Suppressed anion chromatography using mixed zwitter-ionic and carbonate eluents

Effect of mixed eluents which contain zwitterions such as 2-(N-morpholino)ethanesulfonic acid (MES), 3-(N-morpholino)propanesulfonic acid (MOPS), 2-(cyclohexylamino)ethanesulfonic acid (CHES) and 3-(cyclohexylamino)-1-propanesulfonic acid (CAPS) and carbonate for suppressed conductivity ion chromatography (IC) were studied. The retention behaviors of all species were affected with different anion exchange columns when adding some zwitterion into carbonate eluent. The retention time of all species, especially those of strong retetion, was substantially shortened in AS14A column with either Na(2)CO(3)/CHES or Na(2)CO(3)/CAPS as eluent while a general increase in retetion time was noticed in AS9-HC column. Low pH of eluent was achieved when zwitterion was added. Without much changes in the background conductivity after suppressed, CHES could be used as suppressed conductivity ion chromatography eluent for determination of species unstable in strong alkaline, such as determination of phosphate in heteropoly acid (HPA) samples in AS14 column. The mixed eluent could also affect the selectivity when it was applied to the study of simultaneous separation of anions and cations in AS9-HC column by suppressed ion chromatography.     

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.     

Determination of arsenic species by inductively coupled plasma mass spectrometry with ion chromatography

Five arsenic species, trimethylarsine oxide, dimethylarsenic acid, monomethylarsonic acid, arsenobetaine and sodium arsenite, in urine were analysed by inductively coupled plasma mass spectrometry with ion chromatography (IC ICP MS). Since the toxicities of different arsenic compounds are different, speciation of arsenic compounds is very important in the investigation of metabolisms. In this paper, we applied ion chromatography (IC) as a separation device and inductively coupled plasma mass spectrometry (ICP MS) as a detection device. For separation of the five arsenic compounds, an anion-exchange column and, as mobile phase, tartaric acid were used. The eluent from the IC column was introduced directly into the nebulizer of the ICP MS and analysed at 75 amu. Detection limits were from 4 to 9 pg as arsenic.     

Column selection for comprehensive multidimensional ion chromatography

This paper discusses the selection of ion chromatography (IC) columns for use in comprehensive multidimensional ion chromatography (IC x IC). First, a single number was determined for a wide range of anions (one number for each anion) using the linear solvent strength model. These numbers were then used to compare the column selectivity characteristics for five different columns. Principal component analysis was used to illustrate selectivity differences between columns. Dionex AS16 and AS20 columns were selected for use in the development of an IC x IC method for the separation of ten anions. To achieve the required speed of analysis in both the first and second separation dimensions, custom column lengths were packed in-house. The use of an eluent suppressor between the first and second columns permits a relatively low flow ratio regime of only <1:20 in the first and second dimensions, respectively, which reduces dilution effects common in comprehensive multidimensional LC. Selection of the second dimension eluent conditions was aided by the development of a spreadsheet based on the linear solvent strength model.     

Successive non-suppressed ion chromatography of common cations and anions using dual columns with single eluent

A successive non-suppressed ion chromatography (IC) system for the determination of common cations (Na+, K+, Mg2+, Ca2+) and anions (Cl-, Br-, NO3-, SO4(2-)) was developed, using two separation columns and a single eluent. 5-Sulfoisophthalic acid eluent was very suitable for such separations with a commercially available cation-exchange column for the mono- and di-valent cations and with an ODS column coated with cetyltrimethylammonium for the anions. Both cations and anions were detected with conductimetrically high sensitivity without any suppressor. After injecting an aliquot of sample solution, the solvent front from the cation-exchange column, including most of the anionic species, was firstly accumulated into the additional 2 ml accumulation loop for 60 s, while the cation IC was performed. Subsequently, the accumulated fraction was introduced into the anion-exchange column and chromatographed. Relative standard deviations (RSDs) of retention times and conductimetric area responses for common cations were within 6% and within 4%, respectively. The linear relationships between molar concentration and detector response ranged from 0.01 to 1.00 mM with r2 of 0.9994 for Na+, 0.9992 for K+, 0.9993 for Mg2+, and 0.9988 for Ca2+. The successive anion IC through the accumulating process was also quantitative, with 95% recovery or over for each analyte. The linear ranges were between 0.01 and 1.00 mM with r2 of 0.9996 for Cl-, 0.9997 for Br-, 0.9993 for NO3-, and 0.9984 for SO4(2-). The method was applied to the determination of common cations and anions in several mineral waters and a hot spring water.     

抑制型电导检测离子色谱法测定饮用水中的痕量溴酸盐

建立一种直接进样测定饮用水中痕量溴酸盐的电导检测离子色谱法。选用Metrosep A Supp 5阴离子交换分离柱,碳酸盐淋洗液。抑制型电导检测采用化学抑制器和CO2抑制器顺序双抑制系统。实验结果显示,溴酸根阴离子与常见共存阴离子完全分离,溴酸盐含量在5~100 μg/L范围内具有良好的线性(r=0.9999),精密度高(相对标准偏差（RSD）<4%),方法的检出限为0.50 μg/L,样品加标平均回收率为96.1%~107%。该方法操作简单,分离效果好,可与常见阴离子实现同时分析,灵敏度高,重现性好,可作为饮用水中溴酸盐的标准测定方法。     

A study of the mechanisms involved in the separation of metal ions with a mixed-bed stationary phase

Summary The optimization of chromatographic methods for the determination of metal species require an understanding of the mechanisms involved. In this work, the separation of Cd, Co, Cu, Fe(II/III), Mn, Pb and Zn using a mixed bed column (IonPac CS5A) and a cation-exchange column (IonPac CS2) is studied as a function of mobile phase composition. The type and concentration of complexing agent and of ionic strength modificators were evaluated. The charge of analytes were calculated using the classical ion exchange approach to highlight the effect of eluent composition on retention. The comparative study enabled us to identify an optimal eluent composition for the separation of the nine metal species.     

强碱阴离子交换树脂及碱性洗脱剂的离子排阻/阴离子交换色谱法同时测定NH4+ ，NO2-和NO3-（英文）

Ion-exclusion/anion-exchange chromatography(IEC/AEC) on a combination of a strongly basic anion-exchange resin in the OH——form with basic eluent has been developed.The separation mechanism is based on the ion-exclusion/penetration effect for cations and the anion-exchange effect for anions to anion-exchange resin phase.This system is useful for simultaneous separation and determination of ammonium ion(NH+4),nitrite ion(NO-2),and nitrate ion(NO-3) in water samples.The resolution of analyte ions can be manipulated by changing the concentration of base in eluent on a polystyrene-divinylbenzene based strongly basic anion-exchange resin column.In this study,several separation columns,which consisted of different particle sizes,different functional groups and different anion-exchange capacities,were compared.As the results,the separation column with the smaller anion-exchange capacity(TSKgel Super IC-Anion) showed well-resolved separation of cations and anions.In the optimization of the basic eluent,lithium hydroxide(LiOH) was used as the eluent and the optimal concentration was concluded to be 2 mmol/L,considering the resolution of analyte ions and the whole retention times.In the optimal conditions,the relative standard deviations of the peak areas and the retention times of NH+4,NO-2,and NO-3 ranged 1.28%-3.57% and 0.54%-1.55%,respectively.The limits of detection at signal-to-noise of 3 were 4.10 μmol/L for NH+4,1.87 μmol/L for NO-2 and 2.83 μmol/L for NO-3.     

Determination of carbon dioxide and acid components in exhaust gas by suppressed ion chromatography.

Although anions are usually determined by suppressed ion chromatography (IC), carbonate and bicarbonate ions can not be determined, because a mixed solution of sodium carbonate and sodium hydrogencarbonate is used as the eluent. This paper describes an IC method for the determination of carbonate ion and common anions using an IonPac AG17/AS17 column, an EG 40 eluent generator and a conductivity detector. The proposed IC method could determine carbonate ion and anions within 6 min. The relative standard deviations (n = 5) for chloride (0.4 mg L(-1)), nitrite (0.8 mg L(-1)), carbonate (100 mg L(-1)), nitrate (1.0 mg L(-1)) and sulfate (2.0 mg L(-1)) ions were 5.1%, 1.1%, 4.2%, 5.1% and 1.1%, respectively. In addition, the absorbing solution of carbon dioxide was examined, and 2-amino-2-methyl-1-propanol was found to be a good absorbing solution. The proposed IC method was applied to the determination of carbon dioxide and acid components in flue gas and automobile exhaust gas.     

Modification of ion chromatographic separations by ionic and nonionic surfactants

New findings are reported on simple ways to modify an ordinary HPLC column to obtain efficient ion chromatographic (IC) separations. Permanently coating a column with an ionic surfactant is known to produce an effective column for IC. We now show that incorporation of a nonionic surfactant in the coating, or coating in separate layers, results in a dramatic reduction of ion retention times and gives sharper peaks. Dynamic coating by incorporating a small amount of an alcohol, diol or zwitterion in the aqueous mobile phase permits good separations of alkanecarboxylic acids. A mobile phase containing a quaternary ammonium cation and a zwitterion anion provides excellent separations of common anions on a silica C18 column. An aqueous eluent containing a mixture of a zwitterion 4-(2-hydroxyethyl) acid and methanesulfonic acid can be used in conjunction with a standard cation exchange column. After passing through a membrane suppressor, the mobile phase has a slightly acidic pH, permitting divalent transition metal ions (as well as others) to be detected by conductivity.     

Retention behaviour of strong acid anions in ion-exclusion chromatography on sulfonate and carboxylate stationary phases

Some factors influencing the retention of strong-acid anions on ion-exclusion columns were investigated using columns with sulfonate and carboxylate functional groups. The nature of the functional group on the resin, the eluent pH and the eluent ionic strength all significantly affected the retention and separation of these analytes. Retention was observed for all strong-acid anions over the eluent pH range 2.2-5.7 and increased with both decreasing eluent pH and increasing eluent ionic strength. Some separation of strong-acid anions was possible when using a resin with carboxylate functional groups. It has also been demonstrated that strong-acid anions are poor markers of column void volume for ion-exclusion chromatography. A more accurate value was obtained using the neutral polymeric material dextran blue. When using eluents of low ionic strength, poor or fronted peak shapes were observed. A mechanism for these observations is proposed that relates the shape to ionic strength changes across the peak. A system peak was encountered under most experimental conditions. The properties of this peak are discussed and a cause for the system peak postulated.     

离子色谱-非抑制电导法同时测定铵盐、四乙基铵、甲基三乙基铵

建立了离子色谱非抑制电导法同时分离测定铵根与两种季铵盐四乙基铵、甲基三乙基铵的方法。分别实验了在亲水性和疏水性阳离子交换色谱柱上三种铵类的分离效果,研究了使用不同淋洗液和流速情况下离子的分离情况,结果表明使用SH-Cation-101型疏水性阳离子色谱柱,淋洗液采用甲烷磺酸(5.0mmol/L),其中加入乙腈(7%),于0.8mL/min的流速条件下,三种铵类物质分离良好,其中结构极为相似的两种季铵盐四乙基铵和甲基三乙基铵分离度达到1.5以上,分离时间短,3种物质在13min内实现完全分离。采用国产离子色谱仪非抑制电导法检测,无需使用抑制器,成本低,操作简便可行。检测结果的灵敏度高,线性范围铵根为0.5～50mg/L,四乙基铵和甲基三乙基铵为5～500mg/L,相关系数均高于0.999,相对标准偏差均在3%以内,平均加标回收率在98.5%～101.2%。     

On-line separation of Pu(III) and Am(III) using extraction and ion chromatography

An on-line method developed for separating plutonium and americium was developed. The method is based on the use of HPLC pump with three analytical chromatographic columns. Plutonium is reduced throughout the procedure to trivalent oxidation state, and is recovered in the various separation steps together with americium. Light lanthanides and trivalent actinides are separated with TEVA resin in thiocyanate/formic acid media. Trivalent plutonium and americium are pre-concentrated in a TCC-II cation-exchange column, after which the separation is performed in CS5A ion chromatography column by using two different eluents. Pu(III) is eluted with a dipicolinic acid eluent, and Am(III) with oxalic acid eluent. Radiochemical and chemical purity of the eluted plutonium and americium fractions were ensured with alpha-spectrometry.     

Highly selective ion chromatographic determination of ammonium ions in waters with a suppressor as postcolumn reactor

A highly selective ion chromatographic method for the determination of ammonium ions using an anion-exchange separation column with a bipolar ion exchanger was developed. The method is based on the reaction in a suppressor column between ammonium ions and nitrous acid formed from the eluent components followed by the negative conductimetric signal. The determination of more than 0.1 ppm of NH₄⁺ in water is possible in the presence of 100-fold amounts of alkali metals and inorganic anions.     

Determination of perchlorate in drinking water by ion chromatography using macrocycle-based concentration and separation methods

Macrocycle-based ion chromatography provides a convenient, reliable method for the determination of perchlorate ion, which is currently of great interest to the environmental community. This study shows that effective perchlorate determinations can be made using standard conductimetric detection by combining an 18-crown-6-based mobile phase with an underivatized reversed-phase mobile phase ion chromatography (MPIC) column. One unique feature of this method is the flexibility in column capacity that is achieved through simple variations in eluent concentrations of 18-crown-6 and KOH, facilitating the separation of target analyte anions such as perchlorate. Using a standard anion exchange column as concentrator makes possible the determination of perchlorate as low as 0.2 ug/L in low ionic strength matrices. Determination of perchlorate at the sub-ug/L level in pure water and in spiked local city hard water samples with high background ion concentrations can be achieved this way. However, like other IC techniques, this method is challenged to achieve analyses at the ug/L level in the demanding high ionic strength matrix described by the United States Environmental Protection Agency (EPA) (1,000 mg/L chloride, sulfate and carbonate). We approached this challenge by use of the Cryptand C1 concentrator column, provided by Dionex Corporation, to effectively preconcentrate perchlorate while reducing background ion concentrations in the high ionic strength matrix. The retention characteristics of the concentrator column were studied in order to maximize its effectiveness for perchlorate determinations. The method makes possible the determination of perchlorate at the 5 ug/L level in the highest ionic strength matrix described by the EPA.     

Ion-exchange-based eluent-free preconcentration of some anions

Preconcentration procedures based on ion-exchange methods are often used to enhance the sensitivities of analytical techniques where the eluent used for eluting the preconcentrated ions does not influence the subsequent analytical step. Until recently, only a limited use of ion-exchange-based sample preconcentration procedures has been found in those analytical techniques where the eluent components strongly influence the separation procedure [e.g., capillary electrophoresis (CE)]. In this paper, we present a preconcentration procedure based on (i) the preconcentration of anions on an ion-exchange resin, (ii) the subsequent elution of analytes, and (iii) on-line removal of eluent components by chemical suppression using an appropriate suppressor device (either packed-bed suppressor column or micromembrane suppressor). The adjustment of the system parameters, combined with a computer-controlled, sensing/switching system, resulted in a minimal additional dilution of the eluted preconcentrated anions. The efficiency of the proposed enrichment/matrix removal procedure was tested by using off-line CE analysis of collected preconcentrated samples, reaching a LOD of 1 microg/l for a selected anion.     

离子色谱法测定高氯、高钠油田回注水中的阴、阳离子及有机酸

建立了高氯、高钠油田回注水中痕量无机阴、阳离子和有机酸的离子色谱分析方法。对高钠基质中痕量阳离子的测定,选用IonPac CS12A分析柱、H2SO4溶液梯度淋洗、电导检测器检测;对高氯基质中阴离子及有机酸的测定,选用对OH-具有高选择性的高容量的IonPac AS11-HC柱、KOH梯度淋洗、电导检测器检测。在优化的梯度淋洗条件下,高氯或高钠的存在不影响痕量阴离子或阳离子的测定。该方法具有良好的线性(r=0.9926~0.9990)和精密度(测定组分峰面积的相对标准偏差(n=7)在8.0%以下),回收率     

Determination of toluene diisocyanate in synthetic-rubber track by ion chromatography with ultraviolet detection after alkaline suppressor

In the present work,a novel analytical method was proposed for the determination of toluene diisocyanate(TDI)in synthetic- rubber track by ion chromatography(IC)coupled with an ultraviolet detector setting at 212 nm.TDI can be hydrolyzed to toluene diamine(TDA)which can be separated by cation-exchange IC easily.The optimum IC separation was performed on an IonPac CS12A column(150 mm×4.0 mm)using 20 mmol L~(-1)sodium sulfate,10 mmol L~(-1)sulfuric acid and 10%acetonitrile as eluent. It was found that a hi...     

Ion chromatographic separation of car☐ylic acids prediction of retention data

The retention behavior of biologically relevant monovalent (formic, acetic, propionic, lactic and pyruvic) and divalent (oxalic, malonic, succinic, fumaric, maleic and tartaric acids) car☐ylic acids together with inorganic analytes (chloride and sulphate) has been studied. The separation was performed on a latex-based strong anion-exchange resin using carbonate buffer systems in suppressed IC. The retention behaviour of analytes was investigated at different pH values and [HCO₃⁻]+[CO₃²⁻] concentrations. A theoretical model, involving ion-exchange equilibria of sample and eluent anions, was derived and applied to the chromatographic data obtained. Chromatographic ion exchange selectivity values were determined and retention data were calculated for the anions using different carbonate eluent conditions. The average of errors between the predicted and the measured retention volumes of the analytes studied does not exceed 4.0%. The study effectively characteristics the behaviour of different analytes under elution conditions of practical importance.     

Ion chromatographic separations of phosphorus species: a review

The aim of this paper is to review recent literature regarding the determination of phosphorus species by ion chromatography (IC), and describe the implementation of new developments in sample treatment and ion chromatography methodology for the analysis of these compounds. Ion-exchange methods using both carbonate/hydrogencarbonate and hydroxide selective columns in combination with self-regenerating membrane and solid-phase-based suppressors enable determination of phosphate down to ppb levels. New technology, particularly on-line electrolytic hydroxide generators and electrolytic self-regenerating suppressor devices, has allowed the use of elution gradients in both carbonate/hydrogencarbonate and hydroxide selective systems, improving sensitivity and reducing total analysis time for samples containing phosphate together with other inorganic anions. In addition to a review of these developments, optimization and application of chromatographic methods using reversed stationary phases and cationic and/or zwitterionic surfactants is also discussed.The objective of most of the IC methods developed for phosphorus species is the determination of phosphate and total phosphorus. Therefore, sample treatment and separation conditions specifically developed for this purpose are also described. In addition, application of IC to the analysis of other inorganic (reduced and condensed) and organic (phytates, alkyl phosphate, and phosphonates) phosphorus species is discussed along with methodology and relevant applications in water analysis and other miscellaneous fields.