Double gradient ion chromatography on a short carboxybetaine coated monolithic anion exchanger

An ultra-short 1.0 x 0.46 cm carboxybetaine coated monolithic anion exchanger has been used with a new double gradient ion chromatography (DG-IC) technique. The novel monolithic column can be used with flow rate gradients giving excellent peak efficiencies, and retention times can be simultaneously reduced through combining flow gradients with an eluent pH gradient.     

Iminodiacetic acid functionalised monolithic silica chelating ion exchanger for rapid determination of alkaline earth metal ions in high ionic strength samples

Iminodiacetic acid has been covalently bonded to a bare silica monolith to produce the first reported high-performance monolithic chelating ion exchange column. Using the new column, separation and determination of traces of alkaline earth metal ions (low ppm) in high ionic strength samples (up to 2 M NaCl and KCl brines), could be achieved in under 40 s. At an eluent flow rate of 4 mL min(-1) retention time precision was < 1.2% (n = 9) for Mg(II) and Ca(II), with detector linearity (n = 5) over the range 2-10 mg L(-1) of between R2 = 0.985 and R2 = 0.995. In 1 M KCl and NaCl brine samples, detection limits of 0.2 mg L(-1) were possible.     

Determination of trace alkaline earth metals in brines using chelation ion chromatography with an iminodiacetic acid bonded silica column

The chromatographic behaviour of alkaline earth metals on iminodiacetic acid bonded silica was studied. It was found that the ionic strength of the eluent greatly affected both retention time and selectivity by controlling the extent to which either simple ion exchange or surface complexation was responsible for retention. With a 0.1 M KNO3 eluent, the retention order was Mg(II), Sr(II), Ca(II) and Ba(II), indicating a strong contribution to retention from ion exchange. However, when using a 1.5 M KNO3 eluent, Ba(II) was found to elute first, indicating complexation to be more dominant under these conditions (pH 4.2). The effect of the ionic strength of the sample was also studied and it was found that by matching the eluent cation with that of the sample matrix, efficient separations of alkaline earth metals in 1.0 M NaCl and KCl brines could be obtained without matrix system peaks. Using post-column reaction with o-cresolphthalein complexone, trace levels of Ca(II) and Mg(II) were determined in medicinal NaCl saline solution and laboratory-grade KCl.     

Rapid, low pressure, and simultaneous ion chromatography of common inorganic anions and cations on short permanently coated monolithic columns

Short permanently coated reversed-phase silica based monolithic columns have been investigated for the rapid separation of inorganic anions and cations. One 2.5 x 0.46 cm column was permanently coated with didodecyldimethylammonium (DDAB), for anion analysis; and a second 5.0 x 0.46 cm column was coated with dioctylsulphosuccinnate (DOSS), for cation analysis. The use of a single combined eluent of 2.5 mM phthalate/1.5 mM ethylenediamine, at flow rates of between 4.0 and 8.0 mL/min, resulted in the rapid separation of 8 anions (in under 100 s) and 5 cations (in under 100 s) on the above columns when used individually, with detection limits for common anions ranging from approximately 0.25 to 5 mg/L, and between 2.5 and 50 mg/L for alkaline earth metals, by direct and indirect conductivity detection, respectively. However, with both columns subsequently connected in parallel, with the eluent delivered using a flow splitter from a single isocratic pump, the simultaneous analysis of anions and cations was also possible, based on a single conductivity detector. The potential of this system for the rapid, complete screening of water samples for multiple common anions and cations is shown.     

Retention of alkali,alkaline earth and transition metals on an itaconic acid cation-exchange column. Eluent pH,ionic strength and temperature effects upon selectivity

The unusual selectivity of a methylene succinic (itaconic) acid modified polymeric column was investigated for the separation of alkali, alkaline earth, transition and heavy metals employing non-chelating inorganic eluents. The retention of selected metal ions on the column was investigated with simple HNO3 eluents and eluents prepared from KNO3 and KCl salts of varying pH (adjusted using HNO3). From these studies both the effect of eluent ionic strength and pH upon retention was evaluated for the itaconic acid stationary phase. The results obtained showed that despite slow exchange kinetics causing poor efficiencies, acceptable baseline separations of selected alkaline earth and transitions could be obtained under optimum conditions (the baseline separation of Mg(II), Ca(II), Mn(II), Cd(II), Zn(II) and Co(II) was possible using a 15 mM KNO3-5 mM KCl eluent at pH 3.50 in under 25 min). The use of an simple ionic strength step gradient was shown that facilitated the addition of Pb(II) to the above group of metal ions. An investigation into the effect of temperature upon peak efficiency and retention showed increased column temperature could be used to improve the resolution of closely eluting metal ions such as Ca(II) and Sr(II) and Ca(II) and Mn(II).     

Fast ion chromatography of inorganic anions and cations on a lysine bonded porous silica monolith

A 0.46 cm x 10.0 cm silica monolith column was modified through the in situ covalent attachment of lysine (2,6-diaminohexanoic acid) groups. Due to the zwitterionic nature of the resultant stationary phase, the modified monolithic column contained both cation and anion exchange capacity. In the case of cation exchange, the capacity was found to be relatively low at between 5 and 6.5 micromoles Me2+ per column. However, as expected, the lysine monolith exhibited a higher anion exchange capacity at 12-13 micromoles A- per column (at pH 3.0), which was found to be dependent upon column pH, due to the dissociation of the weak acid carboxylic acid groups. High-performance separations of transition metal cations and inorganic anions were achieved using the modified monolith, with the effects of eluent concentration, pH and flow rate evaluated. Using elevated flow rates of up to 5 mL/min the separation of nitrite, bromate, bromide, nitrate, iodide and thiocyanate was possible in approximately 100 s with peak efficiencies of between 50 and 100,000 N/m and retention time %RSD of under 0.3%.     

Ion chromatographic analysis of cyanate in gold processing samples containing large concentrations of copper(I) and other metallocyanide complexes

An ion chromatographic (IC) method was developed for the determination of cyanate in gold cyanidation samples containing large concentrations of metallo-cyanide complexes. The analysis was performed on a Waters HC IC-Pak A anion-exchange column with an anthranilic acid eluent, with detection achieved using indirect UV at 355 nm. Two procedures were developed for removal of the metallo-cyanide complexes prior to the IC analysis. The first was a manual off-line method which used solid-phase extraction cartridges containing a strong anion-exchange resin to trap the complexes and to then enable determination of cyanate without interference. In the second approach, an automated on-line method was developed which used an anion-exchange guard column to trap the complexes and a column switching valve to allow backflushing of the cyanate from the guard column. This enabled the total analysis to be performed in a time of 10–14 min, depending on the sample composition. Finally, a comparison of results obtained by the standard Kjeldahl nitrogen method for cyanate and the IC method revealed an interference in the Kjeldahl method for samples containing large concentrations of Cu(I)-cyanide complexes.     

Zwitterionic ion chromatography with carboxybetaine surfactant-coated particle packed and monolithic type columns

Both particle packed (25 cm x 0.46 cm I.D. SUPELCOSIL 5 microm C18) and monolithic type (10 cm x 0.46 cm I.D. Merck Chromolith Performance C18) reversed-phase substrates were dynamically coated with a carboxybetaine type zwitterionic surfactant ((dodecyldimethyl-amino) acetic acid) and investigated as stationary phases for use in zwitterionic ion chromatography (ZIC). Investigations into eluent concentration and pH were carried out using KCl eluents containing 0.2 mM of the carboxybetaine surfactant to stabilise the column coatings. It was found that eluent concentration decreased anion retention whilst simultaneously increasing peak efficiencies, which may be due to the dissociation of intra- and inter-molecular salts of the carboxybetaine surfactant under higher ionic strength conditions. The Effect of eluent pH was an increase in anion retention with decreased eluent pH due to the increased protonation of the weak acid terminal group of the carboxybetaine, causing both a relative increase in the positive charge of the stationary phase and less repulsion of the anions by the dissociated weak acid group. The carboxybetaine-coated monolithic phase was applied to rapid anion separations using elevated flow rates and flow rate gradients.     

Recent strategies to enhance the performance of polymer monoliths for analytical separations

This review summarizes recent developments made in the incorporation of functional materials into organic polymer monoliths, together with new monolithic forms and formats, which enhance their application as supports and stationary phase materials for sample preparation and chromatographic separations. While polymer monoliths are well‐known supports for the separation of large molecules, recent developments have been made to improve their features for the separation of small molecules. The selectivity and performance of organic polymer monoliths has been improved by the incorporation of different materials, such as metal‐organic frameworks, covalent organic frameworks, or other types of nanostructured materials (carbon nanohorns, nanodiamonds, polyoxometalates, layered double hydroxides, or attapulgite). The surface area of polymer monoliths has been significantly increased by polymer hypercrosslinking, resulting in increased efficiency when applied to the separation of small molecules. In addition, recent exploration of less conventional supports for casting polymer monoliths, including photonic fibres and 3D printed materials, has opened new avenues for the applications of polymer monoliths in the field of separation science. Recent developments made in these topics are covered, focusing on the strategies followed by the authors to prepare the polymer monoliths and the effect of these modifications on the developed analytical applications.     

Low-pressure gradient micro-ion chromatography with ultra-short monolithic anion exchange column

A 1.0 x 0.4 cm silica based monolithic anion exchanger has been produced and evaluated for use within a miniature gradient suppressed ion chromatography system based upon low-pressure micro-scale peristaltic pumps.