Adaptable infrared surface plasmon resonance spectroscopy accessory.

A second generation prototype enabling surface plasmon resonance spectroscopic measurements in the infrared (IR) range is described. The new design (v2) uses the optical train (optics and detector) within conventional FT-IR spectrometers by confining dimensions of the accessory to space available within the sample compartment of the spectrometer. The v2 accessory builds upon knowledge gained from a previous version that was based on a modified commercial variable angle spectroscopic accessory and addresses observed limitations of the original design-improved temporal stability and measurement acquisition speed, crucial to biomolecular binding studies, as well as optical flexibility, a requirement for investigations of novel plasmon-supporting materials. Different aspects of the accessory, including temporal stability, mechanical resilience, and sensitivity to changes in refractive index of a sample were evaluated and presented in this contribution.

Percutaneous interventions in subclavian artery-to-contralateral subclavian vein "necklace" hemodialysis grafts: experience in five patients.

PURPOSE: To describe clinical outcomes of endovascular interventions in the setting of thrombosis or dysfunction of anterior chest wall ("necklace") arteriovenous (AV) hemodialysis grafts. MATERIALS AND METHODS: Eight percutaneous interventions (balloon angioplasty, pharmacologic thrombolysis, and mechanical thrombectomy) were performed in five patients with anterior chest wall AV grafts. Primary, assisted, and secondary patencies, as well as technical success and complication rates, were determined. RESULTS: The technical success rate of percutaneous interventions in re-establishing a normal blood flow pattern within the AV grafts was 100%. Primary patency ranged from one to 23 months (median, 5 months). Primary assisted patency and secondary patency were 36 months and 8 months, respectively, in two patients who underwent more than one intervention. Postintervention access patency ranged from 5 to 36 months (median, 9 months), whereas graft lifetime ranged from 12 to 45 months (median, 24 months). There were no complications related to revascularization procedures. CONCLUSION: Percutaneous interventions can be performed safely and effectively in anterior chest wall AV grafts. Technical success and long-term patency rates appear to be similar to those of percutaneous interventions in upper-extremity hemodialysis AV grafts.

Statistical validation of sulfate quantification methods used for analysis of acid mine drainage.

Turbidimetric method (TM), ion chromatography (IC) and inductively coupled plasma atomic emission spectrometry (ICP-AES) with and without acid digestion have been compared and validated for the determination of sulfate in mining wastewater. Analytical methods were chosen to compare the performance of a portable field turbidimetric instrument and to validate the underlying assumption utilized in conversion of total sulfur to sulfate during ICP-AES analysis. Accuracy and precision of analytical techniques were compared to one another using control and field samples collected from a mine site using the Bonferroni multiple comparison test. Effects of sample dilution, filter pore size and acidification on sulfate quantification were also studied. The results showed that IC and ICP-AES with and without acid digestion provided excellent recoveries in the case of control samples (within 90-110%). These analytical methods also showed lower relative standard deviation for both control and field samples. On the other hand, performance of the turbidimetric method was severely affected by sample dilution and acidification, and also revealed poor sulfate recoveries for control samples ranging from 0 to 83.5%. Analysis of variance (ANOVA) was used to evaluate the response (sulfate concentration) obtained from factorial design. Analytical method had significant effect (P<0.0001) on the sulfate quantification. The interaction between determination method and sample dilution was more significant than other two-way interactions.

Comparative evaluation of short-term leach tests for heavy metal release from mineral processing waste.

Evaluation of metal leaching using a single leach test such as the Toxicity Characteristic Leaching Procedure (TCLP) is often questionable. The pH, redox potential (E(h)), particle size and contact time are critical variables in controlling metal stability, not accounted for in the TCLP. This paper compares the leaching behavior of metals in mineral processing waste via short-term extraction tests such as TCLP, Field Leach Test (FLT) used by USGS and deionized water extraction tests. Variation in the extracted amounts was attributed to the use of different particle sizes, extraction fluid and contact time. In the controlled pH experiments, maximum metal extraction was obtained at acidic pH for cationic heavy metals such as Cu, Pb and Zn, while desorption of Se from the waste resulted in high extract concentrations in the alkaline region. Precipitation of iron, caused by a pH increase, probably resulted in co-precipitation and immobilization of Cu, Pb and Zn in the alkaline pH region. A sequential extraction procedure was performed on the original waste and the solid residue from the E(h)-pH experiments to determine the chemical speciation and distribution of the heavy metals. In the as-received waste, Cu existed predominantly in water soluble or sulfidic phases, with no binding to carbonates or iron oxides. Similar characteristics were observed for Pb and Zn, while Se existed mostly associated with iron oxides or sulfides. Adsorption/co-precipitation of Cu, Se and Pb on precipitated iron hydroxides was observed in the experimental solid residues, resulting in metal immobilization above pH 7.

Determining speciation of Pb in phosphate-amended soils: method limitations.

Determining the effectiveness of in situ immobilization for P-amended, Pb-contaminated soils has typically relied on non-spectroscopic methods. However in recent years, these methods have come under scrutiny due to technical and unforeseen error issues. In this study, we analyzed 18 soil samples via X-ray diffraction (XRD), selective sequential extraction (SSE), and a physiologically based extraction test (PBET). The data were compared against each other and to previous data collected for the soil samples employing X-ray absorption fine structure spectroscopy coupled with linear combination fitting (XAFS-LCF), which spectroscopically speciates and quantifies the major Pb species in the samples. It was observed that XRD was incapable of detecting pyromorphite, the hopeful endpoint of the immobilization strategy for reduced Pb bioavailability in our studies. Further, the SSE and PBET extraction methods demonstrated an increase of recalcitrant Pb forms in comparison to the XAFS-LCF results suggesting that SSE and PBET methods induced the precipitation of pyromorphite during the extraction procedures. The theme of this paper illustrates the experimental concerns of several commonly employed methods to investigate immobilization strategies of amended, metal-contaminated systems which may not be in true equilibrium. We conclude that appropriate application of spectroscopic methods provides more conclusive and accurate results in environmental systems (i.e., Pb, Zn, Cd, etc.) examining P-induced immobilization.