A new method for pretreating blood samples for trace Cr analysis is described. The Advanced Oxidation Process (AOP with H 2 O 2 and 5.5-W irradiation for 60 min) is used to remove biological/ organic species for subsequent analysis. Prior to the AOP pretreatment, acid (HNO 3 ) is used at pH 3.0 to inhibit the enzyme catalase in the blood samples. Catalytic Adsorptive Stripping Voltammetry (CAdSV) at a bismuth film electrode (BiFE) gives Cr concentration of 6.0 ± 0.3 ppb in the blood samples. This concentration was confirmed by dry-ashing the blood samples and subsequent analysis by atomic absorption spectroscopy (AAS). This current method may be used to monitor chromium, a trace metal in humans, and the efficacy and safety of chromium supplements as adjuvant therapy for diabetes.

A bismuth bulk electrode (BiBE) has been investigated as an alternative electrode for the anodic stripping voltammetric (ASV) analysis of Pb(II), Cd(II), and Zn(II). The BiBE, which is fabricated in house, shows results comparable to those of similar analyses at other Bi-based electrodes. Metal accumulation is achieved by holding the electrode potential at −1.4 V (vs. Ag/AgCl) for 180 s followed by a square wave voltammetric stripping scan from −1.4 to −0.35 V. Calibration plots are obtained for all three metals, individually and simultaneously, in the 10-100 μg L −1 range, with a detection limit of 105, 54, and 396 ng L −1 for Pb(II), Cd(II), Zn(II), respectively. A slight reduction in slope is observed for Cd(II) and Pb(II) when the three metals are calibrated simultaneously vs. individually. Comparing the sensitivities of the metals when calibrated individually vs in a mixture reveals that Zn(II) is not affected by stripping in a mixture. However, Pb(II) and Cd(II) have decreasing sensitivities in a mixture. The optimized method has been successfully used to test contaminated river water by standard addition. The results demonstrate the ability of the BiBE as an alternative electrode material in heavy metal analysis.

Optical fluorescence sol-gel sensors have been developed for the detection of carbon dioxide gas in the 0.03-30% range with a detection limit of 0.008% (or 80 ppm) and a quantitation limit of 0.02% (or 200 ppm) CO(2). Sol-gels were spin-coated on glass slides to create an organically modified silica-doped matrix with the 1-hydroxypyrene-3,6,8-trisulfonate (HPTS) fluorescent indicator. The luminescence intensity of the HPTS indicator (513 nm) is quenched by CO(2), which protonates the anionic form of HPTS. An ion pair technique was used to incorporate the lipophilic dye into the hydrophilic sol-gel matrix. TiO(2) particles (<5 microm diameter) were added to induce Mie scattering and increase the incident light interaction with the sensing film, thus increasing the signal-to-noise ratio. Moisture-proof overcoatings have been used to maintain a constant level of water inside the sensor films. The optical sensors are inexpensive to prepare and can be easily coupled to fiber optics for remote sensing capabilities. A fiber-optic bundle was used for the gas detection and shown to work as part of a multianalyte platform for simultaneous detection of multiple analytes. The studies reported here resulted in the development of sol-gel optical fluorescent sensors for CO(2) gas with sensitivity below that in the atmosphere (ca. 387 ppm). These sensors are a complementary approach to current FT-IR measurements for real-time carbon dioxide detection in environmental applications.

An electrochemical technique has been developed for ultra trace (ngL−1) vanadium (V) measurement. Catalytic adsorptive stripping voltammetry for V analysis was developed at mercury-coated gold micro-wire (MWE, 100 μm) electrodes in the presence of gallic acid (GA) and bromate ion. A potential of −0.275 V (vs Ag/AgCl) was used to accumulate the complex in acetate buffer (pH 5.0) at the electrode surface followed by a differential pulse voltammetric scan. Parameters affecting the electrochemical response, including pH, concentration of GA and bromate, deposition potential and time have been optimized. Linear response was obtained in the 0–1000 ngL−1 range (2 min deposition), with a detection limit of 0.88 ngL−1. The method was validated by comparison of results for an unknown solution of V by atomic absorption measurement. The protocol was evaluated in a real sample by measuring the amount of V in river water samples. Thick bismuth film electrodes with protective polystyrene films have also been made and evaluated as a mercury free alternative. However, ngL−1 level detection was only attainable with extended (10 min) deposition times. The proposed use of MWEs for the detection of V is sensitive enough for future use to test V concentration in biological fluids treated by the advanced oxidation process (AOP).

The use of sol-gels as a sensing matrix for the development of unique sensing strategies is discussed. Sol-gels offer almost limitless possibilities for sensing substrates due to the variety of physical properties that can be obtained by altering a number of discussed fabrication conditions and techniques. By careful consideration of the sensing requirements, novel detection methods have been developed for a variety of analytes and applications. Here, sol-gels have been used to monitor pH at the extreme ends of the scale ([H + ] = 1-11 M and [OH − ] = 1-10 M) and in mixed solvent/solute systems using dual sensing approaches. The use of ligand-grafted sol-gel monoliths for optical determination of metal ion species is also discussed. The electrochemical determination of Cr(Ⅵ) by electrodeposited sol-gel modified electrodes is also presented.sol-gel, organofunctional, acid, base, metal ions

Fluorescence sensors based on a trifluoroacetophone compound doped in ethyl cellulose (EC) thin films have been developed for the detection of methanol, ethanol, and 2-propanol (isopropanol, Pr i OH) vapors. Thin-film sensors are prepared with 4-dibutylamino-4'-(trifluoroacetyl)stilbene (Chromoionophore IX or CIX) as the fluorescent dye and its solution in EC was spin-coated onto glass slides. The luminescence intensity of the dye (555 nm) is quenched when exposed to alcohol vapor. Tested in the range of ca. 0 -1.5 × 10 4 ppm (wt) for MeOH and EtOH, and ca. 0 -2.3 × 10 4 ppm for Pr i OH, the sensors gave detection limits of 9, 13, 21 ppm and quantification limits of 32, 43, and 70 ppm, respectively. To enhance the sensitivity of the sensors, TiO2 particles have been added to the films to induce Mie scattering, which increases the incident light interaction with the sensing films. The sensors in this work have been designed to work in a multianalyte platform for the simultaneous detection of multiple gas analytes.

A new complex salt of composition [Co(phen)3]3(V4O12)2Cl·27H2O (phen = 1,10-phenanthroline and [V4O12]4- = tetrameric dodecaoxotetravanadate ion) was synthesized by reacting appropriate salts in aqueous medium. The complex salt has been characterized by elemental analyses, thermogravimetric analysis (TGA), cyclic voltammetry (CV), FT-IR and UV/Vis spectroscopies, solubility product and conductance measurements. Single crystal X-ray structure determination revealed ionic structure consisting of three complex cations, [Co(phen)3]3+, two [V4O12]4- anions, one chloride and twenty seven lattice waters. Detailed structural and spectroscopic analyses of [Co(phen)3]3(V4O12)2Cl·27H2O show that the large anion is stabilized by the large cationic metal complex as there is preferred shape compatibility that leads to a large number of lattice stabilizing non-covalent interactions.

Moisture and contaminant transport in partially saturated, heterogeneous, layered sediments is typically anisotropic. Solute transport parameters, including dispersivity and the adsorption coefficient, and the modeled concentration of reactive minerals may depend on the direction of flow with respect to sedimentary layering. Reaction rates, in contrast, should be independent of flow direction. We determined the influence of flow direction on transport parameters for nonreactive (Br−) and reactive (cobalt ethylenediaminetetraacetic acid [Co(II)EDTA2−]) solutes under partially saturated conditions by imposing flow either parallel to or across sedimentary bedding in 11 intact sediment cores of various textures. Higher dispersivity of nonreactive tracers in parallel‐bed cores suggested fluid channeling through permeable layers, while low‐conductivity layers dampened channeling in cross‐bed samples. Rates of transformation of Co(II)EDTA2− into Co(III)EDTA− and of disassociation of Co2+ and EDTA4− were modeled assuming that the reaction rates were independent of the flow direction. The concentration of Mn oxides that was responsible for the transformation reaction was dependent on the flow direction, which governed the extent of contact between the solution and the solid phase. Similarly, the adsorption constants of Co(II)EDTA2− and Co(III)EDTA− were dependent on the flow direction but were also unique for each experiment. The modeled concentration of reactive minerals was the most sensitive parameter describing the reaction and transformation of Co(II)EDTA2−