Trace metals in size-fractionated particulate matter in a Portuguese hospital: exposure risks assessment and comparisons with other countries

Hospitals are considered as a special and important type of indoor public place where air quality has significant impacts on potential health outcomes. Information on indoor air quality of these environments, concerning exposures to particulate matter (PM) and related toxicity, is limited though. This work aims to evaluate risks associated with inhalation exposure to ten toxic metals and chlorine (As, Ni, Cr, Cd, Pb, Mn, Se, Ba, Al, Si, and Cl) in coarse (PM2.5–10) and fine (PM2.5) particles in a Portuguese hospital in comparison with studies representative of other countries. Samples were collected during 1 month in one urban hospital; elemental PM characterization was determined by proton-induced X-ray emission. Noncarcinogenic and carcinogenic risks were assessed according to the methodology provided by the United States Environmental Protection Agency (USEPA; Region III Risk-Based Concentration Table) for three different age categories of hospital personnel (adults, >20, and <65 years) and patients (considering nine different age groups, i.e., children of 1–3 years to seniors of >65 years). The estimated noncarcinogenic risks due to occupational inhalation exposure to PM2.5-bound metals ranged from 5.88×10−6 for Se (adults, 55–64 years) to 9.35×10−1 for As (adults, 20–24 years) with total noncarcinogenic risks (sum of all metals) above the safe level for all three age categories. As and Cl (the latter due to its high abundances) were the most important contributors (approximately 90 %) to noncarcinogenic risks. For PM2.5–10, noncarcinogenic risks of all metals were acceptable to all age groups. Concerning carcinogenic risks, for Ni and Pb, they were negligible (<1×10−6) in both PM fractions for all age groups of hospital personnel; potential risks were observed for As and Cr with values in PM2.5 exceeding (up to 62 and 5 times, respectively) USEPA guideline across all age groups; for PM2.5–10, increased excess risks of As and Cr were observed particularly for long-term exposures (adults, 55–64 years). Total carcinogenic risks highly (up to 67 times) exceeded the recommended level for all age groups, thus clearly showing that occupational exposure to metals in fine particles pose significant risks. If the extensive working hours of hospital medical staff were considered, the respective noncarcinogenic and carcinogenic risks were increased, the latter for PM2.5 exceeding the USEPA cumulative guideline of 10−4. For adult patients, the estimated noncarcinogenic and carcinogenic risks were approximately three times higher than for personnel, with particular concerns observed for children and adolescents.

Segurança no circuito do medicamento citotóxico: contributos para a avaliação da realidade hospitalar em Portugal

Introdução: O medicamento citotóxico é definido pelas suas características de genotoxicidade, mutagenicidade, carcinogenicidade, teratogenicidade, toxicidade reprodutiva e toxicidade orgânica em baixas doses. Deste modo, existe uma grande preocupação no que concerne ao manuseamento deste tipo de medicamentos, devido aos riscos ocupacionais que podem surtir da exposição a que os profissionais de farmácia envolvidos estão sujeitos. Objectivos: Analisar a realidade da farmácia hospitalar face ao cumprimento das normas e procedimentos preconizados pelas actuais guidelines para o manuseamento seguro de medicamentos citotóxicos, e identificar as lacunas existentes, conduzindo à promoção de práticas centradas na minimização do risco de exposição/contaminação dos profissionais e do ambiente. Material e Métodos: Foi realizada uma pesquisa bibliográfica sistemática sobre o tema, utilizando-se como instrumento de recolha de dados um inquérito por questionário, em que os TDT de Farmácia foram abordados sobre os procedimentos verificados no hospital onde exercem actividade profissional. Resultados: Face ao cumprimento das normas na recepção, armazenamento e transporte de medicamentos citotóxicos, verifica-se que todos os hospitais se encontram acima da média. Apesar desta evidência, é na fase de transporte que se verifica um menor cumprimento. As principais lacunas detectadas foram ao nível da não utilização de EPI nas fases de recepção e armazenamento; a recepção de medicamentos citotóxicos em conjunto com outros medicamentos; a falta de um sistema de ventilação no local de armazenamento e, ainda, ausência de portas de correr e/ou gavetas fechadas nos carros de transporte de medicamentos citotóxicos. Conclusões: Os resultados deste estudo revelam alguma heterogeneidade de procedimentos nos hospitais Portugueses, sugerindo a necessidade de intervenção e reformulação do programa de segurança e gestão de risco desenvolvidos para o manuseamento de citotóxicos.

Polycyclic aromatic hydrocarbon levels in three pelagic fish species from Atlantic Ocean: inter-specific and inter-season comparisons and assessment of potential public health risks

The concentrations of 18 polycyclic aromatic hydrocarbons (PAHs) were determined in three commercially valuable fish species (sardine, Sardina pilchardus; chub mackerel, Scomber japonicus; and horse mackerel, Trachurus trachurus) from the Atlantic Ocean. Specimens were collected seasonally during 2007–2009. Only low molecular weight PAHs were detected, namely, naphthalene, acenaphthene, fluorene and phenanthrene. Chub mackerel (1.80–19.90 microg/kg ww) revealed to be significantly more contaminated than horse mackerel (2.73–10.0 microg/kg ww) and sardine (2.29–14.18 microg/kg ww). Inter-specific and inter-season comparisons of PAHs bioaccumulation were statistically assessed. The more relevant statistical correlations were observed between PAH amounts and total fat content (significant positive relationships, p < 0.05), and season (sardine displayed higher amounts in autumn–winter while the mackerel species showed globally the inverse behavior). The health risks by consumption of these species were assessed and shown to present no threat to public health concerning PAH intakes.

Global material analysis on phosphorus flows, supply horizon and impact assessment on phosphorus depletion

Different problems are daily discuss on environmental aspects such acid rain, eutrophication, global warming and an others problems. Rarely do we find some discussions about phosphorus problematic. Through the years the phosphorus as been a real problem and must be more discussed. On this thesis was done a global material flow analysis of phosphorus, based on data from the year 2004, the production of phosphate rock in that year was 18.9 million tones, almost this amount it was used as fertilizer on the soil and the plants only can uptake, on average, 20% of the input of fertilizer to grow up, the remainder is lost for the phosphorus soil. In the phosphorus soil there is equilibrium between the phosphorus available to uptake from the plants and the phosphorus associate with other compounds, this equilibrium depends of the kind of soil and is related with the soil pH. A reserve inventory was done and we have 15,000 million tones as reserve, the amount that is economical available. The reserve base is estimated in 47,000 million tones. The major reserves can be found in Morocco and Western Sahara, United Sates, China and South Africa. The reserve estimated in 2009 was 15,000 million tone of phosphate rock or 1,963 million tone of P. If every year the mined phosphate rock is around 22 Mt/yr (phosphorus production on 2008 USGS 2009), and each year the consumption of phosphorus increases because of the food demand, the reserves of phosphate rock will be finished in about 90 years, or maybe even less. About the value/impact assessment was done a qualitative analysis, if on the future we don’t have more phosphate rock to produce fertilizers, it is expected a drop on the crops yields, each depends of the kind of the soil and the impact on the humans feed and animal production will not be a relevant problem. We can recovery phosphorus from different waste streams such as ploughing crop residues back into the soil, Food processing plants and food retailers, Human and animal excreta, Meat and bone meal, Manure fibre, Sewage sludge and wastewater. Some of these examples are developed in the paper.

Contribuição para o conhecimento sobre o efeito da utilização de material pozolânico no fabrico de betão

O presente trabalho, realizado no âmbito da Tese de Mestrado, tem como principal objectivo estudar as características pozolânicas dos materiais da zona de Arganil para substituição parcial do cimento Portland com o objectivo de intensificar certas qualidades devido à diminuição da porosidade do betão. Estas qualidades são interessantes quando se procura maior durabilidade. Para tal, foram realizados diversos ensaios para a caracterização física, química e mineralógica dos produtos. Os metacaulinos utilizados foram obtidos de amostras de argila submetidas a calcinação (750oC, durante uma hora), processo que permitiu a desidroxilação quase total da matéria-prima, transformando esta numa fase amorfa e irreversível, com propriedades pozolânicas. São apresentados os resultados dos ensaios de caracterização da matéria-prima, das condições de calcinação e do produto resultante da desidroxilação, nomeadamente a determinação da pozolanicidade e superfície específica e das características fundamentais para a aplicabilidade do produto. Descreve ainda o emprego do metacaulino em betões de resistência convencional. Estudou-se a influência do emprego do metacaulino (15% de substituição de cimento, em massa) na resistência à flexão e à compressão (aos 28 dias) em argamassas e o emprego de metacaulino (10%, 15% e 20% de substituição de cimento, em massa) na resistência à compressão (3, 7 e 28 dias) no betão.

Material compósito - propriedades do aglomerado de gesso e partículas fragmentadas de bambu (phyllostachys edulis)

Neste trabalho estudou-se um compósito de gesso FGD reforçado com fibras vegetais. As fibras utilizadas neste estudo são provenientes de bambu da espécie Phyllostachys edulis e foram trituradas até se obter uma granulometria apropriada à composição de uma pasta de gesso que permitisse a execução de placas de gesso laminado. As placas produzidas foram ensaiadas à flexão e posteriormente submetidas à análise de humidade para aferir a percentagem de água de cristalização nas amostras. Foram ainda produzidos provetes cúbicos com 7cm de aresta para permitira a execução de ensaio à compressão. Foram produzidos dois tipos de pastas, uma sem a adição de partículas de bambu (controlo) e outra com adição de 15% de partículas de bambu.

Mercury, cadmium, lead and arsenic levels in three pelagic fish species from the Atlantic Ocean: intra- and inter-specific variability and human health risks for consumption

Three commonly consumed and commercially valuable fish species (sardine, chub and horse mackerel) were collected from the Northeast and Eastern Central Atlantic Ocean in Portuguese waters during one year. Mercury, cadmium, lead and arsenic amounts were determined in muscles using graphite furnace and cold vapour atomic absorption spectrometry. Maximum mean levels of mercury (0.1715 ± 0.0857 mg/kg, ww) and arsenic (1.139 ± 0.350 mg/kg, ww) were detected in horse mackerel. The higher mean amounts of cadmium (0.0084 ± 0.0036 mg/kg, ww) and lead (0.0379 ± 0.0303 mg/kg, ww) were determined in chub mackerel and in sardine, respectively. Intra- and inter-specific variability of metals bioaccumulation was statistically assessed and species and length revealed to be the major influencing biometric factors, in particular for mercury and arsenic. Muscles present metal concentrations below the tolerable limits considered by European Commission Regulation and Food and Agriculture Organization of the United Nations/World Health Organization (FAO/WHO). However, estimation of non-carcinogenic and carcinogenic health risks by the target hazard quotient and target carcinogenic risk, established by the US Environmental Protection Agency, suggests that these species must be eaten in moderation due to possible hazard and carcinogenic risks derived from arsenic (in all analyzed species) and mercury ingestion (in horse and chub mackerel species).

Polycyclic aromatic hydrocarbons in gas and particulate phases of indoor environments influenced by tobacco smoke: levels, phase distributions, and health risks

As polycyclic aromatic hydrocarbons (PAHs) have a negative impact on human health due to their mutagenic and/or carcinogenic properties, the objective of this work was to study the influence of tobacco smoke on levels and phase distribution of PAHs and to evaluate the associated health risks. The air samples were collected at two homes; 18 PAHs (the 16 PAHs considered by U.S. EPA as priority pollutants, dibenzo[a,l]pyrene and benzo[j]fluoranthene) were determined in gas phase and associated with thoracic (PM10) and respirable (PM2.5) particles. At home influenced by tobacco smoke the total concentrations of 18 PAHs in air ranged from 28.3 to 106 ngm 3 (mean of 66.7 25.4 ngm 3),∑PAHs being 95% higher than at the non-smoking one where the values ranged from 17.9 to 62.0 ngm 3 (mean of 34.5 16.5 ngm 3). On average 74% and 78% of ∑PAHs were present in gas phase at the smoking and non-smoking homes, respectively, demonstrating that adequate assessment of PAHs in air requires evaluation of PAHs in both gas and particulate phases. When influenced by tobacco smoke the health risks values were 3.5e3.6 times higher due to the exposure of PM10. The values of lifetime lung cancer risks were 4.1 10 3 and 1.7 10 3 for the smoking and nonsmoking homes, considerably exceeding the health-based guideline level at both homes also due to the contribution of outdoor traffic emissions. The results showed that evaluation of benzo[a]pyrene alone would probably underestimate the carcinogenic potential of the studied PAH mixtures; in total ten carcinogenic PAHs represented 36% and 32% of the gaseous ∑PAHs and in particulate phase they accounted for 75% and 71% of ∑PAHs at the smoking and non-smoking homes, respectively.

Desenvolvimento de uma ferramenta para cálculo de estruturas em material compósito

Os desafios à engenharia moderna são cada vez maiores, pretendendo-se quase sempre obter estruturas mais leves, com propriedades mecânicas atrativas e muitas vezes com geometrias complexas. Com tais requisitos, um dos materiais que tem vindo a ter uma crescente aplicação é o material compósito. Contudo, no que toca ao cálculo estrutural destes materiais, tudo se torna mais complexo, já que são materiais que geralmente são formados por empilhamento de várias camadas de material heterogéneo, podendo estas encontrarem-se dispostas segundo diferentes orientações. Assim, a utilização de um software que permita a previsão das propriedades mecânicas de uma estrutura em material compósito através da micromecânica, a aplicação da Teoria Clássica dos Laminados e de um critério de rotura, como por exemplo o de Tsai-Hill, é fundamental para agilizar o processo de estudo da estrutura a fabricar. Para dar uma resposta a tal necessidade foi desenvolvida uma aplicação, em MATLAB® GUI, denominada CAFE – Composite Analysis For Engineers, com ambiente gráfico apelativo, que permite determinar todas as variáveis importantes no estudo de estruturas em material compósito. Esta aplicação visa suportar e agilizar a aprendizagem desta área do conhecimento, permitindo também o acesso ao código de cálculo por parte do utilizador, de modo a conhecerem-se as equações utilizadas e, eventualmente, ser alvo de futuros desenvolvimentos. O programa desenvolvido foi alvo de validação, recorrendo-se para tal, a uma comparação dos resultados obtidos entre o respetivo programa e por um outro programa de grande fiabilidade. Assim sendo, concluiu-se que o software CAFE apresenta resultados válidos, encontrando-se apto a ser utilizado.

Deteção eletroquímica da norfloxacina e trimetoprim em amostras de urina utilizando polímero molecularmente impresso modificado e grafeno

A norfloxacina e o trimetoprim são dois antibióticos antibacterianos usados para o tratamento de infeções urinárias, intestinais e respiratórias. A maioria dos fármacos exige uma dosagem que garanta os níveis de segurança e eficácia de atuação. A necessidade de dosear os medicamentos e os seus metabolitos é assim um controlo imperioso e em muitos casos regular no tratamento de um paciente. Neste trabalho desenvolveram-se dois sensores eletroquímicos para a deteção da norfloxacina (NFX) e do trimetoprim (TMP), usando como superfície de suporte o carbono vítreo. A busca de novos materiais que conferiram maior seletividade e sensibilidade aos sistemas de deteção e por outro lado apresentem menores riscos para o paciente quando usados em dispositivos que permitam uma análise point-of-care, é especialmente importante e pode ser uma parte crucial do processo de decisão clínica. Assim, os polímeros molecularmente impresos enquadram-se nesse perfil e o seu uso tem vindo a ser cada vez mais avaliado. A impressão molecular é uma tecnologia capaz de produzir polímeros que incorporam as moléculas do analito e que após remoção por solventes específicos, permitem dotá-los de locais específicos de reconhecimento estereoquímico. A seleção do pirrol como polímero molecularmente impresso (MIP) permitiu construir com sucesso os sensores para doseamento dos antibióticos. A fim de aumentar a sensibilidade do método incorporou-se grafeno na superfície do elétrodo. Este material tem vindo a ser largamente utilizado devido às suas propriedades: estrutura molecular, condutividade elétrica e aumento da superfície são algumas das características que mais despertam o interesse para a sua aplicação neste projeto. Os sensores desenvolvidos foram incorporados em sistemas eletroquímicos. Os métodos voltamétricos aplicados foram a voltametria cíclica, a voltametria de onda quadrada e ainda a impedância. As condições de análise foram otimizadas no que respeita à polimerização do pirrol (concentração do polímero, número de ciclos de eletropolimerização e respetivos potenciais aplicados, tempo de incubação, solvente de remoção do analito), ao pH da solução do fármaco, à gama de concentrações dos antibióticos e aos parâmetros voltamétricos dos métodos de análise. Para cada um dos antibióticos um elétrodo não-impresso foi também preparado, usando o procedimento de polimerização mas sem a presença da molécula do analito, e foi usado como controlo. O sensor desenvolvido para o trimetoprim foi usado no doseamento do fármaco em amostras de urina. As amostras foram analisadas sem qualquer diluição, apenas foram centrifugadas para remoção de proteínas e algum interferente. Os sensores construídos apresentaram comportamento linear na gama de concentrações entre 102 e 107 mol/L. Os resultados mostram boa precisão (desvios padrão inferiores a 11%) e os limites de deteção foram de 8,317 e 1,307 mol/L para a norfloxacina e o trimetoprim, respetivamente. Para validação do método foram ainda efetuados ensaios de recuperação tendo obtido valores superiores a 94%.

Polycyclic aromatic hydrocarbons in commercial squids from different geographical origins: levels and risks for human consumption

The concentrations of 18 polycyclic aromatic hydrocarbons (PAHs) were determined in five commercially valuable squid species from different geographical origins (Atlantic, Indic and Pacific Oceans). Out of the 18 quantified PAHs (the 16 PAHs considered by US EPA as priority pollutants, dibenzo(a,l)pyrene and benzo(j)fluoranthene) only dibenz(a,h)anthracene was not detected. The total concentrations of PAHs varied by a factor of more than 100-fold, from 0.22 (Loligo gahi) to 60.9 lg/kg ww (Loligo reynaudii). Intraand inter-specific variability of PAH levels was statistically assessed. Nine carcinogenic (probable/possible) PAHs accounted for 1% (L. reynaudii) to 26% (Loligo opalescens) of the total PAHs content being the main contributors naphthalene (in Loligo duvaucelii, L. reynaudii and Loligo vulgaris species), chrysene (in L. opalescens) and indeno(1,2,3-cd)pyrene (in L. gahi). PAHs source analysis indicated that four of the five zones of capture of the different squid species are significantly affected by both petrogenic and pyrolytic sources. Assessment of the target carcinogenic risks, established by the US EPA, suggested that L. gahi (Atlantic Ocean) and L. opalescens (from Pacific Ocean) may pose additional risks for consumers, if not eaten in moderation, derived from benzo(a)pyrene ingestion.

Impact of vehicular traffic emissions on particulate-bound PAHs: levels and associated health risks

Considering vehicular transport as one of the most health‐relevant emission sources of urban air, and with aim to further understand its negative impact on human health, the objective of this work was to study its influence on levels of particulate‐bound PAHs and to evaluate associated health risks. The 16 PAHs considered by USEPA as priority pollutants, and dibenzo[a, l]pyrene associated with fine (PM2.5) and coarse (PM2.5–10) particles were determined. The samples were collected at one urban site, as well as at a reference place for comparison. The results showed that the air of the urban site was more seriously polluted than at the reference one, with total concentrations of 17 PAHs being 2240% and 640% higher for PM2.5 and PM2.5–10, respectively; vehicular traffic was the major emission source at the urban site. PAHs were predominantly associated with PM2.5 (83% to 94% of ΣPAHs at urban and reference site, respectively) with 5 rings PAHs being the most abundant groups of compounds at both sites. The risks associated with exposure to particulate PAHs were evaluated using the TEF approach. The estimated value of lifetime lung cancer risks exceeded the health‐based guideline levels, thus demonstrating that exposure to PM2.5‐bound PAHs at levels found at urban site might cause potential health risks. Furthermore, the results showed that evaluation of benzo[a] pyrene (regarded as a marker of the genotoxic and carcinogenic PAHs) alone would probably underestimate the carcinogenic potential of the studied PAH mixtures.

PAH air pollution at a Portuguese urban area: carcinogenic risks and sources identification

This study aimed to characterize air pollution and the associated carcinogenic risks of polycyclic aromatic hydrocarbon (PAHs) at an urban site, to identify possible emission sources of PAHs using several statistical methodologies, and to analyze the influence of other air pollutants and meteorological variables on PAH concentrations.The air quality and meteorological data were collected in Oporto, the second largest city of Portugal. Eighteen PAHs (the 16 PAHs considered by United States Environment Protection Agency (USEPA) as priority pollutants, dibenzo[a,l]pyrene, and benzo[j]fluoranthene) were collected daily for 24 h in air (gas phase and in particles) during 40 consecutive days in November and December 2008 by constant low-flow samplers and using polytetrafluoroethylene (PTFE) membrane filters for particulate (PM10 and PM2.5 bound) PAHs and pre-cleaned polyurethane foam plugs for gaseous compounds. The other monitored air pollutants were SO2, PM10, NO2, CO, and O3; the meteorological variables were temperature, relative humidity, wind speed, total precipitation, and solar radiation. Benzo[a]pyrene reached a mean concentration of 2.02 ngm−3, surpassing the EU annual limit value. The target carcinogenic risks were equal than the health-based guideline level set by USEPA (10−6) at the studied site, with the cancer risks of eight PAHs reaching senior levels of 9.98×10−7 in PM10 and 1.06×10−6 in air. The applied statistical methods, correlation matrix, cluster analysis, and principal component analysis, were in agreement in the grouping of the PAHs. The groups were formed according to their chemical structure (number of rings), phase distribution, and emission sources. PAH diagnostic ratios were also calculated to evaluate the main emission sources. Diesel vehicular emissions were the major source of PAHs at the studied site. Besides that source, emissions from residential heating and oil refinery were identified to contribute to PAH levels at the respective area. Additionally, principal component regression indicated that SO2, NO2, PM10, CO, and solar radiation had positive correlation with PAHs concentrations, while O3, temperature, relative humidity, and wind speed were negatively correlated.

Role of abrasive material on micro-abrasion wear tests

Micro-abrasion wear tests with ball-cratering configuration are widely used. Sources of variability are already studied by different authors and conditions for testing are parameterized by BS EN 1071-6: 2007 standard which refers silicon carbide as abrasive. However, the use of other abrasives is possible and allowed. In this work, ball-cratering wear tests were performed using four different abrasive particles of three dissimilar materials: diamond, alumina and silicon carbide. Tests were carried out under the same conditions on a steel plate provided with TiB2 hard coating. For each abrasive, five different test durations were used allowing understanding the initial wear phenomena. Composition and shape of abrasive particles were investigated by SEM and EDS. Scar areas were observed by optical and electronic microscopy in order to understand the wear effects caused by each of them. Scar geometry and grooves were analyzed and compared. Wear coefficient was calculated for each situation. It was observed that diamond particles produce well-defined and circular wear scars. Different silicon carbide particles presented dissimilar results as consequence of distinct particle shape and size distribution.

Drilling damage in composite material

The characteristics of carbon fibre reinforced laminates have widened their use from aerospace to domestic appliances, and new possibilities for their usage emerge almost daily. In many of the possible applications, the laminates need to be drilled for assembly purposes. It is known that a drilling process that reduces the drill thrust force can decrease the risk of delamination. In this work, damage assessment methods based on data extracted from radiographic images are compared and correlated with mechanical test results—bearing test and delamination onset test—and analytical models. The results demonstrate the importance of an adequate selection of drilling tools and machining parameters to extend the life cycle of these laminates as a consequence of enhanced reliability.