APPLICATION OF FACTOR-ANALYSIS TO CORRECTION OF SPECTRAL OVERLAP INTERFERENCE IN INDUCTIVELY COUPLED PLASMA ATOMIC EMISSION-SPECTROMETRY

Correction of spectral overlap interference in inductively coupled plasma atomic emission spectrometry by factor analysis is attempted. For the spectral overlap of two known lines, a data matrix can be composed from one or two pure spectra and a spectrum of the mixture. The data matrix is decomposed into a spectra matrix and a concentration matrix by target transformation factor analysis. The component concentration of interest in a binary mixture is obtained from the concentration matrix and interference from the other component is eliminated. This method is applied to correcting spectral interference of yttrium on the determination of copper and aluminium: satisfactory results are obtained. This method may also be applied to correcting spectral overlap interference for more than two lines. Like other methods of correcting spectral interferences, factor analysis can only be used for additive spectral overlap. Results obtained from measurements on copper/yttrium mixtures with different white noise added show that random errors in measurement data do not significantly affect the results of the correction method.

EVALUATION OF THE RELIABILITY OF KALMAN FILTERING RESULTS IN INDUCTIVELY COUPLED PLASMA ATOMIC EMISSION-SPECTROMETRY

This paper deals with the evaluation of the reliability of the analytical results obtained by Kalman filtering. Two criteria for evaluation were compared: one is based on the autocorrelation analysis of the innovation sequence, the so-called NAC criterion; the other is the innovations number, which actually is the autocorrelation coefficient of the innovation sequence at the initial wavelength. Both criteria allow compensation for the wavelength positioning errors in spectral scans, but there exists a difference in the way they work. The NAC criterion can provide information about the reliability of an individual result, which is very useful for the indication of unmodelled emissions, while the innovations number should be incorporated with the normalization of the innovations or seek the help of the sequence itself for the same purpose. The major limitation of the NAC criterion is that it does not allow the theoretical modelling of continuous backgrounds, which, however, is convenient in practical analysis and can be taken with the innovations number criterion.

EVALUATION OF THE EFFECT OF WAVELENGTH POSITIONING ERRORS ON KALMAN FILTERING RESULTS IN INDUCTIVELY COUPLED PLASMA ATOMIC EMISSION-SPECTROMETRY

This work evaluates the effect of wavelength positioning errors in spectral scans on analytical results when the Kalman filtering technique is used for the correction of line interferences in inductively coupled plasma atomic emission spectrometry (ICP-AES). The results show that a positioning accuracy of 0.1 pm is required in order to obtain accurate and precise estimates for analyte concentrations. The positioning error in sample scans is more crucial than that in model scans. The relative bias in measured analyte concentration originating from a positioning error in a sample scan increases linearly with an increase in the magnitude of the error and the peak distance of the overlapping lines, but is inversely proportional to the signal-to-background ratio. By the use of an optimization procedure for the positions of scans with the innovations number as the criterion, the wavelength positioning error can be reduced and, correspondingly, the accuracy and precision of analytical results improved.

High resolution time-of-flight spectrometer for crossed molecular beam study of elementary chemical reactions

In this article, we describe an apparatus in our laboratory for investigating elementary chemical reactions using the high resolution time-of-flight Rydberg tagging method. In this apparatus, we have adopted a rotating source design so that collision energy can be changed for crossed beam studies of chemical reactions. Preliminary results on the HI photodissociation and the F atom reaction with H-2 are reported here. These results suggest that the experimental apparatus is potentially a powerful tool for investigating state-to-state dynamics of elementary chemical reactions. (c) 2005 American Institute of Physics.

Interface of chip-based capillary electrophoresis-inductively coupled plasma-atomic emission spectrometry (CE-ICP-AES)

An interface of chip-based capillary electrophoresis (CE)-inductively coupled plasma-atomic emission spectrometry (ICP-AES) that is based on cross-flow nebulization has been developed. A polydimethylsiloxane (PDMS) CE-chip with conventional cross channel layout was used. A stainless steel tube was placed orthogonal to the exit of the CE separation channel for cross flow nebulization. A supplementary flow of buffer solution at the channel exit was used to improve nebulization efficiency. Two capillaries were inserted into the CE chip near the inlet of the separation channel for sample and buffer solution injection. Syringe pumps were used to manipulate the flow rate and flow direction of the sample, buffer, and supplementary buffer solution. Peak broadening due to the shape (bulb and tube-shaped) and size of the spray chambers was studied. The smaller tube-shaped spray chamber was used because of smaller peak broadening effect due to aerosol transport. The nebulization and transport efficiency of the CE-ICP interface was approximately 10%. Ba2+ and Mg2+ ions were eluted from the CE-chip within 30 s. Resolution of the Ba2+ and Mg2+ peaks was 0.7 using the chip-based CE-ICP-AES system.

A high resolution study of the chlorophyll and bacteriochlorophyll pigment distributions in a calcite/gypsum microbial mat

Application of a high resolution high performance liquid chromatography-mass spectrometry method to the study of a microbial mat system has permitted the identification of a greater number of pigments derived from green bacteria than reported in a previous study. Although the green bacteria found in the mat were identified as Chloroflexus-like, bacteriochlorophylls and bacteriophaeophytins c that can be attributed to Chloroflexaceae on the basis of literature reports account for less than 10% of the pigments derived from green bacteria in the mat. Analysis of the bacteriochlorophylls and bacteriophaeophytins c and d using atmospheric pressure chemical ionisation-liquid chromatography-tandem mass spectrometry reveals complex depth profiles, signalling inputs from a number of organisms. The pigment compositions provide evidence for green bacteria living in close proximity to the living cyanobacterial mat. Depth profiles of pigments derived from green, purple and cyanobacteria indicate that the remnants of mats present in the deeper part of the section contain a record dominated by signatures from anoxygenic photoautotrophs.

High-resolution spectroscopy of globular cluster post-Asymptotic Giant Branch stars

We present model atmosphere analyses of high resolution Keck and VLT optical spectra for three evolved stars in globular clusters, viz. ZNG-1 in M 10, ZNG-1 in M 15 and ZNG-1 in NGC 6712. The derived atmospheric parameters and chemical compositions confirm the programme stars to be in the post- Asymptotic Giant Branch (post-AGB) evolutionary phase. Differential abundance analyses reveal CNO abundance patterns in M 10 ZNG-1, and possibly M 15 ZNG-1, which Suggest that both objects may have evolved off the AGB before the third dredge-up occurred. The abundance pattern of these stars is similar to the third class of optically, bright post-AGB objects discussed by van Winckel (1997). Furthermore, M 10 ZNG-1 exhibits a large C underabundance (with Delta[C/O] similar to -1.6 dex), typical of other hot post-AGB objects. Differential Delta[alpha/Fe] abundance ratios in both M 10 ZNG-1 and NGC 6712 ZNG-1 are found to be approximately 0.0 dex, with the Fe abundance of the former being in disagreement with the cluster metallicity of M 10. Given that the Fe absorption features in both M 10 ZNG-1 and NGC6712 ZNG-1 are well observed and reliably modelled, we believe that these differential Fe abundance estimates to be secure. However, our Fe abundance is difficult to explain in terms of previous evolutionary processes that Occur oil both the Horizontal Branch and the AGB.

Multi-epoch high-resolution spectroscopy of SN2011fe - Linking the progenitor to its environment

This study attempts to establish a link between the reasonably well known nature of the progenitor of SN2011fe and its surrounding environment. This is done with the aim of enabling the identification of similar systems in the vast majority of the cases, when distance and epoch of discovery do not allow a direct approach. To study the circumstellar environment of SN2011fe we have obtained high-resolution spectroscopy of SN2011fe on 12 epochs, from 8 to 86 days after the estimated date of explosion, targeting in particular at the time evolution of CaII and NaI. Three main absorption systems are identified from CaII and NaI, one associated to the Milky Way, one probably arising within a high-velocity cloud, and one most likely associated to the halo of M101. The Galactic and host galaxy reddening, deduced from the integrated equivalent widths (EW) of the NaI lines are E(B-V)=0.011+/-0.002 and E(B-V)=0.014+/-0.002 mag, respectively. The host galaxy absorption is dominated by a component detected at the same velocity measured from the 21-cm HI line at the projected SN position (~180 km/s). During the ~3 months covered by our observations, its EW changed by 15.6+/-6.5 mA. This small variation is shown to be compatible with the geometric effects produced by therapid SN photosphere expansion coupled to the patchy fractal structure of the ISM. The observed behavior is fully consistent with ISM properties similar to those derived for our own Galaxy, with evidences for structures on scales

In situ, high-resolution imaging of labile phosphorus in sediments of a large eutrophic lake

Understanding the labile status of phosphorus (P) in sediments is crucial for managing a eutrophic lake, but it is hindered by lacking in situ data particularly on a catchment scale. In this study, we for the first time characterized in situ labile P in sediments with the Zr-oxide diffusive gradients in thin films (Zr-oxide DGT) technique at a two-dimensional (2D), submillimeter resolution in a large eutrophic lake (Lake Taihu, China, with an area of 2338km²). The concentration of DGT-labile P in the sediment profiles showed strong variation mostly ranging from 0.01 to 0.35mgL^-1 with a considerable number of hotspots. The horizontal heterogeneity index of labile P varied from 0.04 to 4.5. High values appeared at the depths of 0-30mm, likely reflecting an active layer of labile P under the sediment-water interface (SWI). Concentration gradients of labile P were observed from the high-resolution 1D DGT profiles in both the sediment and overlying water layers close to the SWI. The apparent diffusion flux of P across the SWI was calculated between -21 and 65ngcm^-2d^-1, which showed that the sediments tended to be a source and sink of overlying water P in the algal- and macrophyte-dominated regions, respectively. The DGT-labile P in the 0-30mm active layer showed a better correlation with overlying water P than the labile P measured by ex situ chemical extraction methods. It implies that in situ, high-resolution profiling of labile P with DGT is a more reliable approach and will significantly extend our ability in in situ monitoring of the labile status of P in sediments in the field.

High-resolution photoionization of Xe + ions: Experiment and theory

High-resolution photoionization measurements of Xe + ions have been performed at the Advanced Light Source in Berkeley, California, USA. The experimental cross sections are compared with results from Dirac-Coulomb R-matrix calculations.

High-resolution seismic reflection investigation of gas accumulation and seepage in the tidal channels of the Ria of Aveiro barrier lagoon (Portugal)

O metano é um gás de estufa potente e uma importante fonte de energia. A importância global e impacto em zonas costeiras de acumulações e escape de gás metano são ainda pouco conhecidas. Esta tese investiga acumulações e escape de gás em canais de maré da Ria de Aveiro com dados de cinco campanhas de reflexão sísmica de alta resolução realizadas em 1986, 1999, 2002 e 2003. Estas incluem três campanhas de Chirp (RIAV99, RIAV02 e RIAV02A) e duas campanhas de Boomer (VOUGA86 e RIAV03). O processamento dos dados de navegação incluíram filtros de erros, correcções de sincronização de relógios de sistemas de aquisição de dados, ajuste de “layback” e estimativa da posição de “midpoint”. O processamento do sinal sísmico consistiu na correcção das amplitudes, remoção de ruído do tipo “burst”, correcções estáticas, correcção do “normal move-out”, filtragem passabanda, desconvolução da assinatura e migração Stolt F-K. A análise da regularidade do trajecto de navegação, dos desfasamentos entre horizontes e dos modelos de superfícies foi utilizada para controlo de qualidade, e permitiu a revisão e melhoria dos parâmetros de processamento. A heterogeneidade da cobertura sísmica, da qualidade do sinal, da penetração e da resolução, no seu conjunto constrangeram o uso dos dados a interpretações detalhadas, mas locais, de objectos geológicos da Ria. É apresentado um procedimento para determinar a escolha de escalas adequadas para modelar os objectos geológicos, baseado na resolução sísmica, erros de posicionamento conhecidos e desfasamentos médios entre horizontes. As evidências de acumulação e escape de gás na Ria de Aveiro incluem turbidez acústica, reflexões reforçadas, cortinas acústicas, domas, “pockmarks” e alinhamentos de “pockmarks” enterradas, horizontes perturbados e plumas acústicas na coluna de água (flares). A estratigrafia e a estrutura geológica controlam a distribuição e extensão das acumulações e escape de gás. Ainda assim, nestes sistemas de baixa profundidade de água, as variações da altura de maré têm um impacto significativo na detecção de gás com métodos acústicos, através de alterações nas amplitudes originais de reflexões reforçadas, turbidez acústica e branqueamento acústico em zonas com gás. Os padrões encontrados confirmam que o escape de bolhas de gás é desencadeado pela descida da maré. Há acumulações de gás em sedimentos Holocénicos e no substrato de argilas e calcários do Mesozóico. Evidências directas de escape de gás em sondagens em zonas vizinhas, mostraram gás essencialmente biogénico. A maioria do gás na área deve ter sido gerado em sedimentos lagunares Holocénicos. No entanto, a localização e geometria de estruturas de escape de fluidos em alguns canais de maré, seguem o padrão de fracturas do substrato Mesozóico, indicando uma possível fonte mais profunda de gás e que estas fracturas funcionam como condutas preferenciais de migração dos fluidos e exercem um controlo estrutural na ocorrência de gás na Ria.

Assessment of nutritional and metabolic profiles of pea shoots: The new ready-to-eat baby-leaf vegetable

Pea-shoots are a new option as ready-to-eat baby-leaf vegetable. However, data about the nutritional composition and the shelf-life stability of these leaves, especially their phytonutrient composition is scarce. In this work, the macronutrient, micronutrient and phytonutrients profile of minimally processed pea shoots were evaluated at the beginning and at the end of a 10-day storage period. Several physicochemical characteristics (color, pH, total soluble solids, and total titratable acidity) were also monitored. Standard AOAC methods were applied in the nutritional value evaluation, while chromatographic methods with UV–vis and mass detection were used to analyze free forms of vitamins (HPLC-DAD-ESI-MS/MS), carotenoids (HPLC-DAD-APCI-MSn) and flavonoid compounds (HPLC-DAD-ESI-MSn). Atomic absorption spectrometry (HR-CS-AAS) was employed to characterize the mineral content of the leaves. As expected, pea leaves had a high water (91.5%) and low fat (0.3%) and carbohydrate (1.9%) contents, being a good source of dietary fiber (2.1%). Pea shoots showed a high content of vitamins C, E and A, potassium and phosphorous compared to other ready-to-eat green leafy vegetables. The carotenoid profile revealed a high content of β-carotene and lutein, typical from green leafy vegetables. The leaves had a mean flavonoid content of 329 mg/100 g of fresh product, mainly composed by glycosylated quercetin and kaempferol derivatives. Pea shoots kept their fresh appearance during the storage being color maintained throughout the shelf-life. The nutritional composition was in general stable during storage, showing some significant (p < 0.05) variation in certain water-soluble vitamins.

Teor mineral e capacidade antioxidante em chás e infusões

Mestrado em Engenharia Química – Ramo Optimização Energética na Indústria Química

Effet du calcium, plomb et cuivre sur la bioaccumulation du cadmium et la production des phytochélatines par Chlamydomonas reinhardtii

Dans les milieux contaminés par les métaux, les organismes vivants sont exposés à plusieurs d’entre eux en même temps. Les modèles courants de prédiction des effets biologiques des métaux sur les organismes (p. ex., modèle du ligand biotique, BLM ; modèle de l’ion libre, FIAM), sont des modèles d’équilibre chimique qui prévoient, en présence d'un deuxième métal, une diminution de la bioaccumulation du métal d’intérêt et par la suite une atténuation de ses effets. Les biomarqueurs de toxicité, tels que les phytochélatines (PCs), ont été utilisés comme étant un moyen alternatif pour l’évaluation des effets biologiques. Les phytochélatines sont des polypeptides riches en cystéine dont la structure générale est (γ-glu-cys)n-Gly où n varie de 2 à 11. Leur synthèse semble dépendante de la concentration des ions métalliques ainsi que de la durée de l’ exposition de l’organisme, aux métaux. L'objectif de cette étude était donc de déterminer, dans les mélanges binaires de métaux, la possibilité de prédiction de la synthèse des phytochélatines par les modèles d’équilibres chimiques, tel que le BLM. Pour cela, la quantité de phytochélatines produites en réponse d’une exposition aux mélanges binaires : Cd-Ca, Cd-Cu et Cd-Pb a été mesurée tout en surveillant l’effet direct de la compétition par le biais des concentrations de métaux internalisés. En effet, après six heures d’exposition, la bioaccumulation de Cd diminue en présence du Ca et de très fortes concentrations de Pb et de Cu (de l’ordre de 5×10-6 M). Par contre, avec des concentrations modérées de ces deux métaux, le Cd augmente en présence de Cu et ne semble pas affecté par la présence de Pb. Dans le cas de la compétition Cd-Cu, une bonne corrélation a été observée entre la production de PC2, PC3 et PC4 et la quantité des métaux bioaccumulés. Pour la synthèse des phytochélatines et la bioaccumulation, les effets étaient considérés comme synergiques. Dans le cas du Cd-Ca, les quantités de PC3 et PC4 ont diminué avec le métal internalisé (effet antagoniste), mais ce qui était remarquable était la grande quantité de cystéine (GSH) et PC2 qui ont été produites à de fortes concentrations du Ca. Le Pb seul n’a pas induit les PCs. Par conséquent, il n’y avait pas de variation de la quantité de PCs avec la concentration de Pb à laquelle les algues ont été exposées. La détection et la quantification des PCs ont été faites par chromatographie à haute performance couplée d’un détecteur de fluorescence (HPLC-FL). Tandis que les concentrations métalliques intracellulaires ont été analysées par spectroscopie d’absorption atomique (AAS) ou par spectrométrie de masse à source plasma à couplage inductif (ICP-MS).