasing) and 1950 (increasing–decreasing only among women). Conclusions: Hip fracture risk was higher for those born during major economically/politically unstable periods. Although bone quality reflects lifetime exposure, conditions at birth may determine future risk for hip fractures.

Evolution of Drug Resistance: Insight on TEM -Lactamases Structure and Activity and Beta-Lactam Antibiotics

Extended-spectrum β-lactamases (ESBLs) prevalence was studied in the north of Portugal, among 193 clinical isolates belonging to citizens in a district in the boundaries between this country and Spain from a total of 7529 clinical strains. In the present study we recovered some members of Enterobacteriaceae family, producing ESBL enzymes, including Escherichia coli (67.9%), Klebsiella pneumoniae (30.6%), Klebsiella oxytoca (0.5%), Enterobacter aerogenes (0.5%), and Citrobacter freundii (0.5%). β-lactamases genes blaTEM, blaSHV, and blaCTX-M were screened by polymerase chain reaction (PCR) and sequencing approaches. TEM enzymes were among the most prevalent types (40.9%) followed by CTX-M (37.3%) and SHV (23.3%). Among our sample of 193 ESBL-producing strains 99.0% were resistant to the fourth-generation cephalosporin cefepime. Of the 193 isolates 81.3% presented transferable plasmids harboring genes. Clonal studies were performed by PCR for the enterobacterial repetitive intragenic consensus (ERIC) sequences. This study reports a high diversity of genetic patterns. Ten clusters were found for E. coli isolates and five clusters for K. pneumoniae strains by means of ERIC analysis. In conclusion, in this country, the most prevalent type is still the TEM-type, but CTX-M is growing rapidly.

Earthquakes in western Iberia: improving the understanding of lithospheric deformation in a slowly deforming region

Mainland Portugal, on the southwestern edge of the European continent, is located directly north of the boundary between the Eurasian and Nubian plates. It lies in a region of slow lithospheric deformation (< 5 mm yr(-1)), which has generated some of the largest earthquakes in Europe, both intraplate (mainland) and interplate (offshore). Some offshore earthquakes are nucleated on old and cold lithospheric mantle, at depths down to 60 km. The seismicity of mainland Portugal and its adjacent offshore has been repeatedly classified as diffuse. In this paper, we analyse the instrumental earthquake catalogue for western Iberia, which covers the period between 1961 and 2013. Between 2010 and 2012, the catalogue was enriched with data from dense broad-band deployments. We show that although the plate boundary south of Portugal is diffuse, in that deformation is accommodated along several distributed faults rather than along one long linear plate boundary, the seismicity itself is not diffuse. Rather, when located using high-quality data, earthquakes collapse into well-defined clusters and lineations. We identify and characterize the most outstanding clusters and lineations of epicentres and correlate them with geophysical and tectonic features (historical seismicity, topography, geologically mapped faults, Moho depth, free-air gravity, magnetic anomalies and geotectonic units). Both onshore and offshore, clusters and lineations of earthquakes are aligned preferentially NNE-SSW and WNW-ESE. Cumulative seismic moment and epicentre density decrease from south to north, with increasing distance from the plate boundary. Only few earthquake lineations coincide with geologically mapped faults. Clusters and lineations that do not match geologically mapped faults may correspond to previously unmapped faults (e.g. blind faults), rheological boundaries or distributed fracturing inside blocks that are more brittle and therefore break more easily than neighbour blocks. The seismicity map of western Iberia presented in this article opens important questions concerning the regional seismotectonics. This work shows that the study of low-magnitude earthquakes using dense seismic deployments is a powerful tool to study lithospheric deformation in slowly deforming regions, such as western Iberia, where high-magnitude earthquakes occur with long recurrence intervals.

Toxicity assessment of crude and partially purified extracts of marine Synechocystis and Synechococcus cyanobacterial strains in marine invertebrates

Among the Cyanoprokaryota, the genera Synechocystis and Synechococcus have rarely been studied with respect to potential toxicity. This is particularly true with marine environments where studies about the toxicity of cyanobacteria are restricted to filamentous forms at the warmer temperate and tropical regions and also to filamentous forms at cold seas such as the Baltic Sea. In this study, we describe the effects of cyanobacterial strains of the Synechocystis and Synechococcus genera isolated from the marine coast of Portugal, on marine invertebrates. Crude and partially purified extracts at a concentration of 100 mg/ml of freeze-dried material of the marine strains were tested for acute toxicity in nauplii of the brine shrimp Artemia salina, in the rotifer Brachionus plicatillis and in embryos of the sea urchin Paracentrotus lividus and the mussel Mytilus galloprovincialis. The cyanobacterial extracts, especially the crude extract, had an impact on A. salina nauplii. No significant toxic effects were registered against the rotifer. A negative impact of all strains was recorded on the embryonic development of the sea urchin, with toxic effects resulting in an inhibition of embryogenesis or development of smaller larvae. To the mussel embryos, the effects of cyanobacterial extracts resulted in a complete inhibition of embryogenesis. The results of all assays indicate that Synechocystis and Synechococcus marine strains contained toxic compounds to marine invertebrates.

Penicillium glabrum cork colonising isolates – preliminary analysis of their genomic similari

Cork stopper manufacturing process includes an operation, known as stabilisation, by which humid cork slabs are extensively colonised by fungi. The effects of fungal growth on cork are yet to be completely understood and are considered to be involved in the so called “cork taint” of bottled wine. It is essential to identify environmental constraints which define the appearance of the colonising fungal species and to trace their origin to the forest and/or as residents in the manufacturing space. The present article correlates two sets of data, from consecutive years and the same season, of systematic biologic sampling of two manufacturing units, located in the North and South of Portugal. Chrysonilia sitophila dominance was identified, followed by a high diversity of Penicillium species. Penicillium glabrum, found in all samples, was the most frequent isolated species. P. glabrum intra-species variability was investigated using DNA fingerprinting techniques revealing highly discriminative polymorphic markers in the genome. Cluster analysis of P. glabrum data was discussed in relation to the geographical location of strains, and results suggest that P. glabrum arise from predominantly the manufacturing space, although cork resident fungi can also contrib

Evaluation of Opuntia spp. bioactive products as promising natural chemotherapeutical agents- an in vitro approach

Dissertation to obtain a Master Degree in Biotechnology