Simultaneous determination of silicate and phosphate in environmental waters using pre-column derivatization ion-pair liquid chromatography

A highly sensitive HPLC method for the simultaneous determination of soluble silicate and phosphate in environmental waters was developed, using ion-pair liquid chromatography preceded by the formation of their yellow α-heteropolymolybdates. The moderate-pH mobile phase enabled to use a highly efficient reversed-phase silica column. The pre-column coloring reactions at moderate-pH were reproducible for both silicate and phosphate in all quantification ranges with R.S.D.s less than 2% and 5%, respectively. The linear calibration lines between concentrations (mg-SiO₂/L and mg-PO₄/L) and peak area intensities were obtained for silicate and phosphate both with acceptable determination coefficients (r²) of 0.9999. The limits of determination for both analytes were 0.007 mg-SiO₂/L and 0.003 mg-PO₄/L, which were calculated theoretically using 10σ/slope. The four-digit dynamic ranges were obtained for 0.007-10 mg-SiO₂/L and 0.003-20 mg-PO₄/L. The developed method was applied for the analysis of tap water, river water, coastal seawater, well water, hot-spring water, commercial mineral water, and laboratory water. The results were very reasonable and acceptable from the environmental viewpoints, which were well correlated with those confirmed by the molybdenum-blue spectrophotometry.     

Simultaneous determination of silicate and phosphate in boiler water at power plants based on series flow cells by using flow injection spectrophotometry

A new flow injection spectrophotometric method is described for the simultaneous determination of silicate and phosphate. Effects on the sensitivity of the method of the wavelength, temperature, length of reaction coils, pump rates, acidity, sampling volume, concentration of the chromogenic reagent, etc. were also investigated. The optimum conditions were ascertained.The principle of the method is that total concentration of silicate plus phosphate is determined when a injected sample plug is passing through the first flow cell and then the concentration of silicate is serially) determined at a second flow cell of the same detector after continuously masking the yellow molybdophosphate in the sample zone. Finally, the concentration of phosphate is obtained by difference.Silicate and phosphate are determined in boiler water at power plants; 60-120 samples h⁻¹ be analyzed. Determination ranges are 0.05-22 mg l⁻¹ for silicate and 0.1-24 mg l⁻¹ for phosphate. Relative standard deviations for metasilicate and orthophosphate were ≤1.2 and 1.3%, respectively. Recovery ranges of silicate and phosphate in the samples are 98-103%.     

A selective lon-exchange separation and spectrophotometric determination of traces of copper in silicate rocks

Summary A combined cation-exchange separation-spectrophotometric procedure has been worked out for the accurate determination of traces of copper in silicate rocks. Silicates are opened up with sulfuric and hydrofluoric acids. The residue is taken up into a 0.5 M hydrochloric acid −0.05 M oxalic acid −1% hydrogen peroxide solution and loaded on a strongly acidic cation-exchange resin column. Polyvalent ions including ferric ions do not adsorb on the column, while copper (II) retains together with divalent metal ions as well as aluminum (III). Copper (II) can selectively be eluted by a small volume of 0.05 M thiosulfate solution. This fraction is sufficiently pure to allow a direct spectrophotometric determination of copper with Na-DDTC without the addition of tartrate and EDTA as masking agents. Quantitative results are quoted for the determination of copper in international standard rocks of the Geological Survey of Japan (GSJ) and the U.S. Geological Survey (USGS).     

Stopped-flow injection simultaneous determination of phosphate and silicate using molybdenum blue

Kinetic information for the phosphate–molybdate–ascorbic acid reaction can be obtained by making use of a very simple manually operated stopped-flow injection (FI) system. Various parameters (concentrations of reagents, flow rate, mixing coils, and volume of flow cell) were investigated for determination of phosphate. A stopped-FI system should be arranged for low degree of mixing (of reactants) and low dispersion so that good signals of rate changes will be observed. Simultaneous determination of phosphate and silicate by the stopped-FI technique is proposed, using a laboratory-made semi-automatic stopped-FI Analyzer with LED-based photometer. It is based on kinetic separation of phosphate and silicate using molybdenum blue. The proposed procedure has been demonstrated for the application to water samples. The results obtained agree with that of a standard method.     

Simultaneous determination of oxalate, thiosulfate, and thiocyanate in urine by ion-exclusion chromatography with electrochemical detection

Summary A sensitive ion-exclusion chromatographic method has been developed for determination of oxalate, thiosulfate, and thiocyanate. The method is based on separation of these anions on a polymethacrylate-based, weakly acidic cation-exchange resin (TSKgel OApak-A) and detection by means of a glassy carbon (GC) electrode electrochemically modified with polyvinylpyridine (PVP), palladium, and iridium oxide (PVP/Pd/IrO₂). The electrochemical behavior of oxalate, thiosulfate, and thiocyanate at this chemically modified electrode (CME) have been investigated by cyclic voltammetry. The results indicated that electrocatalytic oxidation of these anions by the electrode was efficient and that the sensitivity, stability, and lifetime of the electrode were relatively high. Combined with ion-exclusion chromatography the PVP/Pd/IrO₂ electrode was used as the working electrode for amperometric detection of these anions. All linear ranges were over two orders of magnitude and detection limits, defined asS/N=3, were 9.0×10⁻⁷ mol L⁻¹ for oxalate, 6.7×10⁻⁷ mol L⁻¹ for thiosulfate, and 5.6×10⁻⁷ mol L⁻¹ for thiocyanate. Correlation coefficients were all>0.998. Coupled with microdialysis sampling the method has been successfully applied to the determination of oxalate, thiosulfate, and thiocyanate in urine.     

Fluorimetric determination of bromate by ion-exchange separation and post-column derivatization

For the determination of bromate in drinking water a stopped-flow post-column reaction was developed following the separation of bromate from the matrix by an anion-exchange column. In the post-column reaction the analyte was used to oxidize the azo dye sulfonaphtholazoresorcinol, SNAR, and the residual amount was converted into a fluorescent binuclear complex by an excess of gallium ions. The fluorescence was monitored at 585 nm, with a maximum excitation wavelength at 521 nm. The determination of bromate is based on the decrease of the fluorescence intensity with increasing bromate concentration. The given hydrodynamic parameters and the condition of equal flow rates of the two branch streams at each T-piece have to be considered as an important criterion for the experimental set-up. The volume flows and the concentrations required for the reagent solutions in the influent of each T-piece were determined as a result of batch experiments and theoretical considerations. The limit of detection was 0.28 g L^–1bromate for the flow method, which shows linearity up to 15 gL^–1 bromate.     

Simultaneous spectrophotometric determination of phosphate and silicate by using principal component artificial neural network

A very sensitive, simple and selective spectrophotometric method for simultaneous determination of phosphate and silicate based on formation of phospho- and silicomolybdenum blue complexes in the presence of ascorbic acid is described. Although the complexes of phosphate and silicate with reagent in the presence of ascorbic acid show a spectral overlap, they have been simultaneously determined by principal component artificial neural network (PC-ANN). The PC-ANN architectures were different for phosphate and silicate. The output of phosphate PC-ANN architecture was used as an input for silicate PC-ANN architecture. This modification improves the capability of silicate PC-ANN model for prediction of silicate concentrations. The linear range was 0.01-3.00 microg mL(-1) for phosphate and 0.01-5.00 microg mL(-1) for silicate. Interference effects of common anions and cations were studied and the proposed method was also applied satisfactorily to the determination of phosphate and silicate in detergents.     

Simultaneous determination of metal ions as complexes of pentamethylene dithiocarbamate in Indus river water,Pakistan

River water samples before and after mixing with industrial effluents were collected at an interval of 4 weeks for one year and analyzed for simultaneous determination of Fe³⁺, Cr³⁺, Mn²⁺, Cu²⁺, Ni²⁺and Co²⁺ after preconcentration using pentamethylene dithiocarbamate (PMDTC) as derivatizing reagent and subsequent solvent extraction by high performance liquid chromatography (HPLC). The average levels (n = 12) of metal ions were found in the range of 14.2–542 μg/L. The results were then compared with a standard flame atomic absorption spectrophotometric method revealed no significant differences.     

High-performance liquid chromatographic determination of clenbuterol and cimaterol using post-column derivatization.

A general high-performance liquid chromatographic method for the simultaneous and rapid determination of cimaterol and clenbuterol is described. Solid samples, such as animal tissues, faeces and feeding-stuffs, are extracted with dilute acid saturated with ethyl acetate. The resulting extracts or liquid samples, such as urine, plasma, blood and bile, are purified via Chem Elut columns. Separation is achieved by ion-pair chromatography on a Nova-Pak C18 column, and highly specific detection is obtained with an adapted version of the post-column derivatization described previously for the determination of clenbuterol in urine and animal tissues. Detection limits for liquids and solids are 0.1 ng/ml and 0.2 ng/g, respectively. The results are in complete agreement with analysis by high-performance thin-layer chromatography and gas chromatography-mass spectrometry, applied for confirmation after the same sample pretreatment. With this simple method, complete analysis of a liquid sample needs about 30 min and, even without an automatic sampler, 40 samples can be completely analysed in one day. This method has been used on a routine scale for nearly two years.     

离子排斥色谱结合光度检测的水质监测系统用于测定离子型营养物（英文）

A unified ion-exclusion chromatography(IEC) system for monitoring anionic and cationic nutrients like NH + 4,NO 2,NO 3,phosphate ion,silicate ion and HCO 3 was developed and applied to several environmental waters.The IEC system consisted of four IEC methodologies,including the IEC with ultraviolet(UV) detection at 210 nm for determining NH + 4 on anion-exchange separation column in OH form connected with anion-exchange UV-conversion column in I form in tandem,the IEC with UV-detection at 210 nm for determining simultaneously NO 2 and NO 3 on cation-exchange separation column in H + form,the IEC with UV-detection at 210 nm for determining HCO 3 on cation-exchange separation column in H + form connected with anion-exchange UV-conversion column in I form in tandem,and the IEC with visible-detection based on molybdenum-blue reaction for determining simultaneously silicate and phosphate ions on cation-exchange separation column in H + form.These IEC systems were combined through three manually-driven 6-port column selection valves to select each separation column to determine selectively the ionic nutrients.Using this sequential water quality monitoring system,the analytical performances such as calibration linearity,reproducibility,detection limit and recovery were also tested under the optimized chromatographic conditions.This novel water quality monitoring system has been applied successfully for the determination of the ionic eutrophication components in sub-urban river waters.     

Liquid chromatographic determination of aliphatic amines in water using solid support assisted derivatization with 9-fluorenylmethyl chloroformate

Summary A simple and sensitive method has been developed for the liquid chromatographic determination of short-chain aliphatic amines in water. Analytes are retained in solid-phase extraction (SPE) cartridges, and then derivatized by drawing an aliquot of the fluorogeneic reagent 9-fluorenylmethyl chloroformate (FMOC) through the cartridges. After a certain reaction time the derivatives formed are desorbed with acetonitrile. The collected extracts are then chromatographed on a LiChrospher 100 RP₁₈ 125 mm×4 mm i.d., 5 μm, column using an acetonitrile-water gradient. The influence of experimental conditions (SPE material, volume of sample, concentration of FMOC, time of reaction and pH) has been investigated. Optimal results have been obtained with C₁₈ SPE cartridges using a sample volume of 5.0 mL. For derivatization, 0.25 mL aliquots of 25 mM FMOC have been used, the reaction time being only 2 min. The method has been applied to the quantification of several aliphatic amines: methylamine, ethylamine, dimethylamine,n-butylamine,n-pentylamine andn-hexylamine. Under the proposed conditions the percentages of analytes retained plus derivatized were of about 54–107% compared to those obtained with direct solution derivatization. The method provided good reproducibility, linearity and accuracy within the 0.050–1.0 mg L⁻¹ concentration range. The limits of detection were in the 0.25–5.0 μg L⁻¹ range. The utility of the described approach has been tested by analysing tap water, river water and industrial waste water.     

亲水作用色谱柱与阳离子交换树脂柱结合分离无机离子（英文）

A combination of hydrophilic interaction chromatographic(HILIC) column and a weakly acidic cation-exchange resin(WCX) column was used for simultaneous separation of inorganic anions and cations by ion chromatography(IC).Firstly,the capability of HILIC column for the separation of analyte ions was evaluated under acidic eluent conditions.The columns used were SeQuant ZIC-HILIC(ZIC-HILIC) with a sulfobetaine-zwitterion stationary phase(ZIC-HILIC) and Acclaim HILIC-10 with a diol stationary phase(HILIC-10).When using tartaric acid as the eluent,the HILIC columns indicated strong retentions for anions,based on ion-pair interaction.Especially,HILIC-10 could strongly retain anions compared with ZIC-HILIC.The selectivity for analyte anions of HILIC-10 with 5 mmol/L tartaric acid eluent was in the order of I-> NO-3 > Br-> Cl-> H2PO-4.However,since HILIC-10 could not separate analyte cations,a WCX column(TSKgel Super IC-A/C) was connected after the HILIC column in series.The combination column system of HILIC and WCX columns could successfully separate ten ions(Na+,NH+4,K+,Mg2+,Ca2+,H2PO-4,Cl-,Br-,NO-3 and I-) with elution of 4 mmol/L tartaric acid plus 8 mmol/L 18-crown-6.The relative standard deviations(RSDs) of analyte ions by the system were in the ranges of 0.02%-0.05% in retention times and 0.18%-5.3% in peak areas through three-time successive injections.The limits of detection at signal-to-noise ratio of 3 were 0.24-0.30 μmol/L for the cations and 0.31-1.2 μmol/L for the anions.This system was applied for the simultaneous determination of the cations and the anions in a vegetable juice sample with satisfactory results.     

A comprehensive chromatographic comparison of amphetamine and methylamphetamine extracted from river water using molecular imprinted polymers and without the need for sample derivatization

This work explores the differences between two GCMS instruments for the determination of amphetamine and methylamphetamine extracted from water samples (ultra pure water and river water) without the necessity for derivatization. The instruments contained different generations of gas chromatograph and mass selective detector components and revealed significantly different results when presented with the same samples. The extraction methodology also compared two SPE systems. The extraction efficiency of commercially available molecular imprinted polymers as a sorbent in SPE was compared with commonly used hydrophilic balance sorbent. Molecular imprinted polymers provided excellent recoveries (81 ± 2% and 108 ± 3% at 30 μg L^?1, and 94 ± 2% and 94 ± 2% at 200 μg L^?1 for amphetamine and methylamphetamine, respectively). The best LOD obtained was sufficient for the determination of both drugs extracted from river water (0.029 ± 0.003 and 0.015 ± 0.004 μg L^?1 for amphetamine and methylamphetamine, respectively). These were comparable to literature values obtained through conventional extraction and analysis using LC‐MS/MS but had the advantage of being achieved using an underivatized GCMS method.     

Determination of organic acids in air by capillary electrophoresis and ion-exclusion chromatography

Summary A capillary electrophoretic (CE) method for the determination of organic acids in the low ppm range is described. The buffer consisted of 5 mM 2,6-pyridinedicarboxylic acid and 0.5 mM cetyltrimethylammonium bromide, pH 5.6. The former served as background electrolyte for indirect UV detection at 200 nm, whereas the latter was used to reverse electroosmotic flow. In <5 min 8 low molecular mass organic acids (oxalic, formic, malonic, glutaric, glycolic, acetic, lactic and propanoic) and two inorganic acids (hydrochloric and sulphuric) were separated. Detection limits for anions tested were 0.04 mg L⁻¹ (lactic acid) to 0.6 mg L⁻¹ (malonic acid). The method was applied to the determination of organic acids in air samples. The CE results when compared with ion-exclusion chromatography (IEC) agreed well. The use of electrokinetic injection in CE proved beneficial for preconcentration of organic acids in real samples. Using electrokinetic injection, preconcentration factors ranging from 14 (hydrochloric acid) to 3 (propanoic acid) were obtained. Presented at Balaton Symposium on High-Performance Separation Methods, Siófok, Hungary, September 1–3, 1999     

Flow-injection spectrophotometric determination of silicate,phosphate and arsenate with on-line column separation

The simultaneous determination of silicate, phosphate and arsenate by using flow-injection analysis with on-line column separation is described. Determinations are based on measurement of the absorbance at 810 nm of the heteropoly blue formed with ascorbic acid as reducing reagent. Effects of flow rates, temperature of reaction coils and sample injection volumes are reported; optimum conditions are 0.25 ml min^?1 for the ascorbic acid stream, 95°C for the reaction coils and 300 μl for the injection volume. With the anion-exchange column (TSK-gel SAX), the optimal flow rate of the eluent is 0.75 ml min^?1. Relative retention times depend on the concentration of the KCl/NH₃/EDTA eluting solution; separation and simultaneous determination of the three ions are satisfactory at around 10^?4 mol l^?1 concentrations of the three ions.     

Trace anion determination in concentrated hydrofluoric acid solutions by two-dimensional ion chromatography I. Matrix elimination by ion-exclusion chromatography

Since years, ion exclusion chromatography (ICE) has been the standard method to separate strong acid analyte anions from concentrated weak acid matrices such as hydrofluoric acid (HF). In this work, the commercially available IonPac ICE-AS 1 column was used to separate trace levels of chloride, nitrate, sulfate and phosphate from HF solutions at 20% (w/w). The efficiency of the separation was studied in more detail using techniques such as ion chromatography (IC), inductively coupled plasma optical emission spectrometry (ICP-OES) and ICP-mass spectrometry (ICP-MS). For 20% (w/w) HF solutions and at a water carrier flow-rate of 0.50 ml/min, the cut window was set from 8.5 to 14.5 min. Under these conditions, analyte recoveries of better than 90% were obtained for chloride, nitrate and sulfate, but only about 75% for phosphate. The HF rejection efficiency was better than 99.9%. It was found that the ICP techniques, measuring total element levels and not species, yielded significantly higher recoveries for phosphorus and sulfur compared to IC. Evidence will be given that part of the added phosphorus (approximately 15% for an addition of 10 mg PO4/kg) is present as mono-fluorophosphoric acid (H2FPO3). In the case of sulfate, the difference between IC and ICP-MS could be attributed to an important matrix effect from the residual HF concentration.     

高效液相色谱法测定蜂产品中链霉素残留量

采用双试剂柱后衍生法,在C18柱上以0.01mol L1 庚烷磺酸钠 乙腈(65 35)为流动相,以荧光检测器(λex=263nm,λem=447nm)检测蜂蜜中链霉素的残留量,优化了蜂蜜样品的前处理方法和高效液相色谱条件,包括流动相组成和流速、衍生化试剂的处理、样品前处理过程中淋洗液和提取液的用量等,并选用三氯乙酸溶液(1 1)作为沉淀剂,建立了一种较好的链霉素检测方法。     

An improved ion chromatographic method for determination of trace levels of perchlorate in environmental water

An improved ion chromatographic (IC) method was developed to determine trace levels of perchlorate in environmental water samples. Perchlorate was separated in the hydroxide selective column IonPac AS16 using NaOH as an eluent with an organic modifier. To eliminate the coelution of perchlorate and 4-chlorobenzene sulfonate (4-CBS), an organic solvent as modifier was added to the eluent. Of four organic solvents studied, acetonitrile proved to be the most efficient based on the retention time of perchlorate and 4-CBS. To improve the method sensitivity, a concentrator column (AG19) was used to concentrate perchlorate online. With the adoption of a preconcentration step, the sensitivity of our method was improved and the method detection limit (MDL) was reduced to 0.1 μg/L. The linear range was from 0.2 μg/L to 200 μg/L with a linear correlation coefficient of 0.9989 and the relative standard deviation (RSD) of peak area for eleven successive injections of 0.5 μg/L perchlorate was 4.2%. The method had been applied to the determination of perchlorate in some real environmental water samples and recovery was between 93% and 113%. __________ Translated from Chemical Journal of Chinese Universities, 2007, 28(7), 1246–1250 [译自: 高等学校化学学报]