Simultaneous flow injection preconcentration of lead and cadmium using cloud point extraction and determination by atomic absorption spectrometry

A flow injection (FI) micelle-mediated separation/preconcentration procedure for the determination of lead and cadmium by flame atomic absorption spectrometry (FAAS) has been proposed. The analytes reacted with 1-(2-thiazolylazo)-2-naphthol (TAN) to form hydrophobic chelates, which were extracted into the micelles of 0.05% (w/v) Triton X-114 in a solution buffered at pH 8.4. In the preconcentration stage, the micellar solution was continuously injected into a flow system with four mini-columns packed with cotton, glass wool. or TNT compresses for phase separation. The analytes-containing micelles were eluted from the mini-columns by a stream of 3 mol L(-1) HCl solution and the analytes were determined by FAAS. Chemical and flow variables affecting the preconcentration of the analytes were studied. For 15 mL. of preconcentrated solution, the enhancement factors varied between 15.1 and 20.3, the limits of detection were approximately 4.5 and 0.75 mu g L(-1) for lead and cadmium, respectively. For a solution containing 100 and 10 mu g L(-1) of lead and cadmium, respectively, the R.S.D. values varied from 1.6 to 3.2% (n = 7). The accuracy of the preconcentration system was evaluated by recovery measurements on spiked water samples. The method was susceptible to matrix effects, but these interferences were minimized by adding barium ions as masking agent in the sample solutions, and recoveries from spiked sample varied in the range of 95.1-107.3%. (C) 2008 Elsevier B.V. All rights reserved.

Indoors lead corrosion: Reassessing the role of formaldehyde

The present work is focused on the role of formaldehyde in indoors Pb corrosion, that is still a controversial issue. Pb coupons were exposed to the atmosphere produced by formaldehyde aqueous solutions (1% and 4% in volume) and corrosion was followed by Raman Microscopy. The compounds formed in both experiments were the same, but were not in agreement with previously reported results in the literature, that identified plumbonacrite, hidrocerussite and Pb oxide. The experiments here reported have clearly shown that formates are produced on Pb surfaces exposed to formaldehyde and that oxidants, such as H(2)O(2), are not necessary. Formaldehyde oxidation also occurs with powdered PbO in a controlled environment. The Raman spectra of the Pb formates are much more complex than the Pb(HCO(2))(2) spectrum and change when exposed to room conditions, by a slow reaction with CO(2), forming Pb carbonates (hidrocerussite and plumbonacrite mostly) and Pb(HCO(2))(2). Such spectral change may be responsible for the differences in terms of chemical composition of the corrosion layer when the data here reported is compared with the literature. Other factors that must be considered are the storage conditions (particularly relative humidity and CO(2) concentration) and time; the effect of metal composition cannot be discarded as it is well known that the presence of other metals can change significantly the Pb resistance to oxidation. (C) 2010 Elsevier B.V. All rights reserved.

Exploring the emission intensities of ICP OES aided by chemometrics in the geographical discrimination of mineral waters

A rapid method for classification of mineral waters is proposed. The discrimination power was evaluated by a novel combination of chemometric data analysis and qualitative multi-elemental fingerprints of mineral water samples acquired from different regions of the Brazilian territory. The classification of mineral waters was assessed using only the wavelength emission intensities obtained by inductively coupled plasma optical emission spectrometry (ICP OES), monitoring different lines of Al, B, Ba, Ca, Cl, Cu, Co, Cr, Fe, K, Mg, Mn, Na, Ni, P, Pb, S, Sb, Si, Sr, Ti, V, and Zn, and Be, Dy, Gd, In, La, Sc and Y as internal standards. Data acquisition was done under robust (RC) and non-robust (NRC) conditions. Also, the combination of signal intensities of two or more emission lines for each element were evaluated instead of the individual lines. The performance of two classification-k-nearest neighbor (kNN) and soft independent modeling of class analogy (SIMCA)-and preprocessing algorithms, autoscaling and Pareto scaling, were evaluated for the ability to differentiate between the various samples in each approach tested (combination of robust or non-robust conditions with use of individual lines or sum of the intensities of emission lines). It was shown that qualitative ICP OES fingerprinting in combination with multivariate analysis is a promising analytical tool that has potential to become a recognized procedure for rapid authenticity and adulteration testing of mineral water samples or other material whose physicochemical properties (or origin) are directly related to mineral content.

Modeling of Effect of Plastic Deformation on Barkhausen Noise and Magnetoacoustic Emission in Iron With 2% Silicon

Before one models the effect of plastic deformation on magnetoacoustic emission (MAE), one must first treat non-180 degrees domain wall motion. In this paper, we take the Alessandro-Beatrice-Bertotti-Montorsi (ABBM) model and modify it to treat non-180 degrees wall motion. We then insert a modified stress-dependent Jiles-Atherton model, which treats plastic deformation, into the modified ABBM model to treat MAE and magnetic Barkhausen noise (HBN). In fitting the dependence of these quantities on plastic deformation, we apply a model for when deformation gets into the stage where dislocation tangles are formed, noting two chief effects, one due to increased density of emission centers owing to increased dislocation density, and the other due to a more gentle increase in the residual stress in the vicinity of the dislocation tangles as deformation is increased.

An In-Depth Study of the Barkhausen Emission Signal Properties of the Plastically Deformed Fe-2%Si Alloy

This paper presents the results of the in-depth study of the Barkhausen effect signal properties for the plastically deformed Fe-2%Si samples. The investigated samples have been deformed by cold rolling up to plastic strain epsilon(p) = 8%. The first approach consisted of time-domain-resolved pulse and frequency analysis of the Barkhausen noise signals whereas the complementary study consisted of the time-resolved pulse count analysis as well as a total pulse count. The latter included determination of time distribution of pulses for different threshold voltage levels as well as the total pulse count as a function of both the amplitude and the duration time of the pulses. The obtained results suggest that the observed increase in the Barkhausen noise signal intensity as a function of deformation level is mainly due to the increase in the number of bigger pulses.

Lack of magnetoacoustic emission in iron with 6.5% silicon

The phenomenon of magnetoacoustic emission (MAE) has been ascribed usually to one of two origins: either (1) motion of non-180 degrees domain walls or (2) creation or annihilation of domains. In this paper, we present strong evidence for the argument that the only origin for MAE is motion of non-180 degrees domain walls. The proof is evident as a result of measurements of zero MAE for a wide range of stress in the isotropic zero magnetostrictive polycrystalline alloy of iron with 6.5% silicon. We also explain why it was that the alternative origin was proposed and how the data in that same experiment can be reinterpreted to be consistent with the non-180 degrees wall motion origin. (C) 2008 Elsevier B.V. All rights reserved.

Estimating wave spectra from the motions of moored vessels: Experimental validation

The practicability of estimating directional wave spectra based on a vessel`s 1st order response has been recently addressed by several researchers. Different alternatives regarding statistical inference methods and possible drawbacks that could arise from their application have been extensively discussed, with an apparent preference for estimations based on Bayesian inference algorithms. Most of the results on this matter, however, rely exclusively on numerical simulations or at best on few and sparse full-scale measurements, comprising a questionable basis for validation purposes. This paper discusses several issues that have recently been debated regarding the advantages of Bayesian inference and different alternatives for its implementation. Among those are the definition of the best set of input motions, the number of parameters required for guaranteeing smoothness of the spectrum in frequency and direction and how to determine their optimum values. These subjects are addressed in the light of an extensive experimental campaign performed with a small-scale model of an FPSO platform (VLCC hull), which was conducted in an ocean basin in Brazil. Tests involved long and short crested seas with variable levels of directional spreading and also bimodal conditions. The calibration spectra measured in the tank by means of an array of wave probes configured the paradigm for estimations. Results showed that a wide range of sea conditions could be estimated with good precision, even those with somewhat low peak periods. Some possible drawbacks that have been pointed out in previous works concerning the viability of employing large vessels for such a task are then refuted. Also, it is shown that a second parameter for smoothing the spectrum in frequency may indeed increase the accuracy in some situations, although the criterion usually proposed for estimating the optimum values (ABIC) demands large computational effort and does not seem adequate for practical on-board systems, which require expeditious estimations. (C) 2009 Elsevier Ltd. All rights reserved.

Silicon Field-Emission Devices Fabricated Using the Hydrogen Implantation-Porous Silicon (HI-PS) Micromachining Technique

This paper presents a relatively simple method to fabricate field-emitter arrays from silicon substrates. These devices are obtained from silicon micromachining by means of the HI-PS technique-a combination of hydrogen ion implantation and porous silicon used as sacrificial layer. Also, a new process sequence is proposed and implemented to fabricate self-aligned integrated field-emission devices based on this technique. Electrical characteristics of the microtips obtained show good agreement with the Fowler-Nordheim theory, which are suitable for the proposed application.

Synthesis and characterization of semiconductor polymers having different phenylene-vinylene conjugation lengths

We have synthesized phenylene-vinylene (PV) polymers containing segments with different conjugation lengths interspaced by random distributed aliphatic segments. Infrared (IR) and ultraviolet-visible (UV-vis) spectroscopies, hydrogen nuclear magnetic resonance ((1)H NMR) spectrometry and differential scanning calorimetry (DSC) were used to characterize the prepared copolymers` structures. Polymers molecular weights were determined by gel permeation chromatography (GPC). The effect of polymer structure and composition on emission properties was studied by fluorescence (PL) spectroscopy under different irradiation wavelength. The emission energy shift due to segments with longer conjugation lengths was minor owed to the low polymerization degree achieved.

Chlorophyll a fluorescence and ultrastructural changes in chloroplast of water hyacinth as indicators of environmental stress

Chlorophyll a fluorescence parameters and transmission electron microscopy (TEM) were used to assess the stress conditions in water hyacinth along the Paraiba do Sul River (PSR), an important River in southeastern Brazil. The data were obtained at the end of the dry season of 2005 and at the end of the wet season of 2006. Changes in F-o and F-m parameters were observed as differentiated responses, depending on the season. Non-photochemical dissipation (qN and NPQ) from plants was greater in the most industrialized region of the PSR in both seasons. However, F-v/F-m for all samples ranged between 0.77 and 0.81, showing that high maximum quantum yield was maintained. Although the F-v/F-m suggests that the plants were exhibiting normal photochemical activities, ultrastructural changes in chloroplasts showed thylakoids disorganization. Plants from the most industrialized region showed non-stacking grana thylakoids disposition. In spite of these alterations, the membrane integrity was maintained, suggesting an adaptation to adjustment to adverse environmental conditions. (C) 2008 Elsevier B.V. All rights reserved.

Spatial Modeling of a Soil Fertility Index using Visible-Near-Infrared Spectra and Terrain Attributes

Our objective was to develop a methodology to predict soil fertility using visible near-infrared (vis-NIR) diffuse reflectance spectra and terrain attributes derived from a digital elevation model (DEM). Specifically, our aims were to: (i) assemble a minimum data set to develop a soil fertility index for sugarcane (Sarcharum officinarum L.) (SFI-SC) for biofuel production in tropical soils; (ii) construct a model to predict the SFI-SC using soil vis-NIR spectra and terrain attributes; and (iii) produce a soil fertility map for our study area and assess it by comparing it with a green vegetation index (GVI). The study area was 185 ha located in sao Paulo State, Brazil. In total, 184 soil samples were collected and analyzed for a range of soil chemical and physical properties. Their vis-NIR spectra were collected from 400 to 2500 nm. The Shuttle Radar Topographic Mission 3-arcsec (90-m resolution) DEM of the area was used to derive 17 terrain attributes. A minimum data set of soil properties was selected to develop the SFI-SC. The SFI-SC consisted of three classes: Class 1, the highly fertile soils; Class 2, the fertile soils; and Class 3, the least fertile soils. It was derived heuristically with conditionals and using expert knowledge. The index was modeled with the spectra and terrain data using cross-validated decision trees. The cross-validation of the model correctly predicted Class 1 in 75% of cases, Class 2 in 61%, and Class 3 in 65%. A fertility map was derived for the study area and compared with a map of the GVI. Our approach offers a methodology that incorporates expert knowledge to derive the SFI-SC and uses a versatile spectro-spatial methodology that may be implemented for rapid and accurate determination of soil fertility and better exploration of areas suitable for production.

Soil CO(2) emission estimated by different interpolation techniques

Soil CO(2) emissions are highly variable, both spatially and across time, with significant changes even during a one-day period. The objective of this study was to compare predictions of the diurnal soil CO(2) emissions in an agricultural field when estimated by ordinary kriging and sequential Gaussian simulation. The dataset consisted of 64 measurements taken in the morning and in the afternoon on bare soil in southern Brazil. The mean soil CO(2) emissions were significantly different between the morning (4.54 mu mol m(-2) s(-1)) and afternoon (6.24 mu mol m(-2) s(-1)) measurements. However, the spatial variability structures were similar, as the models were spherical and had close range values of 40.1 and 40.0 m for the morning and afternoon semivariograms. In both periods, the sequential Gaussian simulation maps were more efficient for the estimations of emission than ordinary kriging. We believe that sequential Gaussian simulation can improve estimations of soil CO(2) emissions in the field, as this property is usually highly non-Gaussian distributed.

Greenhouse gases emission from soil contaminated with automobile industry residue in Brazil

Solid waste of the automobile industry containing large amounts of heavy metals might affect the emission of greenhouse gases (GHG) when applied to the soil. Accumulation of inorganic chemical elements in the environment generally occurs due to human activity (industry, agriculture, mining and waste landfills). Residues from human activities may release heavy metals to the soil solution, causing toxicity to plants and other soil organisms. Heavy metals may also be adsorbed to clay minerals and/or complexed by the soil organic matter, becoming a potential source of pollutants. Not much is known about the behavior of solid wastes in tropical soil as regarded as source of greenhouse gases (GHG). The emission of GHG (CO(2), CH(4) and N(2)O) was evaluated in incubated soil samples collected in an area contaminated with a solid residue from an automobile industry. Samples were randomly collected at 0 to 0.2 m (a mix of soil and residue), 0.2 to 0.4 m (only residue) and 0.4 to 0.6 m (only soil). A contiguous uncontaminated area, cultivated with sugarcane, was also sampled following the same protocol. Canonical Discriminant Analysis and Principal Component Analysis were applied to the data to evaluate the GHG emission rates. Emission rates of GHG were greater in the samples from the contaminated than the sugarcane area, particularly high during the first days of incubation. CO(2) emissions were greater in samples collected at the upper layer for both areas, while CH(4) and N(2)O emissions were similar in all samples. The emission rates of CH(4) were the most efficient variables to differentiate contaminated and uncontaminated areas.

Determination of heavy metals by inductively coupled plasma-optical emission spectrometry in fish from the Piracicaba River in Southern Brazil

A total of 202 fish, representing 16 species, were collected during 2008 (March-October) in the Tanquan region of the Piracicaba River using nets. Flesh samples were collected and analyzed, using inductively coupled plasma-optical emission spectroscopy for Al, As, Cd, Co Cr, Cu, Mn, Mo, Ni, Ph, Se, Sn, Sr, and Zn. The results showed that the flesh of these fish all contained extremely high levels of Al and Sr, and moderately high levels of Cr, As, Zn, Ni. Mn and Pb. The metals were higher in these fish during rainy season, with fish collected during the months of March and October being the highest. In addition, the accumulation of metals was species-dependent. Cascudos (Hypostomus punctatus) and piranhas (Serrasalmus spilopleura) exhibited high levels of almost all of the metals, while curimbata (Prochilodus lineatus) had moderate levels. A few species, including pacu (Piaractus mesopotamicus) and dourado (Salminus maxillosus), had very low levels of most metals. The results show that the Piracicaba River Basin is widely contaminated with high levels of many toxic heavy metals, and that human consumption of some fish species is a human health concern. (C) 2009 Elsevier B.V. All rights reserved.

Violet ZnSe/ZnS as an Alternative to Green CdSe/ZnS in Nanocrystal-Fluorescent Protein FRET Systems

Fluorescent proteins from the green fluorescent protein family strongly interact with CdSe/ZnS and ZnSe/ZnS nanocrystals at neutral pH. Green emitting CdSe/ZnS nanocrystals and red emitting fluorescent protein dTomato constitute a 72% efficiency FRET system with the largest alteration of the overall photoluminescence profile, following complex formation, observed so far. The substitution of ZnSe/ZnS for CdSe/ZnS nanocrystals as energy donors enabled the use of a green fluorescent protein, GFP5, as energy acceptor. Violet emitting ZnSe/ZnS nanocrystals and green GFP5 constitute a system with 43% FRET efficiency and an unusually strong sensitized emission. ZnSe/ZnS-GFP5 provides a cadmium-free, high-contrast FRET system that covers only the high-energy part of the visible spectrum, leaving room for simultaneous use of the yellow and red color channels. Anisotropic fluorescence measurements confirmed the depolarization of GFP5 sensitized emission.