Fluorescence spectroscopy of U(VI)-silicates and U(VI)-contaminated Hanford sediment

Time-resolved U(VI) laser fluorescence spectra (TRLFS) were recorded for a series of natural uranium-silicate minerals including boltwoodite, uranophane, soddyite, kasolite, sklodowskite, cuprosklodowskite, haiweeite, and weeksite, a synthetic boltwoodite, and four U(VI)-contaminated Hanford vadose zone sediments. Lowering the sample temperature from RT to ~5.5 K significantly enhanced the fluorescence intensity and spectral resolution of both the minerals and sediments, offering improved possibilities for identifying uranyl species in environmental samples. At 5.5 K, all of the uranyl silicates showed unique, well-resolved fluorescence spectra. The symmetric O = U = O stretching frequency, as determined from the peak spacing of the vibronic bands in the emission spectra, were between 705 to 823 cm−1 for the uranyl silicates. These were lower than those reported for uranyl phosphate, carbonate, or oxy-hydroxides. The fluorescence emission spectra of all four sediment samples were similar to each other. Their spectra shifted minimally at different time delays or upon contact with basic Na/Ca-carbonate electrolyte solutions that dissolved up to 60% of the precipitated U(VI) pool. The well-resolved vibronic peaks in the fluorescence spectra of the sediments indicated that the major fluorescence species was a crystalline uranyl mineral phase, while the peak spacing of the vibronic bands pointed to the likely presence of uranyl silicate. Although an exact match was not found between the U(VI) fluorescence spectra of the sediments with that of any individual uranyl silicates, the major spectral characteristics indicated that the sediment U(VI) was a uranophane-type solid (uranophane, boltwoodite) or soddyite, as was concluded from microprobe, EXAFS, and solubility analyses

Silver containing sorbents: Physicochemical and biological properties

AbstractNew silver containing sorbents, based on mineral carriers, such as alumina and silica systems with a meso- and macro- porous structure, have a higher mechanical resistance and, hydrophilic and hydrophobic chemical composition of the surface. These sorbents are easy to find and relatively inexpensive, compared to their known equivalents. They are furthermore characterised by high specific surface and simple preparation, whilst the addition of silver considerably increases their antiseptic activity. The results of research of the physical, chemical and biological properties of the developed substances, as well as bio-comparability of sorbents with biological tissues, are presented in this paper. The modified material acts simultaneously as the carrier for active substances to the area of therapeutic application and as a sorbent used to remove toxic agents from such areas. This approach led us to modify the sorbent, and prolong the delivery of substances such as silver, as an effective antibacterial and antimycotic agent

Electrochemical Microsensors for the Detection of Cadmium(II) and Lead(II) Ions in Plants

Routine determination of trace metals in complex media is still a difficult task for many analytical instruments. The aim of this work was to compare three electro-chemical instruments [a standard potentiostat (Autolab), a commercially available miniaturized potentiostat (PalmSens) and a homemade micropotentiostat] for easy-to-use and sensitive determination of cadmium(II) and lead(II) ions. The lowest detection limits (hundreds of pM) for both metals was achieved by using of the standard potentiostat, followed by the miniaturized potentiostat (tens of nM) and the homemade instrument (hundreds of nM). Nevertheless, all potentiostats were sensitive enough to evaluate contamination of the environment, because the environmental limits for both metals are higher than detection limits of the instruments. Further, we tested all used potentiostats and working electrodes on analysis of environmental samples (rainwater, flour and plant extract) with artificially added cadmium(II) and lead(II). Based on the similar results obtained for all potentiostats we choose a homemade instrument with a carbon tip working electrode for our subsequent environmental experiments, in which we analyzed maize and sunflower seedlings and rainwater obtained from various sites in the Czech Republic

Control of the Accumulation of Non-Process Elements in Pulp Mills with Bleach Filtrate Reuse: A Chemical Equilibrium Approach to Predicting the Partitioning of Metals in Pulp Mill and Bleach Plant Streams

The overall goal of this project was to develop fundamental, experimentally based methods for predicting the solubility or organic and inorganic matter and their interactions in recycled effluent from kraft pulp mills and bleach plants. This included: characterizing the capacity of wood pulp and dissolved organic matter to bind metal ions, developing a thermodynamic database of properties needed to describe the solubility of inorganic matter in pulp mill streams, incorporation of the database into equilibrium calculation software for predicting the solubility of the metals of interest, and evaluating its capability to predict the distribution of the metals between pulp fibers, inorganic precipitates, and solution

EBB 332-4 - TEMBIKAR & KACA NOV 05.

5,10,15,20-Tetraferrocenyl porphyrin, H(2)TFcP, a simple example of a donor-acceptor system, was tested as ligand for the development of a novel multi-transduction chemical sensors aimed at the determination of transition metal ions. The fluorescence energy transfer between ferrocene donor and porphyrin acceptor sub-units was considered. The simultaneously measured optical and potentiometric responses of solvent polymeric membranes based on H(2)TFcP permitted the detection of lead ions in sample solutions, in the concentration range from 2.7 x 10(-7) to 3.0 x 10(-3) M. The detection limit of lead determination was 0.27 mu M, low enough to perform the direct analysis of Pb2+ in natural waters

Peptide immobilisation on porous silicon surface for metal ions detection

In this work, a Glycyl-Histidyl-Glycyl-Histidine (GlyHisGlyHis) peptide is covalently anchored to the porous silicon PSi surface using a multi-step reaction scheme compatible with the mild conditions required for preserving the probe activity. In a first step, alkene precursors are grafted onto the hydrogenated PSi surface using the hydrosilylation route, allowing for the formation of a carboxyl-terminated monolayer which is activated by reaction with N-hydroxysuccinimide in the presence of a peptide-coupling carbodiimide N-ethyl-N'-(3-dimethylaminopropyl)-carbodiimide and subsequently reacted with the amino linker of the peptide to form a covalent amide bond. Infrared spectroscopy (FT-IR) and X-ray photoelectron spectroscopy are used to investigate the different steps of functionalization

Recent Trends in Monitoring of European Water Framework Directive Priority Substances Using Micro-Sensors: A 2007–2009 Review

This review discusses from a critical perspective the development of new sensors for the measurement of priority pollutants targeted in the E.U. Water Framework Directive. Significant advances are reported in the paper and their advantages and limitations are also discussed. Future perspectives in this area are also pointed out in the conclusions. This review covers publications appeared since December 2006 (the publication date of the Swift report). Among priority substances, sensors for monitoring the four WFD metals represent 81% of published papers. None of analyzed publications present a micro-sensor totally validated in laboratory, ready for tests under real conditions in the field. The researches are mainly focused on the sensing part of the micro-sensors. Nevertheless, the main factor limiting micro-sensor applications in the environment is the ruggedness of the receptor towards environmental conditions. This point constitutes the first technological obstacle to be overcome for any long-term field tests

Sunflower Plants as Bioindicators of Environmental Pollution with Lead (II) Ions

In this study, the influence of lead (II) ions on sunflower growth and biochemistry was investigated from various points of view. Sunflower plants were treated with 0, 10, 50, 100 and/or 500 μM Pb-EDTA for eight days. We observed alterations in growth in all experimental groups compared with non-treated control plants. Further we determined total content of proteins by a Bradford protein assay. By the eighth day of the experiment, total protein contents in all treated plants were much lower compared to control. Particularly noticeable was the loss of approx. 8 μg/mL or 15 μg/mL in shoots or roots of plants treated with 100 mM Pb-EDTA. We also focused our attention on the activity of alanine transaminase (ALT), aspartate transaminase (AST) and urease. Activity of the enzymes increased with increasing length of the treatment and applied concentration of lead (II) ions. This increase corresponds well with a higher metabolic activity of treated plants. Contents of cysteine, reduced glutathione (GSH), oxidized glutathione (GSSG) and phytochelatin 2 (PC2) were determined by high performance liquid chromatography with electrochemical detection. Cysteine content declined in roots of plants with the increasing time of treatment of plants with Pb-EDTA and the concentration of toxic substance. Moreover, we observed ten times higher content of cysteine in roots in comparison with shoots. The observed reduction of cysteine content probably relates with its utilization for biosynthesis of GSH and phytochelatins, because the content of GSH and PC2 was similar in roots and shoots and increased with increased treatment time and concentration of Pb-EDTA. Moreover, we observed oxidative stress caused by Pb-EDTA in roots where the GSSG/GSH ratio was about 0.66. In shoots, the oxidative stress was less distinctive, with a GSSG/GSH ratio 0.14. We also estimated the rate of phytochelatin biosynthesis from the slope of linear equations plotted with data measured in the particular experimental group. The highest rate was detected in roots treated with 100 μM of Pb-EDTA. To determine heavy metal ions many analytical instruments can be used, however, most of them are only able to quantify total content of the metals. This problem can be overcome using laser induced breakdown spectroscopy, because it is able to provide a high spatial-distribution of metal ions in different types of materials, including plant tissues. Data obtained were used to assemble 3D maps of Pb and Mg distribution. Distribution of these elements is concentrated around main vascular bundle of leaf, which means around midrib