Influence of acidic eluent for retention behaviors of common anions and cations by ion-exclusion/cation-exchange chromatography on a weakly acidic cation-exchange resin in the H+ -form.

Influence of acidic eluent on retention behaviors of common anions and cations by ion-exclusion/cation-exchange chromatography (ion-exclusion/CEC) were investigated on a weakly acidic cation-exchange resin in the H(+)-form with conductivity. Sensitivities of analyte ions, especially weak acid anions (F(-) and HCOO(-)), were affected with degree of background conductivity level with pK(a1) (first dissociation constant) of acid in eluent. The retention behaviors of anions and cations were related to that of elution dip induced after eluting acid to separation column and injecting analyte sample. These results were largely dependent on the natures of acid as eluent. Through this study, succinic acid as the eluent was suitable for simultaneous separation of strong acid anions (SO(4)(2-), Cl(-), NO(3)(-) and I(-)), weak acid anions (F(-), HCOO(-) and CH(3)COO(-)), and cations (Na(+), K(+), NH(4)(+), Mg(2+) and Ca(2+)). The separation was achieved in 20 min under the optimum eluent condition, 20 mM succinic acid/2 mM 18-crown-6. Detection limits at S/N=3 ranged from 0.10 to 0.51 microM for strong acid anions, 0.20 to 5.04 microM for weak acid anions and 0.75 to 1.72 microM for cations. The relative standard deviations of peak areas in the repeated chromatographic runs (n=10) were in the range of 1.1-2.9% for anions and 1.8-4.5% for cations. This method was successfully applied to hot spring water containing strong acid anions, weak acid anions and cations, with satisfactory results.

Vacancy ion-exclusion chromatography of inorganic acids on a weakly acidic cation-exchange resin column.

Vacancy ion-exclusion chromatography (VIEC) for inorganic acids such as H(2)SO(4), HCl, H(3)PO(4), HNO(3), HI and HF is tested on a polymethacrylate-based weakly acidic cation-exchange resin column in the H(+)-form. That is, mixture of inorganic acids in the mobile phase is adsorbed to the resin phase passing through the separation column, and each vacant peak induced by injecting water is determined. Retention times are dependent on the degrees of retention for each analyte in the resin phase. In VIEC, well-shaped peaks of inorganic acids are produced, leading to efficient separations. However, retention behaviors of inorganic acids were strongly affected by the concentrations of the acids in the mobile phase. Sulfosalicylic acid was mixed with inorganic acids in the mobile phase prior to the introduction of a separation column in order to obtain the well-resolutions in the lower concentrations of the acids. By using this method, the separations of inorganic acids could be achieved in the range of 0.01-1 mM, and the linear ranges could be extended over two-orders of magnitude. This is considered since the protonated carboxylic groups fixed on the resin phase were increased with increasing the acid concentrations in the mobile phase, and the penetration effects for the acids to the resin phase were thus enhanced. The detection limits (S/N=3) were below 1.0 microM for all analyte acids. Precision values for retention times were below 0.32% and for peak area were below 0.91%.

Selective and simultaneous determination of phosphate and silicate ions in leaching process waters for ceramics glaze raw materials of narutal origin by ion-exclusion chromatography coupled with UV-detection after postcolumn derivatization.

The selective and simultaneous ion-exclusion chromatography (IEC) with UV-detection on a weakly acidic cation-exchange resin column in the H+ -form (TSKgel Super IC-A/C) was developed and applied for the simultaneous determination of phosphate and silicate ions as the water quality parameters required for optimizing the water-leaching process for ceramics glaze raw materials of natural origin including feldspar, woods-ash, and straw-ash. Phosphate and silicate ions in these water-leaching process water samples were separated selectively from the coexisting anions such as sulfate, chloride, nitrate and carbonate ions, based on the ion-exclusion separation mechanism. They were detected selectively and simultaneously by a postcolumn derivatization with molybdenum-yellow using the UV-detector. Under the optimized separation and detection conditions (eluent, 0-1 mM sulfuric acid; reactant, 10 mM sodium molybdate-25 mM sulfuric acid; detector, UV at 370 nm; temperature, 45 degrees C), the linearity of calibration was in the range 0.1 - 10 ppm for both phosphate and silicate ions, and the detection limits at S/N = 3 were 2.58 ppb for silicate ions and 4.75 ppb for phosphate ions. The effectiveness of this method was demonstrated in practical applications to the water-leaching process for some ceramics glaze raw materials.

Ion-exclusion/adsorption chromatography of dimethylsulfoxide and its derivatives for the evaluation to quality-test of TiO(2)-photocatalyst in water.

Ion-exclusion/adsorption chromatography of dimethylsulfoxide (DMSO) and its derivatives, i.e., methanesulfinic acid (MSI), methanesulfonic acid (MSA) and sulfuric acid (SA), was developed in order to clear the decomposition mechanism of DMSO on quality-test of TiO(2)-photocatalyst in water. The separation was achieved by the adsorption effect for DMSO and ion-exclusion effect for MSI, MSA and SA under optimum conditions, using a weakly acidic cation-exchange resin column with 20mM succinic acid as the eluent. In this system, DMSO and MSI with UV at 195nm and MSA and SA with conductivity detection were consecutively determined by single injection and single separation column. This method was used to monitor the artificial decomposition of DMSO induced by a photocatalyst. The concentration of DMSO by active oxygens (e.g., OH radical) generated from surface of photocatalyst was found to be decreased through the stoichiometric reaction in the order of MSI, MSA and SA.

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 (NH(4)(+)) and hydrazine (N(2)H(5)(+)) ions was developed by connecting an anion-exchange column in the I(-)-form after the separation column. For example, NH(4)(+) is converted to a UV-absorbing molecule, NH(4)I, 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(+), NH(4)(+) and N(2)H(5)(+) could be successfully obtained as well as the well-resolved separation. The calibration graphs of the analyte cations detected with UV at 230nm were linear in the range of 0.001-5.0mM. The detection limits at S/N=3 of the cations were below 0.1muM. This method was applied to real water analysis, the determination of NH(4)(+) in river and rain waters, or that of N(2)H(5)(+) 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.

High-speed ion-exclusion chromatography of dissolved carbon dioxide on a small weakly acidic cation-exchange resin column with ion-exchange enhancement columns of conductivity detection.

The high-speed ion-exclusion chromatographic determination of dissolved carbon dioxide, i.e., carbonic acid, hydrogencarbonate or carbonate, with conductivity detection was obtained using a small column packed with a weakly acidic cation-exchange resin in the H+-form (40 mm long x 4.6 mm i.d., 3 microm-particle and 0.1 meq./ml-capacity). Two different ion-exchange resin columns, which were a strongly acidic cation-exchange resin in the K+-form and a strongly basic anion-exchange resin in the OH- -form, were connected after the separation column. The sequence of columns could convert dissolved carbon dioxide to KOH having high conductivity response. The enhancement effect for dissolved carbon dioxide could retain even on the vast chromatographic runs, by using the enhancement columns with high ion-exchange capacity above 1.0 meq./ml. The retention time was in 60 s at flow-rate of 1.2 ml/min. The calibration graph of dissolved carbon dioxide estimated as H2CO3- was linear in the range of 0.005-10 mM. The detection limit at signal to noise of 3 was 0.15 microM as H2CO3-. This method was applicable to several rainwater and tap water samples.

Ion chromatographic determination of hydroxide ion on monolithic reversed-phase silica gel columns coated with nonionic and cationic surfactants.

The determination of hydroxide by ion chromatography (IC) is demonstrated using a monolithic octadecylsilyl (ODS)-silica gel column coated first with a nonionic surfactant (polyoxyethylene (POE)) and then with a cationic surfactant (cetyltrimethylammonium bromide (CTAB)). This stationary phase, when used in conjunction with a 10 mmol/l sodium sulfate eluent at pH 8.2, was found to be suitable for the rapid and efficient separation of hydroxide from some other anions, based on a conventional ion-exchange mechanism. The peak directions and detection responses for these ions were in agreement with their known limiting equivalent ionic conductance values. Under these conditions, a linear calibration plot was obtained for hydroxide ion over the range 16 micromol/l to 15 mmol/l, and the detection limit determined at a signal-to-noise ratio of 3 was 6.4 micromol/l. The double-coated stationary phase described above was shown to be superior to a single coating of cetyltrimethylammonium bromide alone, in terms of separation efficiency and stability of the stationary phase. A range of samples comprising solutions of some strong and weak bases was analyzed by the proposed method and the results obtained were in good agreement with those obtained by conventional potentiometric pH measurement.

Determination of monovalent inorganic anions in high-ionic-strength samples by electrostatic ion chromatography with suppressed conductometric detection.

A new ion chromatographic (IC) system has been established by using micelles of 3-(N,N-dimethylmyristylammonio)propanesulfonate (Zwittergent 3-14) loaded onto a reversed-phase packed column as the separation column with an electronic rotary switching valve packed-bed suppressor for conductometric detection of inorganic anions. An aqueous H3BO3-Na2B4O7 solution has been demonstrated to be the most desirable eluent for this IC system. The relationship between retention time and the concentration of the borate eluent was determined for a series of model anionic analytes and this relationship was found to be opposite to that exhibited in a conventional anion-exchange IC system. The rapid elution and complete separation of monovalent inorganic anions were obtained by initially using a high-concentration borate solution as the eluent for a short-period, and then switching to a lower-concentration borate eluent to complete the separation. Detection limits for nitrite, bromide, nitrate, and chlorate were 0.85, 0.88, 0.95 and 4.8 microM, respectively, when a 7.0 mM Na2B4O7 eluent was used. Moreover, the ability to directly detect these monovalent anions in samples containing high concentrations of sulfate and/or chloride ions provided a major advantage of this approach.

Vacancy ion-exclusion/adsorption chromatography of aliphatic amines on a polymethacrylate-based weakly basic anion-exchange column.

Vacancy ion-exclusion/adsorption chromatography has been applied to investigate the separation behavior of five aliphatic amines (ethylamine, propylamine, butylamine, pentylamine and hexylamine) on a polymethacrylate-based weakly basic anion-exchange column (Tosoh TSKgel DEAE-5PW). This system is consisted of analytes as a mobile phase and water as an injected sample. In the vacancy ion-exclusion/adsorption chromatography, the elution order was as follows: ethylamine < propylamine < butylamine < pentylamine < hexylamine, depending on their hydrophobicity. The retention times of the amines were decreased with decreasing their concentrations in the mobile phase. The retention times and resolutions of the amines were increased by adding a basic compound (e.g., lithium hydroxide or heptylamine) and by increasing the pH of mobile phase (pH > 11). This was because the dissociations of amine samples in the mobile phase were suppressed and thus the hydrophobic adsorption effects were enhanced. The linearity of calibration graphs could be obtained from the peak areas of the amine samples injected to the 0.05, 0.5 and 5 mM of amine mobile phase at pH 11 by heptylamine. The detection limits of aliphatic amines as injected samples were around 1 microM for five aliphatic amines at three different amine mobile phases. From these results, the retention behaviors of aliphatic amines on vacancy ion-exclusion/adsorption chromatography were concluded to be governed by the hydrophobic adsorption effect.

Highly sensitive determination of hydrazine ion by ion-exclusion chromatography with ion-exchange enhancement of conductivity detection.

An ion-exclusion chromatography method with ion-exchange enhancement of conductivity was developed for the selective separation and sensitive determination of hydrazine ion from alkali/alkaline earth metal cations and ammonium ion. Hydrazine ion was separated by ion-exclusion/penetration effect from other cations on a weakly basic anion-exchange column in the OH- form (TSKgel DEAE-5PW). Moreover, two different ion-exchange resin columns were inserted between the separating column and conductimetric detector in order to improve the sensitivity of hydrazine ion. The first enhancement column packed with a strongly basic anion-exchange resin in the SO4(2-) form (TSKgel SAX) for hydrazine ion can convert from N2H5OH to (N2H5)2SO4. Moreover, the second enhancement column packed with a strongly acidic cation-change resin in the H+ form (TSKgel SCX) can convert to H2SO4. As a result, the sensitivity of hydrazine ion using two conductivity enhancement columns could be 26.8-times greater than using the separating column alone. This method was effectiveness also for the enhancement of ammonium ion (6.1-times) and sodium ion (1.2-times). The calibration graph of hydrazine ion detected as H2SO4 was linear over the concentration range of 0.001-100 ppm (r2 = 0.9988). The detection limit of hydrazine ion in this system was 0.64 ppb. Therefore, hydrazine ion in real boiler water sample could be accurately determined, avoiding the interference of other cations.

Determination of some aliphatic carboxylic acids in anaerobic digestion process waters by ion-exclusion chromatography with conductimetric detection on a weakly acidic cation-exchange resin column.

The determination of seven aliphatic carboxylic acids, formic, acetic, propionic, isobutyric, n-butyric, isovaleric and n-valeric acids in anaerobic digestion process waters was examined using ion-exclusion chromatography with conductimetric detection. The analysis of these biologically important carboxylic acids is necessary as a measure for evaluating and controlling the process. The ion-exclusion chromatography system employed consisted of polymethacrylate-based weakly acidic cation-exchange resin columns (TSKgel OApak-A or TSKgel Super IC-A/C). weakly acidic eluent (benzoic acid), and conductimetric detection. Particle size and cation-exchange capacity were 5 microm and 0.1 meq./ml for TSKgel OApak-A and 3 microm and 0.2 meq./ml for TSKgel Super IC-A/C, respectively. A dilute eluent (1.0-2.0 mM) of benzoic acid was effective for the high resolution and highly conductimetric detection of the carboxylic acids. The good separation of isobutyric and n-butyric acids was performed using the TSKgel Super IC-A/C column (150 mm x 6.0 mm i.d. x 2). The simple and good chromatograms were obtained by the optimized ion-exclusion chromatography conditions for real samples from mesophilic anaerobic digestors, thus the aliphatic carboxylic acids were successfully determined without any interferences.

Dodecylsulfate-coated monolithic octadecyl-bonded silica stationary phase for high-speed separation of hydrogen, magnesium and calcium in rainwater.

The high-speed determination of hydrogen, magnesium and calcium ions by ion chromatography (IC) is demonstrated on a monolithic octadecyl-boned silica (ODS) column coated with lithium dodecylsulfate (Li-DS). This stationary phase, when used in conjunction with a 2 mM ethylenediamine and 0.1 mM Li-DS solution as eluent at pH 6.0, was found to be suitable for the rapid and efficient separation of hydrogen and magnesium and calcium in the order H+ < Mg2+ < Ca2+ within 4 min at a flow rate of 4.0 ml/min. Under the conditions, linear calibration plots of conductivity versus concentration were obtained for the cations over about three orders of magnitude, and the detection limits were 1 microM for H+, 2 microM for Mg2+ and Ca2+. Rainwater was analyzed directly using this IC system with satisfactory results.

Ion-exclusion chromatography with conductimetric detection of aliphatic carboxylic acids on a weakly acidic cation-exchange resin by elution with benzoic acid-beta-cyclodextrin.

In this study, an aqueous solution consisting of benzoic acid with low background conductivity and beta-cyclodextrin (beta-CD) of hydrophilic nature and the inclusion effect to benzoic acid were used as eluent for the ion-exclusion chromatographic separation of aliphatic carboxylic acids with different pKa values and hydrophobicity on a polymethacrylate-based weakly acidic cation-exchange resin in the H+ form. With increasing concentration of beta-cyclodextrin in the eluent, the retention times of the carboxylic acids decreased due to the increased hydrophilicity of the polymethacrylate-based cation-exchange resin surface from the adsorption of OH groups of beta-cyclodextrin. Moreover, the eluent background conductivity decreased with increasing concentration of beta-cyclodextrin in 1 mM benzoic acid, which could result in higher sensitivity for conductimetric detection. The ion-exclusion chromatographic separation of carboxylic acids with high resolution and sensitivity was accomplished successfully by elution with a 1 mM benzoic acid-10 mM cyclodextrin solution without chemical suppression.

Selective determination of ammonium ions by high-speed ion-exclusion chromatography on a weakly basic anion-exchange resin column.

This paper describes an ion-exclusion chromatographic system for the rapid and selective determination of ammonium ion. The optimized ion-exclusion chromatographic system was established with a polymethacrylate-based weakly basic anion-exchange resin column (TSKgel DEAE-5PW) as the separation column, an aqueous solution containing 0.05 mM tetramethylammonium hydroxide (pH 9.10) as eluent with conductimetric detection for the analyte determination. Under the optimum chromatographic conditions, ammonium ion was determined within 2.3 min with a detection limit (S/N=3) better than 0.125 microM. Ammonium ion in rain and river waters was precisely determined using this ion-exclusion chromatographic system.

High-speed simultaneous ion-exclusion/cation-exchange chromatography of anions and cations on a weakly acidic cation-exchange resin column.

The simultaneous ion-exclusion/cation-exchange separation column packed with a polymethacrylate-based weakly acidic cation-exchange resin of 3 microm particle size was used to achieve the simultaneous high-speed separation of anions and cations (Cl(-), NO3(-), SO4(2-), Na(+), K(+), NH4(+), Ca(2+) and Mg(2+)) commonly found in environmental samples. The high-speed simultaneous separation is based on a combination of the ion-exclusion mechanism for the anions and the cation-exchange mechanism for cations. The complete separation of the anions and cations was achieved in 5 min by elution with 15 mM tartaric acid-2.5 mM 18-crown-6 at a flow-rate of 1.5 ml/min. Detection limits at S/N=3 ranged from 0.36 to 0.68 microM for anions and 0.63-0.99 microM for cations. This method has been applied to the simultaneous determination of anions and cations in several environmental waters with satisfactory results.