电厂燃煤中主要有害元素的种类、迁移及潜在环境影响

Distributions of elements especially hazard trace elements in coals and their wastes from a coal fired power plant have been studied in detail using knowledge of Geology, Mineralogy, Geochemistry and Environmental chemistry. The key work is on the small particle sizes of fly ashes which escaped from electric precipitator and discharged into atmosphere. By means of X-ray powder diffraction (XRD) and scanning electron microscopy with energy-dispersive spectrometer (SEM-EDS), the characteristics of minerals and morphologies were studied. Different types of fly ash were formed in different stages and processes. More than 50% of small fly ashes belonged to inhalable particles (PM10). The very fine fly ashes preferred to attach on surface of bigger fly ash or conglutinate with each other and this decreased the environmental impact of tiny fly ashes. The trace elements in coal, fly ashes, slags and small particle sizes of fly ashes had been analysed by means of Neutron Activation Analysis (INAA), inductively coupled plasma mass spectrometry (ICP-MS), inductively coupled plasma atomic emission spectrometry (ICP-AES). As particle sizes decreasing, distributions of most elements increased, but in contrary to most studies, this increasing trend was not very obviously because of the tendency of attachment of tiny fly ashes. The occurrence of 30 elements including hazard trace elements of Cd, Cr, Ni, Co, Pb, Zn, As, Se, Cu, V was studied by means of sequential chemical extract. The annual discharge of hazard trace elements of slag, fly ash, small fly ash (PM10), tiny fly ash (PM2.5) and air was calculated by mass balance. S, V, Cu, Pb, Se, Mo, Cd from power plant had potential impacts on environment. Hazard trace elements from the power plant had little effect on soil and aerosol comparing to those from other industrial sources and the effects were mostly on downwind direction. Both the high performance electric precipitator and high chimney made the hazard trace elements from power plant being transported far away but little environmental impacts.

Toenail trace element status and risk of Barrett's oesophagus and oesophageal adenocarcinoma. Results from the FINBAR study

Trace elements have been cited as both inhibitory and causative agents of cancer but importantly exposure to them is potentially modifiable. Our study aimed to examine toenail trace element status and risk of Barrett's oesophagus (BO) and oesophageal adenocarcinoma (OAC). Toenail clippings from each hallux were obtained from 638 participants of the FINBAR (Factors Influencing the Barrett's Adenocarcinoma Relationship) study comprising 221 healthy controls, 98 reflux oesophagitis, 182 BO and 137 OAC cases. The concentrations of eight toenail trace elements were determined using instrumental neutron activation analysis. Using multivariable adjusted logistic regression analysis, odds ratios (OR) and 95% confidence intervals (CIs) were calculated within tertiles of trace element concentrations. A twofold increased risk of BO was observed, but not OAC, among individuals in the highest tertile of toenail zinc status OR 2.21 (95% CI, 1.11-4.40). A higher toenail selenium status was not associated with risk of OAC OR 0.94 (95% CI, 0.44-2.04) or BO OR 0.89 (95% CI, 0.37-2.12). A borderline significant increased risk of BO was detected with a higher toenail cobalt concentration, OR 1.97 (95% CI, 1.01-3.85). No association was found between toenail levels of chromium, cerium, mercury and OAC or BO risk. This is the first case-control study to investigate a variety of trace elements in relation to OAC and BO risk. Despite antioxidant and proapoptotic properties, no associations were found with selenium. Higher concentrations of toenail zinc and cobalt were associated with an increased BO risk, but not OAC. These findings need confirmation in prospective analysis.

Characterisation of gas and particle emissions from wildfires

Os incêndios florestais são uma importante fonte de emissão de compostos gasosos e de aerossóis. Em Portugal, onde a maioria dos incêndios ocorre no norte e centro do país, os incêndios destroem todos os anos milhares de hectares, com importantes perdas em termos económicos, de vidas humanas e qualidade ambiental. As emissões podem alterar consideravelmente a química da atmosfera, degradar a qualidade do ar e alterar o clima. Contudo, a informação sobre as caraterísticas das emissões dos incêndios florestais nos países do Mediterrâneo é limitada. Tanto a nível nacional como internacional, existe um interesse crescente na elaboração de inventários de emissões e de regulamentos sobre as emissões de carbono para a atmosfera. Do ponto de vista atmosférico da monitorização atmosférica, os incêndios são considerados um desafio, dada a sua variabilidade temporal e espacial, sendo de esperar um aumento da sua frequência, dimensão e severidade, e também porque as estimativas de emissões dependem das caraterísticas dos biocombustíveis e da fase de combustão. O objetivo deste estudo foi quantificar e caraterizar as emissões de gases e aerossóis de alguns dos mais representativos incêndios florestais que ocorreram no centro de Portugal nos verões de 2009 e de 2010. Efetuou-se a colheita de amostras de gases e de duas frações de partículas (PM2.5 e PM2.5-10) nas plumas de fumo em sacos Tedlar e em filtros de quartzo acoplados a um amostrador de elevado volume, respetivamente. Os hidrocarbonetos totais (THC) e óxidos de carbono (CO e CO2) nas amostras gasosas foram analisados em instrumentos automáticos de ionização de chama e detetores não dispersivos de infravermelhos, respetivamente. Para algumas amostras, foram também quantificados alguns compostos de carbonilo após reamostragem do gás dos sacos Tedlar em cartuchos de sílica gel revestidos com 2,4-dinitrofenilhidrazina (DNPH), seguida de análise por cromatografia líquida de alta resolução. Nas partículas, analisou-se o carbono orgânico e elementar (técnica termo-óptica), iões solúveis em água (cromatografia iónica) e elementos (espectrometria de massa com plasma acoplado por indução ou análise instrumental por ativação com neutrões). A especiação orgânica foi obtida por cromatografia gasosa acoplada a espectrometria de massa após extração com recurso a vários solventes e separação dos extratos orgânicos em diversas classes de diferentes polaridades através do fracionamento com sílica gel. Os fatores de emissão do CO e do CO2 situaram-se nas gamas 52-482 e 822-1690 g kg-1 (base seca), mostrando, respetivamente, correlação negativa e positiva com a eficiência de combustão. Os fatores de emissão dos THC apresentaram valores mais elevados durante a fase de combustão latente sem chama, oscilando entre 0.33 e 334 g kg-1 (base seca). O composto orgânico volátil oxigenado mais abundante foi o acetaldeído com fatores de emissão que variaram desde 1.0 até 3.2 g kg-1 (base seca), seguido pelo formaldeído e o propionaldeído. Observou-se que as emissões destes compostos são promovidas durante a fase de combustão latente sem chama. Os fatores de emissão de PM2.5 e PM10 registaram valores entre 0.50-68 e 0.86-72 g kg-1 (base seca), respetivamente. A emissão de partículas finas e grosseiras é também promovida em condições de combustão lenta. As PM2.5 representaram cerca de 90% da massa de partículas PM10. A fração carbonosa das partículas amostradas em qualquer dos incêndios foi claramente dominada pelo carbono orgânico. Foi obtida uma ampla gama de rácios entre o carbono orgânico e o carbono elementar, dependendo das condições de combustão. Contudo, todos os rácios refletiram uma maior proporção de carbono orgânico em relação ao carbono elementar, típica das emissões de queima de biomassa. Os iões solúveis em água obtidos nas partículas da pluma de fumo contribuíram com valores até 3.9% da massa de partículas PM2.5 e 2.8% da massa de partículas de PM2.5-10. O potássio contribuiu com valores até 15 g mg-1 PM2.5 e 22 g mg-1 PM2.5-10, embora em massa absoluta estivesse maioritariamente presente nas partículas finas. Os rácios entre potássio e carbono elementar e entre potássio e carbono orgânico obtidos nas partículas da pluma de fumo enquadram-se na gama de valores relatados na literatura para emissões de queima de biomassa. Os elementos detetados nas amostras representaram, em média, valores até 1.2% e 12% da massa de PM2.5 e PM2.5-10, respetivamente. Partículas resultantes de uma combustão mais completa (valores elevados de CO2 e baixos de CO) foram caraterizadas por um elevado teor de constituintes inorgânicos e um menor conteúdo de matéria orgânica. Observou-se que a matéria orgânica particulada é composta principalmente por componentes fenólicos e produtos derivados, séries de compostos homólogos (alcanos, alcenos, ácidos alcanóicos e alcanóis), açúcares, biomarcadores esteróides e terpenóides, e hidrocarbonetos aromáticos policíclicos. O reteno, um biomarcador das emissões da queima de coníferas, foi o hidrocarboneto aromático dominante nas amostras das plumas de fumo amostradas durante a campanha que decorreu em 2009, devido ao predomínio de amostras colhidas em incêndios em florestas de pinheiros. O principal açúcar anidro, e sempre um dos compostos mais abundantes, foi o levoglucosano. O rácio levoglucosano/OC obtido nas partículas das plumas de fumo, em média, registaram valores desde 5.8 a 23 mg g-1 OC. Os rácios levoglucosano/manosano e levoglucosano/(manosano+galactosano) revelaram o predomínio de amostras provenientes da queima de coníferas. Tendo em conta que a estimativa das emissões dos incêndios florestais requer um conhecimento de fatores de emissão apropriados para cada biocombustível, a base de dados abrangente obtida neste estudo é potencialmente útil para atualizar os inventários de emissões. Tem vindo a ser observado que a fase de combustão latente sem chama, a qual pode ocorrer simultaneamente com a fase de chama e durar várias horas ou dias, pode contribuir para uma quantidade considerável de poluentes atmosféricos, pelo que os fatores de emissão correspondentes devem ser considerados no cálculo das emissões globais de incêndios florestais. Devido à falta de informação detalhada sobre perfis químicos de emissão, a base de dados obtida neste estudo pode também ser útil para a aplicação de modelos no recetor no sul da Europa.

Theoretical and Experimental Foundations for the Greystar Project. Or application of NAA for remote detection

Dans un monde de détection et prospection minière, une multitude de techniques existent. Une des techniques les plus puissantes est l’activation par neutrons (NAA et PGAA). Toutefois, dans le cadre de la prospection minière, l’utilisation de cette technique nécessite du forage. La motivation du projet GREYSTAR est de permettre l’analyse élémentaire par activation en limitant l’impact environnemental. Les facteurs limitant sont l’activation d’un volume distant et la détection de la radiation émise par ce volume. Ce mémoire examine l’activation par neutrons thermiques et la détection de gammas provenant de la désexcitation des noyaux activés. Une approche expérimentale est présentée avec des simulations pour venir appuyer les données expérimentales. Il en résulte que le projet GREYSTAR tel que décrit dans ce mémoire est prometteur et que davantage de recherche est à prescrire. Les résultats initiaux indiquent que selon le prototype proposé, les limites de détections sont de l’ordre de 2-3 m dans un matériel semblable au granite. On conclut que d’un point de vue de prospection minière, il est intéressant de poursuivre la recherche. De plus, plusieurs autres applications dans les domaines militaire, civil et policier sont prometteuses.

Correlations between chemical composition and provenance of Justino site ceramics by INAA

Instrumental neutron activation analysis (INAA), have been used for the definition of compositional groups of potteries from Justino site, Brazil, according to the chemical similarities of ceramic paste. The outliers were identified by means of robust Mahalanobis distance. The temper effect in the ceramic paste was studied by means of modified Mahalanobis filter. The results were interpreted by means of cluster, principal components, and discriminant analyses. This work provides contributions for the reconstruction of the prehistory of baixo Sao Francisco region, and for the reconstitution of the Brazilian Northeast ceramist population of general frame.

Iron oxide nanoparticles and VO(x)/Hexadecylamine nanotubes composite

In this work, we present the synthesis and characterization of a hybrid nanocomposite constituted by iron oxide nanoparticles and vanadium oxide/Hexadecylamine (VO(x)/Hexa) nanotubes. Transmission Electron Microscopy (TEM) images show small particles (around 20 nm) in contact with the external wall of the multiwall tubes, which consist of alternate layers of VO(x) and Hexa. By Energy Dispersive Spectroscopy (EDS), we detected iron ions within the tube walls and we have also established that the nanoparticles are composed of segregated iron oxide. The samples were studied by Electron Paramagnetic Resonances (EPR) and dc-magnetization as a function of the magnetic field. The analysis of the magnetization and EPR data confirms that a fraction of the V atoms are in the V(4+) electronic state and that the nanoparticles exhibit a superparamagnetic behavior. The percentage of V and Fe present in the nanocomposite was determined using Instrumental Neutron Activation Analysis (INAA). (C) 2008 Elsevier B.V. All rights reserved.

Trace element impurity determination in aspirin tablets by INAA

Instrumental neutron activation analysis (INAA) was applied to assess trace element concentrations in six samples of aspirin tablets acquired in SA o pound Paulo city, Brazil. Concentrations of the elements Br, Ca, Co, Cr, Fe, K, La, Na, Sc and Zn were determined. Comparisons were made between the results obtained with published data for aspirins from foreign countries. Certified reference materials, INCT-MPH-2 Mixed Polish Herbs were analyzed for quality control of the analytical results.

Determination of potassium and sodium in an ash sample by gamma-ray spectroscopy

Neutron activation analysis and gamma-ray spectroscopy were used to determine the quantity of potassium and sodium in an ash sample of Tabebuia sp bombarded with thermal neutrons. These techniques, widely applied in nuclear physics, can be used in the context of wood science as an alternative for the usual physical chemistry methods applied in this area. The quantity of K and Na in an 8.60 +/- 0.10 mg of ash was determined as being 1.3 +/- 0.3 mg and 11.0 +/- 1.8 mu g, respectively. The ratio of Tabebuia sp converted into ash was also determined as 0.758 +/- 0.004%.

Quantitative estimation of Br, Cl, K and Na in sample blood by NAA

Neutron activation analysis, using Au as flux monitor, was applied to determine the concentrations of Br, Cl, K and Na in blood of healthy male and female blood donors, selected from blood banks and hematological laboratories from different regions of Brazil. The aims of this study were to collect more reference values of the Brazilian population as well as to perform hematological investigations. The advantages as well as the limitations of using this nuclear procedure are discussed.

TL, OSL and C-14 dating results of the sediments and bricks from mummified nuns' grave

Este artigo apresenta os resultados de datação por TL e OSL de solos, e fragmentos de tijolos de um túmulo, que foi ocupado por duas freiras mumificadas encontradas no Mosteiro da Luz, localizado no Estado de São Paulo, Brasil. As idades encontradas por TL e OSL foram comparadas às obtidas a partir de C-14 dos colágenos contidos em amostras de osso das múmias. A maioria das idades obtidas são do século XVIII. A espectroscopia de radiação-gama foi utilizada para avaliar concentrações de radioisótopos naturais nas amostras e para calcular as taxas de dose anual que resultaram em 3,0 a 5,3 Gy/kano. As concentrações radioativas são próximas daquelas obtidas através de Análise por Ativação de Nêutrons. Os conteúdos de elementos U, Th e Ce são superiores aos encontrados na maioria dos sedimentos.

Uranium incorporation biokinetics in poultry bones as function of phytase doses

Neutron activation analysis has been used to study uranium incorporation in poultry bones as function of chow doped with : (a) uranium (20 ppm); (b) U-doped food (20 ppm) plus phytase (120 ppm) and (c) U-doped food (20 ppm) plus phytase (180 ppm). To investigate this situation experiments involving several groups of Cobb broilers was performed. Two animals per group were sacrificed weekly up to their adultness and uranium concentration in the tibia was measured. It was observed that the concentration of uranium (mug U/g bone) is decreasing all along the animal life spanning period of 14-42 days. This behavior suggests that the skeleton mass is growing faster than the corresponding accumulation of uranium. The administration of phytase seems not to alter this scenario.

Long-term accumulation of uranium in bones of Wistar rats as a function of intake dosages

Groups of Wistar rats were fed with ration doped with uranyl nitrate at concentration A ranging from 0.5 to 100 ppm, starting after the weaning period and lasting until the postpuberty period when the animals were sacrificed. Uranium in the ashes of bones was determined by neutron activation analysis. It was found that the uranium concentration in the bones. as a function of A, exhibits a change in its slope at similar to20 ppm-a probable consequence of the malfunctioning of kidneys. The uranium transfer coefficient was obtained and an analytical expression was fitted into the data. thus allowing extrapolation down to low doses. Internal and localized doses were calculated. Absorbed doses exceeded the critical dose. even for the lowest uranium dosage.

Uranium metabolism associated with ontogenetic growth of birds: case studies with broilers and ducks

Cobb broilers and domestic ducks, both one-day-old, were treated using ration doped with 20 ppm of uranyl nitrate. Uranium concentrations in the tibia (μg-U/g-bone) were measured by neutron activation analysis as function of the animals’ age, from the neonatal period to maturity. Results show that Uranium and Calcium qualitatively follow the same metabolic pathway, and that adult ducks incorporate on average ten times more Uranium than broilers. Data interpretation shows that the Uranium clearance rate in broilers is substantially higher than that in ducks, suggesting that metabolic characteristics favoring Calcium retention in bone may hinder the elimination of Uranium in ducks. The need for further comparative biochemistry studies between Galliformes and Anseriformes is addressed.

Use of Cathorops spixii as bioindicator of pollution of trace metals in the Santos Bay, Brazil

In the present study Cathorops spixii, was evaluated as a bioindicator fish for trace metal pollution. Concentrations of cobalt (Co), iron (Fe), selenium (Se) and zinc (Zn) were determined by Instrumental Neutron Activation Analysis in liver. Mercury (Hg) and methyl-mercury (MeHg) were analyzed by Cold Vapor Atomic Absorption Spectrometry in muscles and livers. High concentrations of Co, Fe, Se and Zn were observed in C. spixii from Santos Bay in comparison to fish collected in a non-polluted site in the same Brazilian coast. These trace metal concentrations were out of the permissible levels for human consumption. Although, Hg and MeHg levels were low, the C. spixii could still be used as an effective bioindicator to observe trace metal behaviors in the environment in function of the bioaccumulation process observed mainly by other analyzed trace metals. Thus, the use of this species is strongly recommended to monitor the effects and behavior of trace metal pollution in aquatic ecosystems in Brazil due to its bioaccumulation function.

Arsenic and trace metal contents in sediment profiles from the Admiralty Bay, King George Island, Antarctica

Admiralty Bay (Antarctica) hosts three scientific stations (Ferraz, Arctowski and Macchu Picchu), which require the use of fossil fuel as an energy source. Fossil fuels are also considered the main source of pollution in the area, representing important inputs of major pollutants (organic compounds) and trace metals and metalloids of environmental interest. Accordingly, this work presents the results of As, Cd, Cr, Cu, Ni, Pb and Zn in sediment profiles from Admiralty Bay. The sediment results from Ferraz station were slightly higher than the other sampling sites. The highest contents were observed for Cu and Zn (from 44 to 89 mg kg(-1)). Otherwise, by using enrichment factors and geochronology analysis, the most relevant enrichment was observed for As in the samples collected close to the Ferraz station, indicating that increasing As content may be associated with the activities associated with this site. Published by Elsevier Ltd.