Analysis and electroanalysis of perchlorate in water and food samples: a critical review.

Perchlorate, ClO4-, with diverse applications, has become one of the major contaminants in surface and groundwater sources. This highly soluble and stable anion poses a considerable threat to human health given that it contaminates drinking water, vegetables, milk, and other contaminated food products. ClO4- can impair the thyroid function; thus, drinking water with high levels of this anion is a severe problem worldwide. However, due to the high solubility, stability, and mobility of ClO4-, its remediation and monitoring remain a major challenge. Considering the various analytical methods, including electrochemistry, each method has advantages and disadvantages in terms of detection sensitivity, selectivity, analysis time, and cost. Also, sample preconcentration and clean-up must be performed for the analysis of more complex matrices such as food and biological samples to ensure a low detection limit and selectivity. Both ion chromatography (IC) and capillary electrophoresis (CE) coupled with electrochemical detection, in addition to liquid chromatography (LC)-mass spectrometry (MS), are expected to play key roles due to their lower detection limit with excellent sensitivities and selectivity. Herein, we also discuss the perspective on various electrode materials for the detection of ClO4- regarding whether ClO4- can be measured at the lowest levels with the highest selectivity.

Evaluation of hydrophilic interaction chromatography versus reversed-phase chromatography for fast aqueous species distribution analysis of Nickel(II)-Histidine complex species.

Nickel (Ni) is a trace heavy metal of importance in biological and environmental systems, with well documented allergy and carcinogenic effects in humans. With Ni(II) as the dominant oxidation state, the elucidation of the coordination mechanisms and labile complex species responsible for its transportation, toxicity, allergy, and bioavailability is key to understanding its biological effects and location in living systems. Histidine (His) is an essential amino acid that contributes to protein structure and activity and in the coordination of Cu(II) and Ni(II) ions. The aqueous low molecular weight Ni(II)-Histidine complex consists primarily of two stepwise complex species Ni(II)(His)1 and Ni(II)(His)2 in the pH range of 4 to 12. Four chromatographic columns, including the superficially porous Poro-shell EC-C18, Halo RP-amide and Poro-shell bare silica-HILIC columns, alongside a Zic-cHILIC fully porous column, were evaluated for the fast separation of the individual Ni(II)-Histidine species. Of these the Zic-cHILIC exhibited high efficiency and selectivity to distinguish between the two stepwise species Ni(II)His1 and Ni(II)His2 as well as free Histidine, with a fast separation within 120 s at a flow rate of 1 ml/min. This HILIC method utilizing the Zic-cHILIC column was initially optimized for the simultaneous analysis of Ni(II)-His-species using UV detection with a mobile phase consisting of 70% ACN and sodium acetate buffer at wwpH 6. Furthermore, the aqueous metal complex species distribution analysis for the low molecular weight Ni(II)-histidine system was chromatographically determined at various metal-ligand ratios and as a function of pH. The identities of Ni(II)His1 and Ni(II)-His2 species were confirmed using HILIC electrospray ionization- mass spectrometry (HILIC-ESI-MS) at negative mode.

Profiling of phenolic flavorings using core-shell reversed-phase liquid chromatography with electrochemical detection at a boron-doped diamond electrode.

A high-performance liquid chromatography (HPLC) method equipped with a boron-doped diamond (BDD) electrode was established for the simultaneous determination of phenol, 4-ethylphenol (4-EP), guaiacol, 4-ethylguaiacol (4-EG), 4-vinylguaiacol (4-VG), eugenol, and o-, m- and p-cresol. The separation was performed on a reversed-phase HALO C18 core-shell column (3.0 × 50 mm, 2.7 µm) with a mobile phase comprising 10 mM formate, pH 3, and 15% acetonitrile (ACN) (v/v), a flow rate of 1.5 mL/min, corresponding to a total run time of 9 min. The electrochemical detection (ECD) was set at +1.5 V vs. Pd/H2 in oxidative mode. Under optimized operating conditions, good linearity was obtained for the nine phenolics with corresponding coefficients of determination (R2) above 0.998. The limits of detection (LODs, S/N = 3) were 10 nM-1 µM, with an 80-fold increase in sensitivity for guaiacol achieved with ECD over ultraviolet (UV) detection. The sensitive and selective HPLC-ECD method was successfully applied for the identification and quantification of the nine phenolics in Islay, Irish, Scotch, and Highland whiskey samples, with significantly higher concentrations of the flavorings determined in Islay whiskey.

A review of oxyhalide disinfection by-products determination in water by ion chromatography and ion chromatography-mass spectrometry.

This paper is a review of ion chromatographic (IC) separations of inorganic oxyhalide disinfection by-products (DBPs) in water and beverages. The review outlines the chemical mechanisms of formation, regulation of maximum allowable levels, chromatographic column selection and speciation. In addition, this review highlights the application of IC coupled to mass spectrometry (MS) for trace and elemental composition analysis of oxyhalides, along with the analytical considerations associated to enable sensitive analysis. Furthermore, a review of literature concerning IC determination of inorganic oxyhalide DBPs in environmental matrices, including water, published since 2005 is presented, with a focus on MS detection, and a discussion on the relative performance of the methods. Finally some prospective areas for future research, including fast, selective, multi-analyte analysis, for this application are highlighted and discussed.

Organic solvent and temperature-enhanced ion chromatography-high resolution mass spectrometry for the determination of low molecular weight organic and inorganic anions.

There has recently been increased interest in coupling ion chromatography (IC) to high resolution mass spectrometry (HRMS) to enable highly sensitive and selective analysis. Herein, the first comprehensive study focusing on the direct coupling of suppressed IC to HRMS without the need for post-suppressor organic solvent modification is presented. Chromatographic selectivity and added HRMS sensitivity offered by organic solvent-modified IC eluents on a modern hyper-crosslinked polymeric anion-exchange resin (IonPac AS18) are shown using isocratic eluents containing 5-50 mM hydroxide with 0-80% methanol or acetonitrile for a range of low molecular weight anions (<165 Da). Comprehensive experiments on IC thermodynamics over a temperature range between 20-45 °C with the eluent containing up to 60% of acetonitrile or methanol revealed markedly different retention behaviour and selectivity for the selected analytes on the same polymer based ion-exchange resin. Optimised sensitivity with HRMS was achieved with as low as 30-40% organic eluent content. Analytical performance characteristics are presented and compared with other IC-MS based works. This study also presents the first application of IC-HRMS to forensic detection of trace low-order anionic explosive residues in latent human fingermarks.