Electrochemical methods for speciation of trace elements in marine waters. Dynamic aspects.

The contribution of electrochemical methods to the knowledge of dynamic speciation of toxic trace elements in marine waters is critically reviewed. Due to the importance of dynamic considerations in the interpretation of the electrochemical signal, the principles and recent developments of kinetic features in the interconversion of metal complex species will be presented. As dynamic electrochemical methods, only stripping techniques (anodic stripping voltammetry and stripping chronopotentiometry) will be used because they are the most important for the determination of trace elements. Competitive ligand exchange-adsorptive cathodic stripping voltammetry, which should be considered an equilibrium technique rather than a dynamic method, will be also discussed because the complexing parameters may be affected by some kinetic limitations if equilibrium before analysis is not attained and/or the flux of the adsorbed complex is influenced by the lability of the natural complexes in the water sample. For a correct data interpretation and system characterization the comparison of results obtained from different techniques seems essential in the articulation of a serious discussion of their meaning.

Comparative study between probe focussed sonication and conventional stirring in the evaluation of cadmium and copper in plants.

Ultrasound (US)-assisted extraction has been widely used for metal ion extraction in plants due to its unique properties of decreased extraction time, minimal contamination, low reagent consumption and low cost. However, very few papers present a sound comparison between probe-focussed sonication and conventional stirring in the evaluation of metal ion extraction in plants. In this study, ultrasonic-assisted digestion has been evaluated and compared to magnetic stirring for total copper and cadmium determination by atomic absorption spectrometry in biological samples (plants, plankton and mussels). The same experimental conditions of sample amount and particle size, extractant solution and extraction time were applied for both ultrasound and magnetic stirring-assisted extraction methods in order to truly compare their effect on metal ion solubilisation. To gain further insight in this issue, dried and fresh plants were tested. The results obtained indicated that osmotic tension in cell walls, produced when dried and powdered samples were immersed in the extractant solution, had an important contribution to metal ion solubilisation, the enhancement due to US for the same purpose being negligible.

Impact of total variation minimization in volume rendering visualization of breast tomosynthesis data.

BACKGROUND AND OBJECTIVE: Total Variation (TV) minimization algorithms have achieved great attention due to the virtue of decreasing noise while preserving edges. The purpose of this work is to implement and evaluate two TV minimization methods in 3D. Their performance is analyzed through 3D visualization of digital breast tomosynthesis (DBT) data with volume rendering. METHODS: Both filters were studied with real phantom and one clinical DBT data. One algorithm was applied sequentially to all slices and the other was applied to the entire volume at once. The suitable Lagrange multiplier used in each filter equation was studied to reach the minimum 3D TV and the maximum contrast-to-noise ratio (CNR). Imaging blur was measured at 0° and 90° using two disks with different diameters (0.5 mm and 5.0 mm) and equal thickness. The quality of unfiltered and filtered data was analyzed with volume rendering at 0° and 90°. RESULTS: For phantom data, with the sequential filter, a decrease of 25% in 3D TV value and an increase of 19% and 30% in CNR at 0° and 90°, respectively, were observed. When the filter is applied directly in 3D, TV value was reduced by 35% and an increase of 36% was achieved both for CNR at 0° and 90°. For the smaller disk, variations of 0% in width at half maximum (FWHM) at 0° and a decrease of about 2.5% for FWHM at 90° were observed for both filters. For the larger disk, there was a 2.5% increase in FWHM at 0° for both filters and a decrease of 6.28% and 1.69% in FWHM at 90° with the sequential filter and the 3D filter, respectively. When applied to clinical data, the performance of each filter was consistent with that obtained with the phantom. CONCLUSIONS: Data analysis confirmed the relevance of these methods in improving quality of DBT images. Additionally, this type of 3D visualization showed that it may play an important complementary role in DBT imaging. It allows to visualize all DBT data at once and to analyze properly filters applied to all the three dimensions. Concise Abstract Total Variation (TV) minimization algorithms are one compressed sensing technique that has achieved great attention due to the virtue of decrease noise while preserve edges transitions. The purpose of this work is to solve the same TV minimization problem in DBT data, by studying two 3D filters. The obtained results were analyzed at 0° and 90° with a 3D visualization through volume rendering. The filters differ in their application. One considers a slice-by-slice optimization, sequentially traversing all slices of the data. The other considers the intensity values of adjacent slices to make this optimization on each voxel. The performance of each filter was also tested with a clinical case. The results obtained were very encouraging with a significantly increased contrast to noise ratio at 0° and 90° and a small reduction in blur at 90° (slight reduction of the out-of-plane artifact).

Evaluation of focused ultrasound and ozonolysis as sample treatment for direct determination of mercury by FI-CV-AAS. Optimization of parameters by full factorial design.

Different oxidation methodologies based on ozone and focused ultrasound for the degradation of organic matter and organic-mercury compounds (spiked) present in human urine are discussed. Inorganic and total mercury can be determined in human urine. A flow-injection cold-vapour atomic absorption spectrometer system was used for mercury measurements. Optimization of cold vapour generation was performed with NaBH4 and SnCl2. A two-level full factorial design (2(4)) was applied to understand the cross-effects among the variables influencing the degradation of organic-mercurials and organic matter in urine by KMnO4/HCl/focused ultrasound, namely, KMnO4 and HCl concentration, ultrasonication time and ultrasonication amplitude. Optimization results showed that all variables were significant. New trends in the application of focused ultrasound and ozone are highlighted. As a result of the optimization procedure, one simple, rapid and accurate method was developed for the determination of total mercury in urine samples The method is based on the ultrasound assisted degradation of organo-mercurials and organic matter in urine in the presence of KMnO4/HCl/Focused Ultrasound. The procedure can be accomplished within 3 min, using 50% sonication amplitude provided by a probe ultrasonic device (63 W maximum output power, 22.5 kHz frequency). The method was applied to measure the mercury content in spiked urine from different non-exposed volunteers.

Influence of UV-B radiation on lead speciation in the presence of natural particles of estuarine waters.

The influence of UV-B irradiation on filtered and non-filtered water samples collected in a non-polluted area of Tagus estuary was evaluated in this study. In the laboratory, both samples were titrated with lead (Pb(+2)) followed by differential pulse anodic stripping voltammetry (DPASV), before and after 1 and 10 days under UV-B irradiation. Metal-ligand complexing parameters were obtained based on a macromolecular heterogeneous ligand described by two distinct sites with a labile behavior, and a third small homogeneous weaker group, which concentration was determined from a potentiometric titration. Under UV-B radiation, the complexing strength decreased with time in both (filtered and non-filtered) irradiated samples, but this effect was more pronounced in the non-filtered water, which might be due to some adsorption of dissolved macromolecular ligands on the particles and/or to further degradation of dissolved organic matter (DOM). Furthermore, the presence of particles favored the break-down of the macromolecular ligand under long UV-B exposure time. These results present ecological implications for the estuarine ecosystems such as bioavailability and toxicity.

Dynamic relaxation in algebraic reconstruction technique (ART) for breast tomosynthesis imaging.

BACKGROUND AND OBJECTIVES: A major challenge in Digital Breast Tomosynthesis (DBT) is handling image noise since the 3D reconstructed images are obtained from low dose projections and limited angular range. The use of the iterative reconstruction algorithm Algebraic Reconstruction Technique (ART) in clinical context depends on two key factors: the number of iterations needed (time consuming) and the image noise after iterations. Both factors depend highly on a relaxation coefficient (λ), which may give rise to slow or noisy reconstructions, when a single λ value is considered for the entire iterative process. The aim of this work is to present a new implementation for the ART that takes into account a dynamic mode to calculate λ in DBT image reconstruction. METHODS: A set of initial reconstructions of real phantom data was done using constant λ values. The results were used to choose, for each iteration, the suitable λ value, taking into account the image noise level and the convergence speed. A methodology to optimize λ automatically during the image reconstruction was proposed. RESULTS: Results showed we can dynamically choose λ values in such a way that the time needed to reconstruct the images can be significantly reduced (up to 70%) while achieving similar image quality. These results were confirmed with one clinical dataset. CONCLUSIONS: With simple methodology we were able to dynamically choose λ in DBT image reconstruction with ART, allowing a shorter image reconstruction time without increasing image noise.

Influence of the sediment on lead speciation in the Tagus estuary.

The aim of this work is to study the influence of the Tagus estuarine sediment on lead speciation in the overlying natural water. The water sample in the presence of the sediment was contaminated three times with Pb(II) in a laboratory experiment. In different periods of time, at 1-7 days after each contamination, small volumes of water were titrated with lead. The titration was followed by anodic stripping voltammetry in differential pulse mode. Before and after contamination systematic analysis of the voltammetric parameters (peak current, peak potential and peak width) were carried out to get a clear picture of Pb(II) complexation in the soluble fraction in contact with the sediment. Two main types of organic ligands, macromolecular ligands and small compounds, were detected before contamination. Both of them form labile complexes (degree of lability within the timescale of some milliseconds). The small compounds, with a diffusion coefficient similar to that of the free metal ion, present a homogeneous behaviour in terms of Pb complexation. On the other hand macromolecular ligands, with a diffusion coefficient of 1.2 x 10(-6) cm2s(-1), can be described by two different binding groups, which might be of phenolic and carboxylic type as presented by humic matter. The sediment eliminated lead contamination (10(-6) moldm(-3) was the maximum concentration added) from 12 dm3 of water (surface of 8 dm2) within 2 days. It was also found that the sediment released organic ligands responsible for both labile and inert Pb complexes "seen" by voltammetry. The release of organic ligands that decreases the bioavailability of Pb(II) was clearly detected 1 week after contamination. Therefore, the sediment acts as a buffer for lead through two mechanisms against lead contamination: removing lead ions from the solution and releasing organic ligands to the water column. In a short period of time the sediment responds as a self-cleaning system for Pb(II) contamination in the estuarine water, which may have a very important influence in environmental pollution.

Complexes of vanadyl and uranyl ions with the chelating groups of humic matter.

The uranyl and vanadyl complexes formed with salicylic, phthalic and 3,4-dihydroxybenzoic acids have been studied by potentiometry in order to determine the stability constants of the M(m)L(n) species formed in solution, and the constants for the hydrolysis and polymeric complexes, at 25.0 degrees , in 0.10, 0.40 and 0.70M sodium perchlorate. MINIQUAD was used to process the data to find the best models for the species in solution, and calculate the formation constants. The uranyl-salicylic acid system was also studied by spectrophotometry and the program SQUAD used to process the data obtained. The best models for these systems show that co-ordination of the uranyl ion by carboxylate groups is easier than for the vanadyl ion, whereas the vanadyl ion seems to form more stable complexes with phenolate groups. Both oxo-cations seem to tend to hydrolyse rather than form complexes when the L:M ratios are greater than unity. Although the change in the constants with ionic strength is small, the activity coefficients of the salicylate and phthalate species have been calculated at ionic strengths 0.40 and 0.70M, along with the interaction parameters with Na(+), from the stability constants found for the species ML and H(2)L, according to the Brønsted-Guggenheim expression.

Uranyl complexes of n-alkanediaminotetra-acetic acids.

The uranyl complexes of n-propanediaminetetra-acetic acid, n-butanediaminetetra-acetic acid and n-hexanediaminetetra-acetic acid have been studied by potentiometry, with computer evaluation of the titration data by the MINIQUAD program. Stability constants of the 1:1 and 2:1 metal:ligand chelates have been determined as well as the respective hydrolysis and polymerization constants at 25 degrees in 0.10M and 1.00M KNO(3). The influence of the length of the alkane chain of the ligands on the complexes formed is discussed.

Note on the uranyl complexes of EDTA.

The nature of the EDTA complex of uranium(VI) is discussed, and it is concluded that there is no need to postulate stabilization of the complex by hydrogen-bonding between a protonated nitrogen atom and the uranyl ion.

Influence of organic matter on the uptake of cadmium, zinc, copper and iron by sorghum plants.

This article describes an experiment, carried out under controlled environment conditions, to investigate the effects of a fulvic acid fraction of soil organic matter on growth, cadmium (Cd) uptake and redistribution by sorghum. In addition the uptake of copper (Cu), zinc (Zn) and iron (Fe) was also determined. Sorghum was grown in nutrient solutions with 0, 0.1, 1 and 10 mg Cd dm(-3), in the absence and presence of organic matter (32 mg C dm(-3)), for various periods up to 20 days. A decrease in sorghum biomass due to Cd toxicity was observed at 10 mg Cd dm(-3), but for concentrations of 0.1 and 1 mg Cd dm(-3) the biomass was increased compared with control, without visual toxicity symptoms. The presence of organic matter (OM) further increased biomass production. Cadmium was mainly retained in sorghum roots, as usually found in tolerant plants, but Cd accumulation in sorghum was greater than in other Gramineae, or even more tolerant plants such as lettuce. The presence of OM decreased the bioavailability of Cd that was partially retained in solution by the OM ligands. However, OM promoted the translocation of Cd to shoots, an effect that may pose a risk to public health because plant-animal transfer of Cd could be enhanced. The presence of OM decreased the uptake of Cu, Zn and Fe. The presence (vs. absence) of 0.1 mg Cd dm(-3) enhanced the uptake of Fe, both in the absence and presence of OM.

Matrix effect on paralytic shellfish toxins quantification and toxicity estimation in mussels exposed to Gymnodinium catenatum.

Paralytic shellfish toxins were quantified in whole tissues of the mussel Mytilus galloprovincialis exposed to blooms of the dinoflagellate Gymnodinium catenatum in Portuguese coastal waters. A validated liquid chromatography method with fluorescence detection, involving pre-chromatographic oxidation was used to quantify carbamoyl, N-sulfocarbamoyl and decarbamoyl toxins. In order to test for any matrix effect in the quantification of those toxins, concentrations obtained from solvent and matrix matched calibration curves were compared. A suppression of the fluorescence signal was observed in mussel extract or fraction in comparison to solvent for the compounds dcGTX2 + 3, GTX2 + 3 and GTX1 + 4, while an enhancement was found for C1 + 2, dcSTX, STX, B1, dcNEO and NEO. These results showed that a matrix effect varies among compounds. The difference of concentrations between solvent and matrix matched calibration curves for C1 + 2 (median = 421 ng g⁻¹) exceeded largely the values for the other quantified compounds (0.09-58 ng g⁻¹). Those differences were converted into toxicity differences, using Oshima toxicity equivalence factors. The compounds C1 + 2 and dcNEO were the major contributors to the differences of total toxicity in the mussel samples. The differences of total toxicity were calculated in ten mussel samples collected during a 10-week blooming period in Portuguese coastal lagoon. Values varied between 53 and 218 µg STX equivalents kg⁻¹. The positive differences mean that the estimated toxicity using solvent calibration curves exceed the values taking into account the matrix. For the toxicity interval 200-800 µg STX equivalents kg⁻¹ an increase was found between 44 and 28%.

Improvement in soil and sorghum health following the application of polyacrylate polymers to a Cd-contaminated soil.

Contamination of soils with cadmium (Cd) is a serious global issue due to its high mobility and toxicity. We investigated the application of insoluble polyacrylate polymers to improve soil and plant health. Sorghum was grown in a Cd-contaminated sandy soil. Polyacrylate polymers at 0.2% (w/w) were added to half of the soil. Control soil without plants was also included in the experiment. Growth of sorghum was stimulated in the polymer-amended soil. The concentration of Cd in the shoots, and the activities of catalase and ascorbate peroxidase decreased in plants from polymer-amended soil compared with unamended control. The amount of CaCl(2)-extractable Cd in the polymer-amended soil was 55% of that in the unamended soil. The Cd extracted in sorghum shoots was 0.19 mg per plant grown on soil without polymer and 0.41 mg per plant grown on polymer-amended soil. The total amount of Cd removed from each pot corresponded to 1.5 and more than 6% of soil CaCl(2)-extractable Cd in unamended and polymer-amended soil, respectively. The activities of soil acid phosphatase, beta-glucosidase, urease, protease and cellulase were greatest in polymer-amended soil with sorghum. In conclusion, the application of polyacrylate polymers to reduce the bioavailable Cd pool seems a promising method to enhance productivity and health of plants grown on Cd-contaminated soils.

Competition of copper and/or calcium in nickel-pectin interaction by potentiometric and voltammetric techniques.

The interaction between nickel and pectin extracted from citrus fruit was studied in 0.10 M KNO(3), at pH 5.5 and 25 degrees C. Differential pulse and/or square wave polarography were used to determine free nickel. For a high coverage degree (theta) of the pectin by the metal ion a good fitting was observed between experimental results and the model that includes both complex species, ML and ML(2) (M for the metal ion and L for the ligand). In the ML(2) species, Ni(II) interacts with two carboxylate groups of different chains, resulting in an inter-chain association. For low theta values, the formation of ML(2) is hindered due to the repulsion between the negative charges of carboxylic groups in two independent segments of pectin. The influence of calcium or copper ions on the free nickel concentration, in the presence of pectin, may lead to a decrease in free nickel concentration, contrary to what would be expected from direct competition between Ca(II) or Cu(II) and Ni(II) for the pectin binding sites. This is due to the partial neutralisation of the negative carboxylic charges by the positive charges of the divalent cations, which favours NiL(2) formation through the association of independent chains.

Dynamic versus static ultrasonic sample treatment for the solid-liquid pre-concentration of mercury from human urine.

Dynamic and static ultrasonic procedures involving ultrasonic bath and tandem focused ultrasound (i.e. two probes were used in the same sample treatment) have been assessed in order to implement a reliable solid-liquid back extraction of mercury from commercial resins (dowex and chelex-100), previously used to concentrate Hg(II) from treated urine. The urine had been previously treated with an advanced oxidation process provided by the conjunction of potassium permanganate, hydrochloric acid and high intensity focused ultrasound, which allowed that organic matter degradation was achieved in less than 3min. 95+/-10% of mercury in the certified urine and 97+/-6% of the spiked methyl-mercury was recovered with the dowex resin plus the static ultrasonic procedure, whilst 96+/-11% of the spiked mercury was recovered with the dowex resin plus the dynamic procedure, for which ultrasonication was not necessary. The Hg pre-concentration factor used in this work was 8 (20mL of urine to 2.5mL of acid), but different volume ratios can be used in order to increase this factor.

Determination of Cd and Pb in biological reference materials by electrothermal atomic absorption spectrometry: A comparison of three ultrasonic-based sample treatment procedures.

Three different ultrasonic-based sample treatment approaches, the automated ultrasonic slurry sampling, the ultrasonic assisted acid solid-liquid extraction (ASLE) and the enzymatic probe sonication (EPS) were compared and discussed for the determination of Cd and Pb by ET-AAS in biological reference materials. The sample mass chosen to perform the analysis was 10mg and the liquid volume was 1ml of nitric acid 1M. The best results were obtained with the slurry procedure with which it was possible accurate and precise determination of the Cd and Pb content in four of the five reference materials studied. Optimum performance (total metal extraction) of ASLE assisted by ultrasound for Cd was only achieved in two of the four materials assessed whereas total Pb recovery was only possible in three of the five samples. Total extraction with the enzymatic probe sonication was only obtained for Cd in oyster tissue. Neither ASLE nor EPS were able to extract Cd or Pb from spruce needles. Pb concentration obtained after EPS was found to be highly dependent from sample centrifugation speed and time.

Ozone treatment for mercury determination in white wines.

A method was developed for the generation of mercury vapour by means of cold-vapour flow-injection atomic absorption spectrometry (FI-CV-AAS) from white wine samples after ozonation as sample pre-treatment. Two different reactors designs for sample ozonation were developed and investigated. The limit of detection and the limit of quantification were, respectively, 0.5 and 1.7 microg l(-1), and the relative standard deviation (n=10) was 2% for a concentration of 50 microg l(-1) and 7% for a concentration of 5 microg l(-1). The pre-treatment with ozone has allowed to reduce drastically the amount of chemical reagents (e.g. carrier agent and reducing agent) used in the FI-CV-AAS system. The mercury content of wine samples was also determined by FI-CV-AAS after pre-concentration in the presence of HNO(3) and H(2)O(2). In general, there was no significant difference among data obtained from both methodologies, but pre-treatment with ozone is much faster.