Tunable separation of anions and cations by column switching in ion chromatography

A convenient ion chromatography method has been proposed for the routine and simple determination of anions (Cl⁻, SO₄²⁻ and NO₃⁻) and/or cations (Na⁺, NH₄⁺, K⁺, Mg²⁺ and Ca²⁺) using a single pump, a single eluent and a single detector. The present system used cation-exchange and anion-exchange columns connected in series via two 6-port switching valves or a single 10-port valve. The connection order of the ion-exchange columns could be varied by switching the valve(s). The present system therefore allowed the separation of either cations or anions in a single chromatographic run. While one ion-exchange column is being operated, the other ion-exchange column is being conditioned, i.e., the columns are always ready for analysis at any time. When 2.4 mM 5-sulfosalicylic acid was used as the eluent, the three anions and the five cations could be separated on the anion-exchange column and cation-exchange column, respectively. In order to obtain the separations of the target ions, the injection valve was placed between the two columns. Complete separations of the above anions or cations were demonstrated within 10 min each. The detection limits at S/N = 3 were 19-50 ppb (μg/l) for cations and 10-14 ppb for anions. The relative standard deviations of the analyte ions were less than 1.1, 2.9 and 2.8% for retention time, peak area and peak height, respectively. This proposed technique was applied to the determination of common anions and cations in river water samples.     

Peak parking technique for the simultaneous determination of anions and cations

An ion chromatography method is described for the simultaneous determination of anions (Cl^–, NO₃^–, and SO₄^2–) and cations (Na⁺, NH₄⁺, K⁺, Mg²⁺, and Ca²⁺) using a single pump, a single eluent and a single detector. An anion-exchange column modified with chondroitin sulfate C facilitated the elution of the above three anions using 5 mM tartaric acid as the eluent in isocratic mode, whereas the same eluent facilitated the separation of the above five cations on a commercially-available cation-exchange column. The separation columns were connected in series via two six-port switching valves, so the required cation-exchange or anion-exchange separation could be carried out by selecting the appropriate positions for the switching valves. The separations were completed in 30 min.     

An improved flow analysis-ion chromatography method for determination of cationic and anionic species at trace levels in Antarctic ice cores

A method was developed for the quantitative determination of cations and anions in Antarctic ice cores at μg L⁻¹ and sub-μg L⁻¹ levels by ion chromatography (IC), after ultra-clean decontamination procedures. Strict manipulation and decontamination procedures were used in sub-sampling, in order to minimise sample contamination. Na⁺, NH₄⁺, K⁺, Mg²⁺ and Ca²⁺ were determined by 12-min isocratic elution (H₂SO₄ eluent). Contemporaneously, in a parallel device, F⁻, MSA (methanesulfonic acid), Cl⁻, NO₃⁻ and SO₄²⁻ were analysed in a single 12-min run with multiple-step elution using Na₂CO₃/NaHCO₃ as eluent. Melted ice samples were pumped from their still-closed containers (polystyrene accuvettes with polyethylene caps), shared between the two ion chromatographic systems, online filtered (0.45 μm Teflon membrane) and pre-concentrated (anions and cations pre-concentration columns) using a flow analysis system, thus avoiding uptake of contaminants from the laboratory atmosphere. Sensitivity, linear range, reproducibility and detection limit were evaluated for each chemical species. Anion or cation detection limits ranged from 0.01 to 0.15 μg L⁻¹ by using a relatively small sample volume (1.5 mL). Such values are significantly lower than those reported in literature for almost all the components. These methods were successfully applied to the analysis of cations and anions at trace levels in the Dome C ice core. The composition of the atmospheric aerosol for the last 850 kyr was reconstructed by high-resolution continuous chemical stratigraphies. Concentration trends in the last nine glacial-interglacial climatic cycles were shown and briefly discussed.     

Portable,lightweight, low power,ion chromatographic system with open tubular capillary columns

Basic operation principles of a lightweight, low power, low cost, portable ion chromatograph utilizing open tubular ion chromatography in capillary columns coated with multi-layer polymeric stationary phases are demonstrated. A minimalistic configuration of a portable IC instrument was developed that does not require any chromatographic eluent delivery system, nor sample injection device as it uses gravity-based eluent flow and hydrodynamic sample injection adopted from capillary electrophoresis. As a detection device, an inexpensive commercially available capacitance sensor is used that has been shown to be a suitable substitute for contactless conductivity detection in capillary separation systems. The built-in temperature sensor allows for baseline drift correction typically encountered in conductivity/capacitance measurements without thermostating device. The whole instrument does not require any power supply for its operation, except the detection and data acquisition part that is provided by a USB port of a Netbook computer. It is extremely lightweight, its total weight including the Netbook computer is less than 2.5 kg and it can be continuously operated for more than 8 h. Several parameters of the instrument, such as detection cell design, eluent delivery systems and data treatment were optimized as well as the composition of eluent for non-suppressed ion chromatographic analysis of common inorganic cations (Na⁺, NH₄⁺, K⁺, Cs⁺, Ca²⁺, Mg²⁺, transition metals). Low conductivity eluents based on weakly complexing organic acids such as tartaric, oxalic or pyridine-2,6-dicarboxylic acids were used with contactless capacitance detection for simultaneous separation of mono- and divalent cations. Separation of Na⁺ and NH₄⁺ cations was optimized by addition of 18-crown-6 to the eluent. The best separation of 6 metal cations commonly present in various environmental samples was accomplished in less than 30 min using a 1.75 mM pyridine-2,6-dicarboxylic acid and 3 mM 18-crown-6 eluent with excellent repeatability (below 2%) and detection limits in the low micromolar range. The analysis of field samples is demonstrated; the concentrations of common inorganic cations in river water, mineral water and snow samples were determined.     

Ion-exclusion chromatography with the direct UV detection of non-absorbing inorganic cations using an anion-exchange conversion column in the iodide-form

An ion-exclusion chromatographic method for the direct UV detection of non-absorbing inorganic cations such as sodium (Na⁺), ammonium (NH₄⁺) and hydrazine (N₂H₅⁺) ions was developed by connecting an anion-exchange column in the I⁻-form after the separation column. For example, NH₄⁺ is converted to a UV-absorbing molecule, NH₄I, by the anion-exchange column in the I⁻-form after the ion-exclusion separation on anion-exchange column in the OH⁻-form with water eluent. As a result, the direct UV detection of Na⁺, NH₄⁺ and N₂H₅⁺ could be successfully obtained as well as the well-resolved separation. The calibration graphs of the analyte cations detected with UV at 230 nm were linear in the range of 0.001-5.0 mM. The detection limits at S/N = 3 of the cations were below 0.1 μM. This method was applied to real water analysis, the determination of NH₄⁺ in river and rain waters, or that of N₂H₅⁺ in boiler water, with the satisfactory results. This could be applied also to low- or non-absorbing anions such as fluoride or hydrogencarbonate ions by the combination of a weakly acidic cation-exchange resin in the H⁺-form as the separation column and the anion-exchange conversion column.     

Hydrogen bonded H3O, H2O, HF, F in fluoride metalates (Al, Cr, Fe, Zr, Ta) templated with tren (tris-(2-aminoethyl)amine)

The environment of H₃O⁺, H₂O, HF and F⁻ species (non-bonded to metals) is considered in fluoride metalates which crystallise from the (Al(OH)₃, Cr(OH)₃, FeF₃, ZrF₄, Ta₂O₅)-tren-HF_aq·-ethanol systems (microwave heating at 190 °C during 1 h). The presence of (H₃O)(H₂O)₆⁺ clusters or H₃O⁺ cations, of isolated or associated H₂O molecules, of (HF₂)⁻ and F⁻ anions is evidenced. The thermal stability of the solids depends strongly on the nature of the hydrogen-bonded species associated with the preceding cations or anions and on the formation of water ribbons or layers.     

Preparation and properties of a new solid state borate ion selective electrode and its application

A new borate ion selective electrode using solid salts of Ag₃BO₃, Ag₂S and Cu₂S has been developed. Detailed information is provided concerning the composition, working pH and conditioning of the electrode. An analytically useful potential change occurred from 1 × 10⁻⁶ to 1 × 10⁻¹ M borate ion. The slope of the linear portion was 31 ± 2 mV/10-fold changes in borate concentration. The measurements were made at constant ionic strength (0.1 M NaNO₃) and at room temperature. The effect of Cl⁻, Br⁻, NO₃⁻, SO⁼₄, H₂PO₄⁻ anions and K⁺, Na⁺, Cu²⁺, Ag⁺, Ca²⁺ cations on borate response is evaluated and it was found that only Ag⁺ had a small interference effect. The lifetime of the electrode was more than two years, when used at least 4-5 times a day, and the response time was about 20-30 s. Borate content in waste water of borax factory, tap water of a town situated near to the borax factory and city tap water far from these mines were also determined. The validation was made with differential pulse polarography for the same water sample, and high consistency was obtained.     

On‐site sampling of inorganic contamination on the metal surface and analysis with capillary electrophoresis

Pipes are the primary structural elements used for transporting fluid in various industries. The most common damage mechanism is corrosion, which occurs in pipes surface of turbine. The corrosive compounds for pipes are inorganic ion (Na⁺, Cl^?, NH₄⁺, NO₃^?, etc.) and grinding oil. For rapid and quantitative detection of inorganic ions on site, more reliable and reproducible analytical methods are demanded. A highly efficient solid–liquid sampling collection system is introduced in this work. Papering on the sample surface, inorganic cations and anions were simultaneously collected and analyzed by capillary electrophoresis with indirect ultraviolet detection. As a result, five cations (Na⁺, K⁺, NH₄⁺, Ca²⁺, Mg²⁺) and three anions (Cl^?, NO₃^?, SO₄^2?) were completely separated. The efficiency of the sampling and ability of capillary electrophoresis analysis were presented by the determination of trace‐level (mg/m²) contaminants. The recoveries of cations and anions on the paper from metal surface were between 86.6 and 107.2%, and the relative standard deviations were less than 12.85%.     

Ion chromatographic determination of organic acids in food samples using a permanent coating graphite carbon column

From the viewpoint of a graphite carbon column with excellent durability, it was applied to the ion chromatography (IC) of several organic acids. The carbon column was permanently coated with the cetyltrimethylammonium (CTMA) ion, and the elution behaviors of several organic acids (acetic acid, lactic acid, succinic acid, malic acid, tartaric acid, citric acid) and inorganic anions (Cl⁻, NO₂⁻, NO₃⁻, SO₄²⁻) were examined according to a non-suppressed IC coupled with conductivity detector, when an ion-exchange ability was given to the graphite carbon column. When salicylic acid and sodium salicylate were used as a mobile phase, each organic acid are analyzed approximately 10 min. But the separation of malic acid, chloride and nitrite was difficult. When benzoic acid and 2-amino-2-hydroxymethyl-1,3-puropanediol (tris aminomethane) were used as a mobile phase, tartaric acid and citric acid, etc. with large valency showed tendency to which the width of each peaks extended and retention time increased. However, it was possible to separate excellently for the analytes detected within 10 min. The developed method was then applied to the determination of organic acids in several food samples.     

Polydiphenylamine-dodecyl sulfate films for the simultaneous amperometric determination of electroinactive anions and cations in ion-exclusion cation-exchange chromatography

An amperometric detector with two working electrodes both modified with polydiphenylamine-dodecyl sulfate (PDPA-DS) was successfully used for the simultaneous determination of electroinactive anions (SO₄ ^2–, Cl^–, NO₃ ^–) and cations (Na⁺, NH₄ ⁺ and K⁺) in single-column ion-exclusion cation-exchange chromatography (IEC-CEC). The PDPA-DS chemical modified electrode (CME) was based on the incorporation of dodecyl sulfate (DS) into PDPA by electropolymerization of diphenylamine in the presence of sodium dodecyl sulfate. The electrochemical responses against the anions and cations at the PDPA-DS CME in differential pulse voltammetry were studied. A set of well-defined peaks of electroinactive anions and cations were obtained. The anions and cations were detected conveniently and reproducibly in a linear concentration range 0.01–5.0 mmol/L and their detection limits were in the range 5–9 μmol/L at a signal-to-noise ratio of 3 (S/N = 3). The proposed method was quick, sensitive and simple and was successfully applied to the analysis of lake water samples. The working electrode was stable over one week period of operation with no evidence of chemical and mechanical deterioration.     

Serial separation of cations and anions by ion chromatography using the peak parking technique and sulfosalicylic acid as the eluent

An improvement of the peak parking technique is described for the serial determination of cations (Na⁺, , K⁺, Mg²⁺, and Ca²⁺) and anions (Cl⁻, , and ) using a single pump, a single eluent and a single detector. The present system used commercially-available unmodified cation exchange and anion exchange columns, which were attached to each switching valve. When 1.75 mM 5-sulfosalicylic acid was used as the eluent, serial separation of the above cations and anions was achieved in less than 20 min. The proposed ion chromatographic method was successfully applied to the serial determination of cations and anions in tap water and river water samples. The limits of detection at S/N=3 for an injection of 20 μl were 16–68 ppb (μg/l) for cations and 15–28 ppb for anions.     

Capillary ion electrophoresis-capacitively coupled contactless conductivity detection of inorganic cations in human saliva on a polyvinyl alcohol-coated capillary

Capillary ion electrophoresis–capacitively coupled contactless conductivity detection (CIE-C4D) with a polyvinyl alcohol chemically coated capillary (PVA capillary) was used to analyze inorganic cations (Na⁺, K⁺, NH₄⁺, Mg²⁺, and Ca²⁺) commonly found in human saliva. The PVA capillary, which was made by our laboratory, minimized electro-osmotic flow in the wide pH range of the background electrolyte (BGE), and the PVA layer adsorbed to capillary wall did not affect the conductimetric background level. In this study, we determined an optimized BGE of 30 mM lactic acid/histidine plus 3 mM 18-crown-6 for the CIE-C4D system using the PVA capillary, which could simultaneously improve the separation of Mg²⁺ and Ca²⁺ from Na⁺ and that of K⁺ from NH₄⁺. This system obtained highly reproducible separation of cations in human saliva samples within 8 min at 20 kV without deprotonation. The quantifiability of cations in human saliva samples on the CIE-C4D system was demonstrated through identification by ion chromatography with satisfactory results.     

Aluminum phosphate dispersed on a cellulose acetate fiber surface: Preparation, characterization and application for Li, Na and K separation

Cellulose acetate fibers with supported highly dispersed aluminum phosphate were prepared by reacting aluminum-containing cellulose acetate (Al₂O₃=3.5 wt.%; 1.1 mmol g⁻¹ aluminum atom per gram of the material) with phosphoric acid. Solid-state NMR spectra (CPMAS ³¹P NMR) data indicated that HPO₄²⁻ is the species present on the fiber surface. The specific concentration of acidic centers, determined by ammonia gas adsorption, is 0.50 mmol g⁻¹. The ion exchange capacities for Li⁺, Na⁺ and K⁺ ions were determined from ion exchange isotherms at 298 K and showed the following values (in mmol g⁻¹): Li⁺=0.03, Na⁺=0.44 and K⁺=0.50. The H⁺/Li⁺ exchange corresponds to the model of the ideal ion exchange with a small value of the corresponding equilibrium constant K=1.1×10⁻². Due to the strong cooperative effect, the H⁺/Na⁺ and H⁺/K⁺ ion exchange is non-ideal. These ion exchange equilibria were treated with the use of models of fixed bi- or tridentate centers, which consider the surface of the sorbent as an assemblage of polyfunctional sorption centers. Both the observed ion exchange capacities with respect to the alkaline metal ions and the equilibrium constants were discussed by taking into consideration the sequence of the ionic hydration radii for Li⁺, Na⁺ and K⁺. The matrix affinity order for the ions decreases as the hydration radii of the cations increase, i.e. Li⁺>Na⁺>K⁺. The high values of the separation factors S_Na⁺/Li⁺ and S_K⁺/Li⁺ (up to several hundred) provide quantitative separation of Na⁺ and K⁺ from Li⁺ from a mixture containing these three ions.     

Application of pure silica gel as cation-exchange stationary phase in lon chromatography with indirect photometric detection for common mono-and divalent cations using aromatic monoamines as eluents

Summary A pure silica gel (Pia Seed 5S-60-SIL), synthesized by the hydrolysis of pure tetraethoxysilane [Si(OCH₂CH₃)₄], was applied as a cation-exchange stationary phase in ion chromatography with indirect photometric detection for common mono-and divalent cations (Li⁺, Na⁺, NH₄ ⁺, K⁺, Mg²⁺, and Ca²⁺) using various protonated aromatic monoamines (tyramine [4-(2-aminethyl) phenol], benzylamine, phenylethylamine, 2-methylpyridine and 2,6-dimethylpyridine) as eluet ions. When using 0.75 mM tyramine-0.25 mM oxalic acid-1.5 mM 18-crown-6 (1,4,7,10,13,16-hexaoxacyclooctadecane) at pH 5.0 as the eluent, excellent simultaneous separation and highly sensitive detection at 275 nm for these mono-and divalent cations were achieved on the Pia Seed 5S-60-SIL column (150×4.6 mm I.D.) in 20 min.     

Poly(1-allylimidazole)-grafted silica,a new specific stationary phase for reversed-phase and anion-exchange liquid chromatography

A new specific stationary phase based on poly(1-allylimidazole)-grafted silica has been synthesized and characterized, by infrared spectra, elemental analysis, thermogravimetric analysis and X-ray photoelectron spectroscopy. The results of test showed that poly(1-allylimidazole) can effectively mask the residual silanol groups and reduce the adverse effect of residual silanol. Using this stationary phase, phenol compounds, aniline compounds, and polycyclic aromatic hydrocarbons were successfully separated with symmetric peak shapes in the reversed-phase chromatography. Inorganic anions (IO₃⁻, BrO₃⁻, Br⁻, NO₃⁻, I⁻, SCN⁻) were also separated completely in the anion-exchange chromatography using sodium chloride solution as the mobile phase. The effects of pH and the concentration of eluent on the separation of inorganic anions were studied. The separation mechanism appears to involve the mixed interactions of hydrogen bonding, hydrophobic, π–π, electrostatic, and anion-exchange interactions.     

The Application of Cryptand 22 as a Bifunctional Stationary Phase for Ion Chromatography

Poly (styrene/divinyl benzene) with cryptand 22 as an anchoring group was synthesized and applied as a bifunctional packing material for the separation of both cations and anions. At pH < 2, the resin can be protonated and applied as an anion exchanger for the separation of anions; with water as eluent, inorganic anions such as F^?, Cl^?, Br^?, NO₃^?”, I^? were well separated. After deprotonation at pH> 10, the resin became a cation exchanger and successfully separated alkali metal ions such as Li⁺, K⁺ and Cs⁺ with methanol as eluent. The effects of solvents, flow rate and temperature on the separation of various ions were also investigated.     

Cation effect on anion separations by aza-crown ligands in liquid membranes

New carriers have been prepared based on the aza-18-crown-6 structure to facilitate membrane transport of ions. One of these incorporates four aza-18-crown-6 molecules bonded to a resorcinarene ring. The other, aza-18-crown-6 bonded to an undecyl chain, was studied as a monomeric analog. These carriers have been included in dichloromethane bulk liquid membranes (BLMs) to assess cation influence on competitive transport among anions (ReO₄⁻, NO₃⁻, ClO₄⁻). ReO₄⁻ was investigated as a non-radioactive analog of the pertechnetate anion, which is of interest in nuclear waste separations. The permeability values and selectivity for ReO₄⁻ and ClO₄⁻ were the greatest when neutral source and receiving phases were used with K⁺ as the co-transported cation. The carriers also showed selectivity for ReO₄⁻ and ClO₄⁻ over NO₃⁻ with K⁺ and Na⁺ as the co-transported cations using neutral and basic aqueous phase solutions. It was also found that some cations inhibit anion transport.     

Preparation of a hybrid monolithic stationary phase with allylsulfonate for the rapid and simultaneous separation of cations in capillary ion chromatography

A hybrid monolithic column with sulfonate functionality was successfully prepared for the simultaneous separation of common inorganic cations in ion‐exchange chromatographic mode through a simple and easy single‐step preparation method. The strong cation‐exchange moieties were provided directly from allylsulfonate, which worked as an organic monomer in the single‐step reaction. Inorganic cations (Li⁺, Na⁺, K⁺, NH₄⁺, Cs⁺, Rb⁺, Mg²⁺, Ca²⁺, and Sr²⁺) were separated satisfactorily by using CuSO₄ as the eluent with indirect UV detection. The allysulfonate hybrid monolith showed a better performance in terms of speed and pressure drop than the capillary packed column. The number of theoretical plates achieved was 19 017 plates/m (in the case of NH₄⁺ as the analyte). The relative standard deviations (n = 6) of both retention time and peak height were less than 1.96% for all the analyte cations. The allysulfonate hybrid monolithic column was successfully applied for the rapid and simultaneous separation of inorganic cations in groundwater and the effluent of onsite domestic wastewater treatment system.     

Single-run ion chromatographic separation of inorganic and low-molecular-mass organic anions under isocratic elution: Application to environmental samples

For the isocratic ion chromatography (IC) separation of low-molecular-mass organic acids and inorganic anions three different anion-exchange columns were studied: IonPac AS14 (9 μm particle size), Allsep A-2 (7 μm particle size), and IC SI-50 4E (5 μm particle size). A complete baseline separation for all analyzed anions (i.e., F⁻, acetate, formate, Cl⁻, NO₂⁻, Br⁻, NO₃⁻, HPO₄²⁻ and SO₄²⁻) in one analytical cycle of shorter than 17 min was achieved on the IC SI-50 4E column, using an eluent mixture of 3.2 mM Na₂CO₃ and 1.0 mM NaHCO₃ with a flow rate of 1.0 mL min⁻¹. On the IonPac AS14 column, it was possible to separate acetate from inorganic anions in one run (i.e., less than 9 min), but not formate, under the following conditions: 3.5 mM Na₂CO₃ plus 1.0 mM NaHCO₃ with a flow rate of 1.2 mL min⁻¹. Therefore, it was necessary to adapt a second run with a 2.0 mM Na₂B₄O₇ solution as an eluent under a flow rate of 0.8 mL min⁻¹ for the separation of organic ions, which considerably enlarged the analysis time. For the Allsep A-2 column, using an eluent mixture of 1.2 mM Na₂CO₃ plus 1.5 mM NaHCO₃ with a flow rate of 1.6 mL min⁻¹, it was possible to separate almost all anions in one run within 25 min, except the fluoride-acetate critical pair. A Certified Multianion Standard Solution PRIMUS for IC was used for the validation of the analytical methods. The lowest RSDs (less than 1%) and the best LODs (0.02, 0.2, 0.16, 0.11, 0.06, 0.05, 0.04, 0.14 and 0.09 mg L⁻¹ for F⁻, Ac⁻, For⁻, Cl⁻, NO₂⁻, Br⁻, NO₃⁻, HPO₄²⁻ and SO₄²⁻, respectively) were achieved using the IC SI-50 4E column. This column was applied for the separation of concerned ions in environmental precipitation samples such as snow, hail and rainwater.     

Simultaneous separation of common mono- and divalent cations on silica gels modified with aluminium and zirconium

The modification of silica gel with aluminium and zirconium can be used for the preparation of advanced silica-based cation-exchange stationary phases for use in ion chromatography with conductimetric detection (IC-CD) for cations. Silica gels modified with aluminium (Al-silica) and zirconium (Zr-silica) act as cation-exchangers under strongly acidic conditions. Highly sensitive indirect conductimetric detection and excellently simultaneous separation for common mono- and divalent cations (Li⁺, Na⁺, NH₄⁺, K⁺, Mg²⁺ and Ca²⁺) can be achieved on the Al-silica and Zr-silica columns in IC-CD by using acidic eluents containing 15-crown-5 (1,3,7,10,13-pentaoxacyclopentadecane). The Al-silica and Zr-silica can also be applied successfully as cation-exchange stationary phases in ion-exclusion chromatography for the separation of various aliphatic and benzenecarboxylic acids.