Optimization and assessment of a sequential extraction procedure for calcium carbonate rocks

Sequential extraction analyses are widely used for the determination of element speciation in sediments and soils. Typical sequential extraction protocols were developed to extract from low-carbonate samples and therefore are not necessarily suitable for high-carbonate samples. In this study, we tested increased reagent to sample ratios to adjust an existing sequential extraction procedure to analyze high-CaCO3 samples with concentrations ranging from 70 to above 90 %. Complete dissolution of the CaCO3 phase, and a higher extraction efficiency of manganese associated with the carbonate phase, was achieved when using four times the original reagent to sample ratio in the 2nd extraction step. This increase of reagent did not compromise the extraction of subsequent phases as shown by unaffected Fe concentrations in a low-carbonate sample. Hence, an essential outcome was that increasing the solution to sample ratio did not lead to the dissolution of other sedimentary phases, such as hydrous and crystalline iron oxides or sulfides. Thus, compared to other extraction protocols that use a lower reagent to sample ratio in the carbonate dissolution step, the new protocol allowed the complete extraction of oxide and sulfide phases in the following extraction steps. Furthermore, the study demonstrated the benefit of replacing Na-acetate with NH4-acetate to extract exchangeable ions and carbonates. We observed increased intensities for several analytes, i.e., trace metals such as Mo and As, due to less suppression of the analyte signal by NH4-acetate than by Na-acetate during analysis by inductively coupled plasma optical emission spectrometry (ICP-OES).

A Sensitive and Specific ESI-Positive LC–MS/MS Method for the Quantitation of Estrogens in Human Serum in Under Three Minutes

Amplifex Diene reagent was employed to derivatize estradiol (E2) to enhance the analyte signal at low picogram concentrations. This derivatization enabled measurement of E2 (and other estrogens) in ESI+ mode, earlier retention times for analytes than other methods, avoidance of MS harmful ammonium fluoride in mobile phases, and an LLOQ below 1 pg/mL. The sample preparation workflow involved liquid–liquid extraction followed by Amplifex Diene derivatization for 10 min at ambient temperature. Samples were chromatographed using a standard C18 column and analyzed using a SCIEX 6500+ mass spectrometer. The assay calibrators were prepared in-house, traceable to certified reference materials, and ranged from 1.29 to 624 pg/mL. A method comparison to samples from the CDC HoSt program yielded a correlation coefficient of 0.9858 and bias of −1.37%. The LLOQ using certified reference material was 0.66 pg/mL. The intra-run precision was <9.00% for low- and high-level samples, whereas the inter-run precision was 15.2 and 5.43% for low- and high-level samples, respectively. No interference from other clinically relevant steroids was found. Amplifex Diene derivatized E2 and estrone (E1) was found to be stable for over 6 months, both refrigerated and frozen.

ATR-FTIR Spectroscopy, a New Non-Destructive Approach for the Quantitative Determination of Biogenic Silica in Marine Sediments

Biogenic silica is the major component of the external skeleton of marine micro-organisms, such as diatoms, which, after the organisms death, settle down onto the seabed. These micro-organisms are involved in the CO2 cycle because they remove it from the atmosphere through photosynthesis. The biogenic silica content in marine sediments, therefore, is an indicator of primary productivity in present and past epochs, which is useful to study the CO2 trends. Quantification of biosilica in sediments is traditionally carried out by wet chemistry followed by spectrophotometry, a time-consuming analytical method that, besides being destructive, is affected by a strong risk of analytical biases owing to the dissolution of other silicatic components in the mineral matrix. In the present work, the biosilica content was directly evaluated in sediment samples, without chemically altering them, by attenuated total reflection Fourier transform infrared (ATR-FTIR) spectroscopy. Quantification was performed by combining the multivariate standard addition method (MSAM) with the net analyte signal (NAS) procedure to solve the strong matrix effect of sediment samples. Twenty-one sediment samples from a sediment core and one reference standard sample were analyzed, and the results (extrapolated concentrations) were found to be comparable to those obtained by the traditional wet method, thus demonstrating the feasibility of the ATR-FTIR-MSAM-NAS approach as an alternative method for the quantification of biosilica. Future developments will cover in depth investigation on biosilica from other biogenic sources, the extension of the method to sediments of other provenance, and the use higher resolution IR spectrometers.

Optimization of ZnO Nanorod-Based Surface Enhanced Raman Scattering Substrates for Bio-Applications

Nanorods based on ZnO for surface enhanced Raman spectroscopy are promising for the non-invasive and rapid detection of biomarkers and diagnosis of disease. However, optimization of nanorod and coating parameters is essential to their practical application. With the goal of establishing a baseline for early detection in biological applications, gold-coated ZnO nanorods were grown and coated to form porous structures. Prior to gold deposition, the grown nanorods were 30–50 nm in diameter and 500–600 nm in length. Gold coatings were grown on the nanorod structure to a series of thicknesses between 100 and 300 nm. A gold coating of 200 nm was found to optimize the Rhodamine B model analyte signal, while performance for rat urine depended on the biomarkers to be detected. These results establish design guidelines for future use of Au-ZnO nanorods in the study and early diagnosis of inflammatory diseases.

Study on carbon-induced signal enhancement in inductively coupled plasma mass spectrometry: an approach from the spatial distribution of analyte signal intensities

This study proposed a novel approach for quantifying carbon-induced signal enhancement in ICP-MS considering the spatial distribution of analyte signal intensities.

Determination of the pKa for caffeic acid in mixed solvent using the net analyte signal method and ab initio theory

Due to the biological effects of phenolic acid components, polyphenol-rich foods are a significant part of human and animal diets. In this study, the acidity constants of caffeic acid (3,4-dihydroxycinnamic acid) in binary mixtures of ethanol?water were determined spectrophotometrically using the introduced net analyte signal (NAS) algorithm and an ab initio quantum mechanical method. The NAS is an efficient chemometric algorithm for analysis of acid?base equilibrium systems by a spectrophotometric method. At different pH values, the distribution of acid species is obtained from an absorption data matrix and this procedure enabled the pKa of caffeic acid to be obtained alternatively. The results showed that pKa1 (4.02, 4.26, 4.39, 4.57 and 5.11) and pKa2 (8.43, 8.68, 8.79, 9.00 and 9.34) were increased by increasing the percent ethanol in water (0, 10, 20, 30 and 40 vol. %) and these results were in agreement with the results of the Gaussian method. The ab initio calculated Gibbs energy change showed that para-hydroxy group is more acidic than meta-hydroxy group. The red shifts of different species of caffeic acid obtained using the ab initio quantum mechanical method are in good agreement with the results of UV?Vis spectroscopy.