Single-column method of ion chromatography for the determination of common cations and some transition metals

A single-column method for the simultaneous determination of common cations and transition metals in real samples is proposed in this paper. Eleven cations (copper, lithium, sodium, ammonium, potassium, cobalt, nickel, magnesium, calcium, strontium and zinc) were separated and analyzed by means of ion chromatography using an isocratic elution with 2.5 mM methane sulfonic acid and 0.8 mM oxalic acid as mobile phase, IonPac SCS1 (250 mm x 4 mm I.D.) as the separation column and non-suppressed conductor detection. Optimized analytical conditions were further validated in terms of accuracy, precision and total uncertainty and the results showed the reliability of the IC method. The relative standard deviations (RSDs) of the retention time and peak area were less than 0.04 and 1.30%, respectively. The coefficients of determination for cations ranged from 0.9988 to 1.000. The method developed was successfully applied to determination of cations in samples of beer and bottled mineral water. The spiked recoveries for the cations were 94-106%. The method was applied to beer and beverage without interferences.     

Simultaneous determination of alkali,alkaline earth and transition metal elements in uranium and thorium based nuclear fuel materials by single column ion chromatography

A single-column ion chromatography (SCIC) for the simultaneous determination of alkali, alkaline earth and transition metal elements in UO₂, ThO₂ powders and sintered (Th, U) O₂ pellet is described in this paper. Metrosep cation 1-2 analytical column containing poly butadiene-maleic acid (PBDMA) coated silica has been applied to the ion chromatographic separation of 12 cations (copper, lithium, sodium, ammonium, nickel, potassium, zinc, cobalt, manganese, magnesium, calcium and strontium) using an isocratic elution with tartaric acid and oxalic acid as mobile phase with non-suppressed conductivity detection. Mobile phase composition was optimized to 1 mM tartaric acid and 0.75 mM oxalic acid for the baseline separation of 12 cations. The calibration plots were linear in the range of 0.05–40 mg L⁻¹ with regression coefficients better than 0.998. The relative standard deviations (RSDs) of the retention time, peak area and peak height were less than 1, 2.8 and 3.0%, respectively. The recoveries of the spiked samples for the cations were 94–110%. The method developed was validated by comparison with certified standards of UO₂ and ThO₂ powders.     

On-line concentration of s-triazine herbicides in micellar electrokinetic chromatography using a cationic surfactant

A new method for the simultaneous determination of anions (sulfate, nitrate, and chloride) and cations (sodium, ammonium, potassium, magnesium, and calcium) in acid rain waters was investigated using high-performance ion-exclusion/cation-exchange chromatography with conductimetric detection on a separation column packed with a polymethacrylate-based weakly acidic cation-exchange resin in the hydrogen-form and an eluent comprising 1.5 mM sulfosalicylic acid–6 mM 18-crown-6 at pH 2.6, operated at 1.5 ml/min. Effective separation and highly sensitive conductimetric detection for the anions and the cations was achieved in about 14 min. Since the ionic balance (equivalents of anions/equivalents of cations) of acid rain waters of different pH (4.40–4.67) ranged from 0.97 to 0.94, evaluation of the water quality of acid rain was possible. This method was successfully applied to the simultaneous determination of the anions and the cations in acid rain transported from mainland China and North Korea to central Japan monitored by a meteorological satellite data analyzer.     

Simultaneous separation of inorganic anions and cations by capillary zone electrophoresis

A new capillary electrophoretic approach for simultaneous separation of fast anions and cations is demonstrated. Indirect UV detection at 214 nm in conjunction with electromigration sampling from both ends of the capillary was developed. Two electrolyte systems based on imidazole-nitrate and copper(II)-ethylenediamine-nitrate were investigated for the simultaneous separation of chloride, sulphate, hydrocarbonate, potassium, ammonium, calcium, sodium and magnesium ions. Experimental parameters that were evaluated included a nature of UV chromophore, pH of electrolyte, a nature of complexing agent. The method permits the excellent separation of three anions and five cations in only 4 min using electrolyte system containing 2.5 mmol l⁻¹ Cu(NO₃)₂, 5 mmol l⁻¹ ethylenediamine and 1 mmol l⁻¹ fumaric acid at pH 8.5 adjusted with tetraethylammonium hydroxide.     

Quantitative determination of inorganic minor cations in sodium-, calcium-, magnesium-matrix simulated samples by capillary electrophoresis

The analysis of ammonium, alkali and alkaline-earth trace cations (0.5 ppm) in samples with a calcium, sodium or magnesium matrix (500 ppm) has been achieved using 10 mM imidazole (pH 4.5) electrolyte to which a complexing agent (15-crown-5, oxalic acid or dipicolinic acid) has been specifically added in order to decrease the electrophoretic mobility of the matrix cation and thus to allow the separation of higher mobility cations at sub-ppm concentrations. The influence of several experimental parameters (complexing agent concentration, buffer pH and temperature) have been studied in order to optimize the separation. The complexing agent concentration appears to be the main parameter governing the selectivity of the cations during the analysis of matrix samples. In optimized conditions, we have checked that the separation between minor inorganic cations is not significantly altered by an increase in the matrix cation concentration. As the concentration of the matrix cation increases, the migration times of minor cations remain unchanged even for a 1000 ppm concentration of the matrix cation. Finally, these optimized buffers allow the quantitation of minor cations down to 0.05% (w/w) for calcium- or magnesium- matrix simulated samples and 0.2% (w/w) for sodium-matrix simulated samples.     

Procedure for determination of trace ions in boric acid by matrix volatilization-ion chromatography

A method for determination of anions and cations in boric acid is proposed by matrix volatilization. The boric acid matrix was eliminated as trimethyl borate ester in a vapour phase matrix elimination (VPME) system using a mixture of glycerol-methanol. In this VPME system, in situ reagent purification, sample decomposition and digest evaporation were achieved in a single step. Trace anions were separated on anion-exchange column (IonPac AS17) by an isocratic elution with 15 mM sodium hydroxide and the cations on a cation-exchange column (IonPac CS12) by 20 mM hydrochloric acid as eluents. Method detection limits (3sigma) for most ions ranged from 0.3 to 8 ng/g (ppb). Recovery experiments combined with comparison of data obtained by other methods were employed to verify the accuracy of the proposed method. Application of the method to determine trace levels of anions like acetate, oxalate, sulfate, phosphate and cations such as lithium, sodium, potassium, magnesium and calcium in two highly pure grades of boric acid using ion chromatography is demonstrated.     

Determination of ammonium,calcium, magnesium,potassium and sodium in drinking waters by capillary zone electrophoresis on a column-coupling chip

This work deals with simultaneous determination of ammonium, calcium, magnesium, sodium and potassium in drinking waters by capillary zone electrophoresis (CZE) on a column-coupling (CC) chip with suppressed hydrodynamic and electroosmotic transports. CZE separations were carried out in a propionate background electrolyte at a low pH (3.2) containing 18-crown-6-ether (18-crown-6) to reach a complete resolution of the cations. In addition, triethylenetetramine (TETA) coated the inner wall surface of the chip channels. The concentration limits of detection (cLOD) for the studied cations ranged from 4.9 to 11.5 μg/l concentrations using a 900 nl volume of the sample injection channel. 93–106% recoveries of the cations in drinking waters indicate a good predisposition of the present method to provide accurate analytical results.     

Capillary electrophoresis analysis of inorganic cations in post-blast residue extracts applying a guanidinium-based electrolyte and bilayer-coated capillaries

A new CE method was developed for the identification and quantitation of inorganic cations in post‐blast residues. The simultaneous analysis in 20 min total runtime of eight cations in post‐blast residues (ammonium, potassium, monomethylammonium, calcium, sodium, magnesium, strontium), plus lithium cation as the internal reference, was carried out with a BGE involving a non‐CMR (carcinogenic, mutagenic, and harmful to reproduction) chromophore (guanidinium cation) and a double‐layer modified capillary (hexadimethrine bromide/polyvinylsulfonate). A study of UV detection conditions using guanidinium ion as the probe led us to set the analysis and reference wavelengths and their associated bandwidths as well as the probe concentration fixed at 15 mM. The successive multiple ionic‐polymer layer approach limited the cation adsorption on capillary wall and improved the EOF stability. These caused a significant improvement in method repeatability. Intermediate precisions were 2.4% for corrected areas and 1.3% for normalized migration times. Limits of detection close to 1 mg/L for all cations were obtained. The matrix effects were studied with chemometric approach for different matrices representative of those collected after explosion. Tests with blank matrix extracts of soil, cloth, and with simulated matrix extract containing 800 mg/L Ca²⁺ and 500 mg/L Fe²⁺ were carried out and no significant matrix effects were observed. Finally, analyses of real residues collected after cash dispenser and homemade firework explosions demonstrate excellent correlation between the CE results and those obtained with the ion chromatography method used routinely.     

A novel method for analysis of explosives residue by simultaneous detection of anions and cations via capillary zone electrophoresis

A novel electrolyte has been developed for the simultaneous separation of cations and anions in low explosive residue by capillary electrophoresis. This electrolyte contains 15 mM α-hydroxyisobutyric acid (HIBA) as the buffer, 6 mM imidazole as the cation chromophore, 3 mM 1,3,6-naphthalenetrisulfonic acid (NTS) as the anion chromophore, 4 mM 18-crown-6 ether as a cation selectivity modifier, and 5% (v/v) acetonitrile as an organic modifier. The pH was adjusted to 6.5 using tetramethylammonium hydroxide (TMAOH), an electroosmotic flow modifier. The method was optimized by varying the concentrations of α-HIBA, imidazole, and 1,3,6-NTS at three different pH values. The results provided a simultaneous indirect photometric analysis of both anions and cations with detection limits ranging from 0.5 to 5 ppm for anions and from 10 to 15 ppm for cations with a total run time of under 7 min. The method was then applied to the analysis of Pyrodex^® RS and black powder, as well as several smokeless powders. The results obtained were consistent with previously reported results for separate anion and cation analysis and provide a faster, more complete analysis of each sample in a single chromatographic run.     

Determination of the spectrum of low molecular mass organic acids in urine by capillary electrophoresis with contactless conductivity and ultraviolet photometric detection--an efficient tool for monitoring of inborn metabolic disorders

A mixture of 29 organic acids (OAs) occurring in urine was analyzed by capillary electrophoresis (CE) with capacitively coupled contactless conductivity detection (C⁴D) and UV photometric detection. The optimized analytical system involved a 100 cm long polyacrylamide-coated capillary (50 μm i.d.) and the background electrolyte of 20 mM 2-morpholinoethanesulfonic acid (MES)/NaOH + 10% (v/v) methanol, pH 6.0 (pH is related to the 20 mM MES/NaOH buffer in water). The LOD values obtained by C⁴D for the OAs which do not absorb UV radiation range from 0.6 μM (oxalic acid) to 6.8 μM (pyruvic acid); those obtained by UV photometry for the remaining OAs range from 2.9 μM (5-hydroxy-3-indoleacetic acid) to 10.2 μM (uric acid). The repeatability of the procedure developed is characterized by the coefficients of variation, which vary between 0.3% (tartaric acid) and 0.6% (5-hydroxy-3-indoleacetic acid) for the migration time and between 1.3% (tartaric acid) and 3.5% (lactic acid) for the peak area. The procedure permitted quantitation of 20 OAs in a real urine sample and was applied to monitoring of the occurrence of the inborn metabolic fault of methylmalonic aciduria.     

Use of phosphobetaine-type zwitterionic surfactant for the determination of alkali and alkaline earth metal ions and ammonium ion in human saliva by capillary electrophoresis

With conventional capillary electrophoresis (CE), it was difficult to directly analyze samples containing proteins as a result of the irreversible adsorption of proteins onto the inner surface of the capillary column. This difficulty, however, was completely overcome by adding N-dodecylphosphocholine (DPC, a phosphobetaine-type zwitterionic surfactant) to the background electrolyte (BGE). DPC made two essential contributions to the determination of common inorganic cations in the protein-containing samples: protein adsorption onto the capillary walls was completely avoided, and the resolution of the analyte cations was essentially improved. The optimal BGE for analysis of biological samples was found to be 5 mM DPC, 5 mM copper(II) acetate/10 mM ethylenediamine (pH 8). The detection limits (signal-to-noise ratio =3 and UV at 215 nm) of sodium, potassium, calcium, magnesium, and ammonium ions were 25, 31, 24, 45, and 60 micro M, respectively. These five species of the common inorganic cations in human saliva samples were detected successfully within 2 min by the proposed system with direct sample injection.     

Separation and Determination of Monovalent and Divalent Cations by the Facile Propylsulfonic Acid Functionalized Silica Stationary Phase

A facile strong cation-exchange stationary phase based on propylsulfonic acid functionalized silica was prepared through the oxidation in situ of 3-mercaptopropyl silica and characterized by elemental analysis and X-ray photoelectron spectroscopy. The phase was used to separate monovalent and divalent inorganic cations with strong acid as mobile phase. Simultaneous separation of alkali metals and alkaline earth metals was examined and the cations sodium, magnesium and calcium in tap water were determined.     

Polycarboxylate crown ethers: Synthesis,complexation, applications

Crown ethers derived from tartaric acid present a number of interesting features as receptor frameworks and offer a possibility of enhanced metal cation binding due to favorable electrostatic interactions. The synthesis of polycarboxylate crown ethers from tartaric acid is achieved by simple Williamson ether synthesis using thallous ethoxide or sodium hydride as base. Stability constants for the complexation of alkali metal and alkaline earth cations were determined by potentiometric titration. Complexation is dominated by electrostatic interactions but cooperative coordination of the cation by both the crown ether and a carboxylate group is essential to complex stability. Complexes are stable to pH 3 and the ligands can be used as simultaneous proton and metal ion buffers. The low extractibility of the complexes was applied in a membrane transport system which is a formal model of primary active transport.     

Retention behavior of alkali, alkaline earth and transition metal cations in ion chromatography with an unmodified silica gel column

An unmodified silica gel (Develosil 30-5) column (150×4.6 mm I.D.) has been applied to the ion chromatographic separation of alkali, alkaline earth and transition metal cations. The retention behavior of the above cations on the bare substrate was investigated using a number of weak inorganic and organic acid eluents. During this investigation, several separations were achieved and the most suitable eluent conditions were identified. It was concluded that: (a) 1.5 mM HNO₃-0.5mM pyridine-2,6-dicar☐ylic acid eluent was the most effective for the simultaneous separation of common alkali and alkaline earth metal cations, (b) 1.5 mM oxalic acid eluent resulted in the best separation of alkali, alkaline earth, and transition metal cations, (c) 0.5 mM CuSO₄ eluent could be used for the separation of alkali metal cations alone and (d) 0.5 mM ethylenediamine-oxalic acid eluent at pH 5.5 resulted in themost efficient separation of both alkaline earth and transition metal cations.     

Simultaneous determination of metal ions, amino acids, and other small biogenic molecules in human serum by capillary zone electrophoresis with transient isotachophoretic preconcentration

CE with indirect UV detection was used for the simultaneous determination of lithium, magnesium, calcium, creatinine, carnitine, and a number of amino acids in human serum. The target analytes, positively charged under acidic electrolyte conditions, were separated with positive separation voltage polarity using 10 mM 4-methylbenzylamine, 4.5 mM citric acid, 25% (v/v) methanol at pH 4.05 as background electrolyte providing optimal separation. When analyzing real samples, however, some peaks were broadened due to essentially destacking conditions. In order to maintain the separation efficiency and also enhance the detection sensitivity, transient isotachophoresis (tITP) sample stacking was applied and yielded theoretical plate numbers in the range from 160,000 (arginine) to 350,000 (creatinine). The limit of detection values with tITP preconcentration were 0.11-0.26 mg L(-1) for metal cations, 1.0 mg L(-1) for creatinine, and 1.3-3.9 mg L(-1) for histidine, lysine, arginine, and ornithine. The method precision for peak areas was from 0.4 to 5.0% relative standard deviation using the matrix sodium as internal standard. The accuracy of the developed tITP-CZE system was verified by consistent results for Li+, Mg2+, Ca2+, and creatinine obtained on analyzing two serum certified reference materials. The only sample preparation required was ultrafiltration and acidification (to release protein-bound alkaline earths), and working ranges for individual analytes corresponded well to clinical concentration ranges.     

Simultaneous determination of inorganic and organic anions,alkali, alkaline earth and transition metal cations by capillary electrophoresis with contactless conductometric detection

Simultaneous separation of up to 22 inorganic and organic anions, alkali, alkaline earth and transition metal cations was achieved in less than 3 min in the capillary electrophoresis system with contactless conductometric detector. The sample was injected from both capillary ends (dual opposite end injection) and anionic and cationic species were detected in the center of the separation capillary. The parameters of the separation electrolyte, such as pH, concentration of the electrolyte, concentration of complexing agents and concentration of 18-crown-6 were studied. Best results were achieved with electrolytes consisting of 8 mM L-histidine, 2.8 mM 2-hydroxyisobutyric acid, 0.32 mM 18-crown-6 at pH 4.25 or 9 mM L-histidine, 4.6 mM lactic acid, 0.38 mM 18-crown-6 at pH 4.25. Other electrolytes containing complexing agents such as malic or tartaric acid at various concentrations could also be used. The detection limits achieved for most cations and anions were 7.5 - 62 micro gL(-1) except for Ba2+ (90 micro gL(-1)), Cd 2+, Cr 3+ and F- (125 micro gL(-1)), and fumarate (250 micro gL(-1)). The repeatability of migration times and peak areas was better than 0.4% and 5.9%, respectively. The developed method was applied for analysis of real samples, such as tap, rain, drainage and surface water samples, plant exudates, plant extracts and ore leachates.     

The removal of Cu,Ni, and Zn in industrial soil by washing with EDTA-organic acids

In order to improve the heavy metal removal ability of traditional single washing agents and explore the removal mechanism of heavy metals. Then, the washing reagents that mixed by low-molecular weight organic acids (citric acid, oxalic acid, and tartaric acid) and artificial chelating compound ethylenediaminetetraacetic acid disodium (EDTA) were selected. Furthermore, the effect of soil washing parameters, the variation of leaching toxicity, mobility, stability and speciation of heavy metals were also considered. The results of soil washing experiments showed that mixing an equal volume of 0.05 M EDTA and 0.2 M organic acids (citric acid, oxalic acid, and tartaric acid) could remove more than about 80% heavy metals from soil under the optimal conditions. In addition, the soil leaching toxicity was decreased and the stability of remaining heavy metals was increased, indicating that EDTA-organic acid washing reagents could effectively reduce the ecological risk of contaminated soil. EDTA had a stronger chelating ability with heavy metals than the organic acids, and the organic acids could not only chelate heavy metals but also decrease the pH of the mixture for promoting the desorption of heavy metals. Thus, mixing EDTA and organic acids was advisable method to improve soil washing technology.     

Simultaneous ion-exclusion/cation-exchange chromatography of anions and cations in acid rain waters on a weakly acidic cation-exchange resin by elution with sulfosalicylic acid

A simple, selective, and sensitive method for the simultaneous determination of anions (sulfate, nitrate, and chloride) and cations (sodium, ammonium, potassium, magnesium, and calcium) in acid rain waters was developed using ion-exclusion/ cation-exchange chromatography with conductimetric detection. A weakly acidic cation-exchange resin column (Tosho TSKgel OA-PAK-A) and a sulfosalicylic acid-methanol-water eluent was used. With a mobile phase comprising 1.25 mM sulfosalicylic acid in methanol-water (7.5:92.5) at 1.2 ml/min, simultaneous separation and detection of the above anions and cations was achieved in about 30 min. Linear calibration plots of peak area versus concentration were obtained over the concentration ranges 0-1.0 mM for anions (R=0.9991) and 0-0.5 mM for cations (R=0.9994). Detection limits calculated at S/N=3 ranged from 4.2 to 14.8 ppb for the anions and from 2.4 to 12.1 ppb for the cations. The reproducibility of retention times was 0.14-0.15% relative standard deviation (RSD) for anions and 0.18-0.31% for cations, and reproducibility of chromatographic peak areas was 1.22-1.75% RSD for anions and 1.81-2.10% for cations. The method was applied successfully to the simultaneous determination of anions and cations in aerosols transported from mainland China to central Japan, as determined by a meteorological satellite data analyzer.     

Indirect ultraviolet spectrophotometric detection in the ion chromatography of common mono- and divalent cations on an aluminium adsorbing silica gel column with tyramine-containing crown ethers as eluent

The application of laboratory-made aluminium-adsorbing silica gel (Al-Silica) as a cation-exchange stationary phase to ion chromatography-indirect photometric detection (IC-IPD) for common mono- and divalent cations (Li+, Na+, NH+, K+, Mg2+ and Ca2+) was carried out by using protonated tyramine (4-aminoethylphenol) as eluent ion. When using 1.2 mM tyramine-0.2 mM oxalic acid at pH 4.5 as eluent, incomplete separation of the monovalent cations and complete separation of the divalent cations were achieved in 17 min. Then, the addition of crown ethers in the eluent was carried out for the complete separation of the mono- and divalent cations. As a result, when using 1.2 mM tyramine--0.2 mM oxalic acid at pH 4.5 containing either 5 mM 15-crown-5 (1,4,7,10,13-pentaoxacyclopentadecane) or 0.5 mM and 18-crown-6 (1,4,7,10,13,16-hexaoxacyclooctadecane) as eluent, excellently simultaneous separation of these cations was achieved in 21 min. The proposed IC-IPD was successfully applied to the determination of major cations in natural water samples.     

Ion chromatographic determination of some anions and alkaline cations in liquid crystal materials after ultraviolet irradiation

A method was developed for the quantitative determination of inorganic cations and anions present in liquid crystal materials pretreated with ultraviolet irradiation by ion chromatography. The samples were irradiated at less than 20±2 °C and then pretreated with OnGuard RP and P cartridges to remove the interferential organic compounds prior to ion chromatographic analysis for both cations and anions. With a high capacity and very hydrophilic anion exchange column, four anions (fluoride, chloride, bromide, iodide) were determined in 20 min with gradient of sodium hydroxide. By employing a cation exchange column, five cations (sodium, ammonium, potassium, magnesium, calcium) could be determined in 12 min. The spiked recoveries for the cations and anions were 84.0–108.1% and 86.1–108.2%, respectively.