Chemical Trends in Solid Alkali Pertechnetates.

Insight into the solid-state chemistry of pure technetium-99 (99Tc) oxides is required in the development of a robust immobilization and disposal system for nuclear waste stemming from the radiopharmaceutical industry, from the production of nuclear weapons, and from spent nuclear fuel. However, because of its radiotoxicity and the subsequent requirement of special facilities and handling procedures for research, only a few studies have been completed, many of which are over 20 years old. In this study, we report the synthesis of pure alkali pertechnetates (sodium, potassium, rubidium, and cesium) and analysis of these compounds by Raman spectroscopy, X-ray absorption spectroscopy (XANES and EXAFS), solid-state nuclear magnetic resonance (static and magic angle spinning), and neutron diffraction. The structures and spectral signatures of these compounds will aid in refining the understanding of 99Tc incorporation into and release from nuclear waste glasses. NaTcO4 shows aspects of the relatively higher electronegativity of the Na atom, resulting in large distortions of the pertechnetate tetrahedron and deshielding of the 99Tc nucleus relative to the aqueous TcO4-. At the other extreme, the large Cs and Rb atoms interact only weakly with the pertechnetate, have closer to perfect tetrahedral symmetry at the Tc atom, and have very similar vibrational spectra, even though the crystal structure of CsTcO4 is orthorhombic while that of RbTcO4 is tetragonal. Further trends are observed in the cell volume and quadrupolar coupling constant.

Role of extracellular polymeric substances in bioflocculation of activated sludge microorganisms under glucose-controlled conditions.

Extracellular polymeric substances (EPS) secreted by suspended cultures of microorganisms from an activated sludge plant in the presence of glucose were characterized in detail using colorimetry, X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared (FTIR) spectroscopy. EPS produced by the multi-species community were similar to literature reports of pure cultures in terms of functionalities with respect to C and O but differed subtly in terms of N and P. Hence, it appears that EPS produced by different microorganisms maybe homologous in major chemical constituents but may differ in minor components such as lipids and phosphodiesters. The role of specific EPS constituents on microbial aggregation was also determined. The weak tendency of microorganisms to bioflocculate during the exponential growth phase was attributed to electrostatic repulsion when EPS concentration was low and acidic in nature (higher fraction of uronic acids to total EPS) as well as reduced polymer bridging. However, during the stationary phase, polymeric interactions overwhelmed electrostatic interactions (lower fraction of uronic acids to total EPS) resulting in improved bioflocculation. More specifically, microorganisms appeared to aggregate in the presence of protein secondary structures including aggregated strands, beta-sheets, alpha- and 3-turn helical structures. Bioflocculation was also favored by increasing O-acetylated carbohydrates and overall C-(O,N) and O=C-OH+O=C-OR functionalities.

FTIR spectral components of schwertmannite.

Fourier transform infrared (FTIR) spectral components of three dominant groups of sulfate species in synthetic schwertmannite (Fe(8)O(8)(OH)(6-x)(SO(4))(x)*nH(2)O) are presented. These components were extracted by multivariate curve resolution analysis of spectra obtained from N(2)(g)-dry samples initially reacted in aqueous solutions (pH 3-9) at room temperature. Each component contains complex sets of bands that correspond to mixtures of similar species. We tentatively assign these components to sulfate ions that are hydrogen- (components I and III) and iron-bonded (component I) to schwertmannite. Another component (II) is assigned to protonated sulfate species. Heating experiments to 130 degrees C moreover confirmed this possibility for component II. The spectral components extracted from this study can be used to identify dominant sulfate species in FTIR spectra of naturally occurring schwertmannite samples.

Micro-FTIR study of soot chemical composition-evidence of aliphatic hydrocarbons on nascent soot surfaces.

Previous studies suggest that soot formed in premixed flat flames can contain a substantial amount of aliphatic compounds. Presence of these compounds may affect the kinetics of soot mass growth and oxidation in a way that is currently not understood. Using an infrared spectrometer coupled to a microscope (micro-FTIR), we examined the composition of soot sampled from a set of ethylene-argon-oxygen flames recently characterized (A. D. Abid, et al. Combust. Flame, 2008, 154, 775-788), all with an equivalence ratio Φ=2.07 but varying in maximum flame temperatures. Soot was sampled at three distances above the burner surface using a probe sampling technique and deposited on silicon nitride thin film substrates using a cascade impactor. Spectra were taken and analyses performed for samples collected on the lowest five impactor stages with the cut-off sizes of D(50)=10, 18, 32, 56 and 100 nm. The micro-FTIR spectra revealed the presence of aliphatic C­H, aromatic C­H and various oxygenated functional groups, including carbonyl (C=O), C­O­C and C­OH groups. Spectral analyses were made to examine variations of these functional groups with flame temperature, sampling position and particle size. Results indicate that increases in flame temperature leads to higher contents of non-aromatic functionalities. Functional group concentrations were found to be ordered as follows: [C=O]<[C­O]<[aliphatic C­H]. Aliphatic C­H was found to exist in significant quantities, with very little oxygenated groups present. The ratio of these chemical functionalities to aromatic C­H remains constant for particle sizes spanning 10-100 nm. The results confirm a previous experimental finding: a significant amount of aliphatic compounds is present in nascent soot formed in the flames studied, especially towards larger distances above the burner surface.

In situ studies of soft- and reactive landing of mass-selected ions using infrared reflection absorption spectroscopy.

Grazing incidence infrared reflection absorption spectroscopy (IRRAS) for in situ and in real time characterization of substrates modified by soft and reactive landing (SL and RL) of complex ions was implemented on a mass-selected ion deposition instrument. Ions produced by electrospray ionization were mass-selected using a quadrupole mass filter and deposited onto inert and reactive self-assembled monolayer (SAM) surfaces. Surface composition during and after ion deposition was monitored using IRRAS. Physisorption of a cyclic peptide, Gramicidin S (GS), was studied for 8 h during deposition and additional 12 h after the end of deposition. The integrated signal of the characteristic amide bands followed a linear increase during the deposition and stayed unchanged after the deposition was finished. Similar linear increase in IRRAS signal was obtained following reactive deposition of the protonated dodecanediamine onto SAMs of dithiobis (succinimidyl undecanoate) (NHS-SAM) and 16-mercaptohexadecanoic acid fluoride (COF-SAM) on gold. IRRAS allowed us to monitor for the first time the formation of the amide bond between reactive SAM surfaces and the projectile molecule.

Passive standoff detection of RDX residues on metal surfaces via infrared hyperspectral imaging.

Hyperspectral images of galvanized steel plates, each containing a stain of cyclotrimethylenetrinitramine (RDX), were recorded using a commercial long-wave infrared imaging spectrometer. Demonstrations of passive RDX chemical detection at areal dosages between 16 and 90 microg/cm(2) were carried out over practical standoff ranges between 14 and 50 m. Anomaly and target detection algorithms were applied to the images to determine the effect of areal dosage and sensing distance on detection performance for target RDX. The anomaly detection algorithms included principal component analysis, maximum autocorrelation factors, and principal autocorrelation factors. Maximum difference factors and principal difference factors are novel multivariate edge detection techniques that were examined for their utility in detection of the RDX stains in the images. A target detection algorithm based on generalized least squares was applied to the images, as well, to see if the algorithm can identify the compound in the stains on the plates using laboratory reflection spectra of RDX, cyclotetramethylenetetranitramine (HMX), and 2,4,6-trinitrotoluene (TNT) as the target spectra. The algorithm could easily distinguish between the nitroaromatic (TNT) compound and the nitramine (RDX, HMX) compounds, and, though the distinction between RDX and HMX was less clear, the mean weighted residuals identified RDX as the stain on the plate. Improvements that can be made in this detection technique are discussed in detail. As expected, it was found that detection was best for short distances and higher areal dosages. However, the target was easily detected at all distances and areal dosages used in this study.

Spectroscopic characterization of extracellular polymeric substances from Escherichia coli and Serratia marcescens: suppression using sub-inhibitory concentrations of bismuth thiols.

Free and bound (or capsular) EPS produced by suspended cultures of Escherichia coli and Serratia marcescens were characterized in detail using colorimetric analysis of total proteins and polysaccharides, Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), and Auger electron spectroscopy (AES) in the presence and absence of bismuth-based antifouling agents. Subtle differences in the chemical composition of free and bound EPS were observed for both bacteria in the absence of bismuth. Total polysaccharides and proteins in free and bound EPS decreased upon treatment with subinhibitory concentrations of lipophilic bismuth thiols (bismuth dimercaptopropanol, BisBAL; bismuth ethanedithiol, BisEDT; and bismuth pyrithione, BisPYR), with BisBAL being most effective. Bismuth thiols also influenced acetylation and carboxylation of polysaccharides in EPS from S. marcescens. Extensive homology between EPS samples in the presence and absence of bismuth was observed with proteins, polysaccharides, and nucleic acids varying predominantly only in the total amount produced. Second derivative analysis of the amide I region of FTIR spectra revealed decreases in protein secondary structures in the presence of bismuth thiols. Hence, antifouling properties of bismuth thiols appear to originate in their ability to suppress O-acetylation and protein secondary structure formation in addition to free and bound EPS secretion.

Nanoparticle-based electrochemical immunosensor for the detection of phosphorylated acetylcholinesterase: an exposure biomarker of organophosphate pesticides and nerve agents.

A nanoparticle-based electrochemical immunosensor has been developed for the detection of phosphorylated acetylcholinesterase (AChE), which is a potential biomarker of exposure to organophosphate (OP) pesticides and chemical warfare nerve agents. Zirconia nanoparticles (ZrO(2) NPs) were used as selective sorbents to capture the phosphorylated AChE adduct, and quantum dots (ZnS@CdS, QDs) were used as tags to label monoclonal anti-AChE antibody to quantify the immunorecognition events. The sandwich-like immunoreactions were performed among the ZrO(2) NPs, which were pre-coated on a screen printed electrode (SPE) by electrodeposition, phosphorylated AChE and QD-anti-AChE. The captured QD tags were determined on the SPE by electrochemical stripping analysis of its metallic component (cadmium) after an acid-dissolution step. Paraoxon was used as the model OP insecticide to prepare the phosphorylated AChE adducts to demonstrate proof of principle for the sensor. The phosphorylated AChE adduct was characterized by Fourier transform infrared spectroscopy (FTIR) and mass spectroscopy. The binding affinity of anti-AChE to the phosphorylated AChE was validated with an enzyme-linked immunosorbent assay. The parameters (e.g., amount of ZrO(2) NP, QD-anti-AChE concentration,) that govern the electrochemical response of immunosensors were optimized. The voltammetric response of the immunosensor is highly linear over the range of 10 pM to 4 nM phosphorylated AChE, and the limit of detection is estimated to be 8.0 pM. The immunosensor also successfully detected phosphorylated AChE in human plasma. This new nanoparticle-based electrochemical immunosensor provides an opportunity to develop field-deployable, sensitive, and quantitative biosensors for monitoring exposure to a variety of OP pesticides and nerve agents.

Strategies for detecting organic liquids on soils using mid-infrared reflection spectroscopy.

Stand-off monitoring for chemical spills can provide timely information for cleanup efforts, and mid-infrared reflection spectroscopy is one approach being investigated for spill detection. Using laboratory data, anomaly and target detection strategies were examined for the detection of four different low-volatility organic liquids on two different soil types. Several preprocessing and signal-weighting strategies were studied. Anomaly detection for C-H bands was good using second-derivative preprocessing and provided similar performance to that of target detection approaches such as generalized least-squares and partial least-squares, with detections at soil loads of approximately 3-6 microg/cm2 a real dosage. Good performance was also found for the detection of P=O, O-H, and C=O stretching vibrational modes, but the optimal strategy varied. The simplicity and generality of anomaly detection is attractive; however, target detection provides more capability for classification.

Reactive landing of peptide ions on self-assembled monolayer surfaces: an alternative approach for covalent immobilization of peptides on surfaces.

Soft landing of mass-selected peptide ions onto reactive self-assembled monolayer surfaces (SAMs) was performed using a newly constructed ion deposition apparatus. SAM surfaces before and after soft landing were characterized ex situ using time-of-flight secondary-ion mass spectrometry (TOF-SIMS) and infrared reflection-absorption spectroscopy (IRRAS). We demonstrate that reactive landing (RL) results in efficient covalent linking of lysine-containing peptides onto the SAM of N-hydroxysuccinimidyl ester-terminated alkylthiol on gold (NHS-SAM). Systematic studies of the factors that affect the efficiency of RL revealed that the reaction takes place upon collision and is promoted by the kinetic energy of the ion. The efficiency of RL is maximized at ca. 40 eV collision energy. At high collision energies the RL efficiency decreases because of the competition with scattering of ions off the surface. The reaction yield is independent of the charge state of the projectile ions, suggesting that peptide ions undergo efficient neutralization upon collision. Chemical and physical properties of the SAM surface are also important factors that affect the outcome of RL. The presence of chemically reactive functional groups on the SAM surface significantly improves the reaction efficiency. RL of mass- and energy-selected peptide ions on surfaces provides a highly specific approach for covalent immobilization of biological molecules onto SAM surfaces.

Hygroscopic behavior of substrate-deposited particles studied by micro-FT-IR spectroscopy and complementary methods of particle analysis.

The application of microscopic Fourier transform infrared (micro-FT-IR) spectroscopy combined with complementary methods of particle analysis is demonstrated here for investigations of phase transitions and hygroscopic growth of micron-sized particles. The approach utilizes the exposure of substrate-deposited, isolated particles to humidified nitrogen inside a sample cell followed by micro-FT-IR spectroscopy over a selected sample area. Phase transitions of NaCl, sea salt, NaNO3, and (NH4)2SO4 particles are monitored with this technique to evaluate its utility and applicability for particle hydration studies. The results are found in excellent agreement with literature data in terms of (a) reliable and reproducible detection of deliquescence and efflorescence phase transitions, (b) quantitative measurements of water-to-solute ratios in particles as a function of relative humidity, and (c) changes in the IR spectra resulting from phase transitions and changing relative humidity. Additional methods of particle analysis are employed to complement and assist in the interpretation of particle hygroscopicity data obtained from micro-FT-IR measurements. The analytical approach and the experimental setup presented here are relatively simple, inexpensive, readily available and therefore may be practical for hydration studies of environmental particles collected in both laboratory and field studies.

Quantification of volatile organics in soil aging experiments using fourier transform infrared spectroscopy.

On-line Fourier transform infrared (FT-IR) spectroscopy was applied to monitor the concentration of halogenated volatile organic compounds in a sample-preparation process that simulates long-term, slow accumulation of contaminants in soils (i.e., aging). Artificial aging is conducted by circulating a supercritical fluid solution containing the contaminant(s) of interest through a packed soil column. Mid-infrared spectra of several volatile halocarbons were measured in supercritical Xe and CO(2) to evaluate possible interferences from the strong absorption of CO(2). Although some of the C-X bands were partially masked in supercritical CO(2), all of the compounds studied had distinct spectral features in the region 1400-700 cm(-1) and could be monitored in either solvent. Quantitative measurements of halogenated volatile organics in supercritical CO(2) were demonstrated with CCl(4). Excellent results were obtained over the range 7-280 mM. Representative artificial aging experiments were conducted on two test soils using CCl(4) as the contaminant. On-line (FT-IR) estimates of the aged soil concentrations were 1.3-4.4 times higher than off-line concentrations obtained by gas chromatography/mass spectrometry. The discrepancies were primarily ascribed to post-aging losses that occurred during depressurization and subsequent sample handling. FT-IR spectroscopy is shown to be a powerful tool for monitoring soil loading behavior and for developing artificial aging protocols.

Multivariate curve resolution applied to infrared reflection measurements of soil contaminated with an organophosphorus analyte.

Multivariate curve resolution (MCR) is a powerful technique for extracting chemical information from measured spectra of complex mixtures. A modified MCR technique that utilized both measured and second-derivative spectra to account for observed sample-to-sample variability attributable to changes in soil reflectivity was used to estimate the spectrum of dibutyl phosphate (DBP) adsorbed on two different soil types. This algorithm was applied directly to measurements of reflection spectra of soils coated with analyte without resorting to soil preparations such as grinding or dilution in potassium bromide. The results provided interpretable spectra that can be used to guide strategies for detection and classification of organic analytes adsorbed on soil. Comparisons to the neat DBP liquid spectrum showed that the recovered analyte spectra from both soils showed spectral features from methyl, methylene, hydroxyl, and P=O functional groups, but most conspicuous was the absence of the strong PO-(CH2)3CH3 stretch absorption at 1033 cm(-1). These results are consistent with those obtained previously using extended multiplicative scatter correction.

Kinetic desorption and sorption of U(VI) during reactive transport in a contaminated Hanford sediment.

Column experiments were conducted to investigate U(VI) desorption and sorption kinetics in a sand-textured, U(VI)-contaminated (22.7 micromol kg(-1)) capillary fringe sediment from the U.S. Department of Energy (DOE) Hanford site. Saturated column experiments were performed under mildly alkaline conditions representative of the Hanford site where uranyl-carbonate and calcium-uranyl-carbonate complexes dominate aqueous speciation. A U(VI)-free solution was used to study contaminant U(VI) desorption in columns where different flow rates were applied. Sorbed, contaminant U(VI) was partially labile (11.8%), and extended leaching times and water volumes were required for complete desorption of the labile fraction. Uranium-(VI) sorption was studied after the desorption of labile, contaminant U(VI) using different U(VI) concentrations in the leaching solution. Strong kinetic effects were observed for both U(VI) sorption and desorption, with half-life ranging from 8.5 to 48.5 h for sorption and from 39.3 to 150 h for desorption. Although U(VI) is semi-mobile in mildly alkaline, subsurface environments, we observed substantial U(VI) adsorption, significant retardation during transport, and atypical breakthrough curves with extended tailing. A distributed rate model was applied to describe the effluent data and to allow comparisons between the desorption rate of contaminant U(VI) with the rate of shortterm U(VI) sorption. Desorption was the slower process. We speculate that the kinetic behavior results from transport or chemical phenomena within the phyllosilicate-dominated fine fraction present in the sediment. Our results suggest that U(VI) release and transport in the vadose zone and aquifer system from which the sediment was obtained are kinetically controlled.

Cryogenic laser induced fluorescence characterization of U(VI) in Hanford Vadose Zone pore waters.

Ambient and liquid helium temperature laser-induced time-resolved uranyl fluorescence spectroscopy was applied to study the speciation of aqueous uranyl solutions containing carbonate and phosphate and two porewater samples obtained by ultracentrifugation of U(VI)-contaminated sediments. The significantly enhanced fluorescence signal intensity and spectral resolution found at liquid helium temperature allowed, for the first time, direct fluorescence spectroscopic observation of the higher aqueous uranyl complexes with carbonate: UO2(CO3)2(2-), UO2(CO3)3(4-), and (UO2)2(OH)3CO3-. The porewater samples were nonfluorescent at room temperature. However, at liquid helium temperature, both porewater samples displayed strong, well-resolved fluorescence spectra. Comparisons of the spectroscopic characteristics of the porewaters with those of the standard uranyl-carbonate complexes confirmed that U(VI) in the porewaters existed primarily as UO2(CO3)3(4-) along with a small amount of other minor components, such as dicalcium-urano-tricarbonate complex, Ca2UO2(CO3)3, consistent with thermodynamic calculation. The U(VI)-carbonate complex is apparently the mobile species responsible for the subsurface migration of U(VI), even though the majority of the in-ground U(VI) inventory at the site from which the samples were obtained exists as intragrain U(VI)-silicate precipitates.