Quantitative calibration of spectroscopic signals in combined TG-FTIR system

In thermoanalytical investigations the determination of the composition of the evolved gases is very important, especially when investigating decomposition processes or gas-solid reactions occurring in multi-component systems. The potential of simultaneous techniques, enabling the qualitative analysis of evolved species, such as TG-MS or TG-FTIR has been further improved by the introduction of the pulse thermal analysis (PulseTA^®). This method provides a quantitative calibration by relating the mass spectrometric or FTIR signals to the injected quantity of probe gas.The influence of several experimental parameters such as concentration of the analyzed species, temperature and flow rate of the carrier gas on FTIR signals has been investigated. The reliability of quantifying FTIR signals was checked by relating them to the amount of evolved gases measured by thermogravimetry. In order to extend the opportunities for quantifying FTIR signals, the possibility of the injection of liquids into the carrier gas stream was studied. The linear dependence between the injected amount of liquids and the integral intensity of spectroscopic signals (peak area) enabled easy quantification of FTIR data. Systematic studies on a new method based on isothermal vaporization of liquids further widen the application range of in situ calibrations.     

Selective determination of penicillamine by on-line vapor-phase generation combined with Fourier transform infrared spectrometry

In this work, an on-line system with vapor-phase generation (VPG) and Fourier transform infrared (FTIR) spectrometric detection has been developed as a direct and highly selective analytical technique for the assay of penicillamine (PA). Potassium iodate solution was injected into a reactor, heated at 75 °C, containing PA. The CO generated under these conditions was transported by means of N₂ gas carrier stream to an infrared gas cell and corresponding FTIR spectra were acquired in a continuous mode. The maximum absorbance of CO band at 2170 cm⁻¹, corrected by a baseline established between 2240 and 2000 cm⁻¹ at a nominal resolution of 2 cm⁻¹, was selected as a measurement criterion. Initially, the effect of different chemical, physical and spectroscopic parameters, such as concentration and volume of oxidant, pH, equilibrium time, reactor temperature, reactor volume, N₂ carrier flow rate and number of scans on the analytical signals were evaluated by using a short path length (10 cm) IR gas cell. At optimum experimental conditions, the method provided a relatively broad linear dynamic range of 4-380 mg L⁻¹, a limit of detection of 0.5 mg L⁻¹, a sampling frequency of 15 h⁻¹ and a relative standard deviation (R.S.D.) of 1.6%. Further, the method was successfully applied to the determination of PA in pharmaceutical formulations and results compared well with those obtained by a reference colorimetric method.     

Flow analysis-hydride generation-Fourier transform infrared spectrometric determination of antimony in pharmaceuticals

In this work, a flow analysis system with hydride generation and Fourier transform infrared (FTIR) spectrometric detection has been developed for the determination of antimony in pharmaceuticals. The method is based on the on-line mineralization/oxidation of the organic antimonials present in the sample and pre-reduction of Sb(V) to Sb(III) with K₂S₂O₈ and KI, respectively; prior to the stibine generation. The gaseous SbH₃ is separated from the solution in a gas phase separator, and transported by means of a nitrogen carrier into a short pathway (10 cm) IR gas cell, where the corresponding FTIR spectrum is acquired by accumulating 3 scans in a continuous mode. The 1893 cm⁻¹ band was used for the quantification of the antimony. The procedure is carried out in a closed system, which reduces sample handling and makes possible the complete automation of the antimony determination. The figures of merit of the proposed method (linear range: 0-600 mg l⁻¹, limit of detection (3σ)=0.9 mg l⁻¹, limit of quantification (10σ)=3 mg Sb l⁻¹, precision (R.S.D.) less than 1% and sample frequency=28 h⁻¹), are appropriate for the designed application. Furthermore, precise and accurate results were found for the analysis of different antimonial pharmaceutical samples, indicating that the methodology developed represents a valid alternative for the determination of antimony in pharmaceuticals, which could be suitable for the routine control analysis.     

Improved GC/ECNI-MS sensitivity of decabromodiphenyl ether determination on 30 m columns by increasing the carrier gas flow after a modified gel permeation chromatographic cleanup protocol employing cyclohexane/ethyl acetate as eluent

BDE-209 is the predominant constituent of the commercial mixture decabromodiphenyl ether which is used as brominated flame retardant (BFR). Owing to difficulties associated with the high mass (thermal instability and low vapour pressure), short GC columns (≤15?m) have been suggested for its analysis while longer columns (30–50?m) are suggested for other polybrominated diphenyl ether (PBDE) congeners. To overcome this considerable expenditure in the analysis of PBDEs, we aimed at increasing the sensitivity of BDE-209 analysis by gas chromatography coupled with electron-capture negative ion mass spectrometry (GC/ECNI-MS) on a 30?m column. The chromatographic performance of BDE-209 on the 30?m GC column was improved by increasing the carrier gas flow from initially 1.2?mL?min^?1 to 5 or 10?mL?min^?1 after the last octabromo diphenyl ether (Br₈DE) congener was eluted. With this high carrier gas flow, the column residence time of BDE-209 was shortened by ～25%, the peak height was increased and, consequently, the limit of detection by GC/ECNI-MS in selected ion monitoring (SIM) mode was improved. When this high-flow GC/ECNI-MS-SIM method was applied to a sediment sample, we realized that gel permeation chromatography (GPC) – used for the removal of lipids and/or sulphur – provided low recovery rates for BDE-209. The large molecule BDE-209 eluted late and only 50% was recovered by our previous standard protocol for polyhalogenated compounds. Application of a modified GPC procedure with a longer collection time increased the recovery of BDE-209 in the GPC step to ～90%.     

Sampling and analysis of flue gases from a plasma incinerator

A system is described for monitoring flue gases from a plasma incinerator for polychlorinated biphenyls (PCBs), polychlorinated dibenzodioxins and polychlorinated dibenzofurans. The system is composed of three basic units: sampler/preconcentrator, gas chromatograph and mass-selective detector. The sampler operates by solid sorbent trapping and thermal desorption. The use of two adsorbers allows sampling at a high flow rate (～1 1 min^?1) and subsequent capillary gas chromatographic analysis without the need for cold traps. A sample trapped on the first adsorber is thermally desorbed and transferred by a carrier stream of 40 cm³ min^?1 to a second smaller adsorber and retrapped. It is then thermally desorbed and injected into the capillary column by a carrier gas at an appropriate flow rate. A sequential valve-minder activates the electric actuators of the two six-port valves used in the design and also controls the power required for heating the adsorbers. Operation of the sampler is automated and is initiated by a single push-button switch. In simulation, the system allowed the separation of the major compounds of interest from possible interferences in <15 min and afforded unambiguous identification of the hazardous compounds and their quantification. For a sample volume of 20 1, the minimum detectable concentration of PCBs is 25–50 ng m^?3.     

Fourier transform infrared determination of CO2 evolved from carbonate in carbonated apatites

A quantitative method based on FTIR has been developed to determine carbonate in synthetic apatites. The method measures the evolved CO₂ after reaction of 50 mg apatite with 2 mL of hydrochloric acid (0.5 M) in a reaction vessel, heated to 40?°C. The CO₂ evolved was swept by a carrier of nitrogen to a laboratory-made infrared gas cell of 39 mm pathlength and 490 μL volume. The signals were recorded as a function of time and the areas of the chemigram peaks obtained from the measurements in the wavenumber range of 2500–2150 cm^–1, were interpolated using a calibration curve. The method can be used to study apatites with carbonate contents below 0.2% with a sampling frequency of 8 h^–1.     

Fourier transform infrared spectrometric determination of Malathion in pesticide formulations

An environmentally friendly methodology has been developed for quality control analysis of emulsifiable concentrate pesticide formulations containing Malathion as active ingredient, using flow injection analysis (FIA)-Fourier transform infrared (FTIR) spectrometry. Five microlitres samples were directly injected into a 3 ml closed FIA manifold, in which 2 ml of CHCl₃ was re-circulated at 1.96 ml min⁻¹. After homogenisation and sample measurement, 2 μl volumes of a Malathion standard were injected, taking absorbance measurements after each injection. Peak height of the chemigrams, established from peak area values between 1027 and 1017 cm⁻¹, corrected with a baseline fixed from 1087 to 993 cm⁻¹ were employed for Malathion quantification using the standard addition approach, after reaching the steady state for every injection. A limit of detection of 12 μg ml⁻¹ was achieved. Results found by standard addition-FTIR in commercially available samples showed a good correlation with those obtained by the reference gas chromatography-flame ionisation detection procedure.     

Water splitting in low-temperature ac plasmas at atmospheric pressure

Plasma-induced water splitting at atmospheric pressure has been studied with a novel fan-type Pt reactor and several tubular-type reactors: an all-quartz reactor, a glass reactor, and three metal reactors with Pt. Ni, and Fe as electrodes. Reaction products have been analyzed by using GC (gas chromatography) and Q-MS (quadrupole mass spectrometry). Optical emission spectroscopic studies of the process have been carried out by employing a CCD (charge-coupled device) detector. Water splitting with tubular quartz and glass reactors is probably non-catalytic. However, a heterogeneous catalytic function of surface of metal electrodes has been observed. The variation of hydrogen yield (Y_H) and energy efficiency (E_e) with operational parameters such as input voltages (U_in), flow rates of carrier gas (F_He), and concentrations of water (C_W) has been examined. Plasma-induced water splitting can be described with a kinetic equation of-dC_w/dt = kC_W ^0.2. The rate constants at 3.25 kV are 2.8 × 10⁻⁴, 3.5 × 10⁻³, and 3.4 × 10⁻² mol^0.8L^−0.8 min⁻¹ for tubular glass reactor, a tubular Pt reactor, and a fan-type Pt reactor, respectively. A CSTR (continuous-stirred tank reactor) and PFR (piston-flow reactor) model have been applied to a fan-type reactor and tubular reactor, respectively. A mechanism on the basis of optical emission spectroscopic data has been obtained comprising the energy transfer from excited carrier gas species to water molecules, which split via radicals of HO^·, O^·, and H^· to form H₂ and O₂. The fan-type Pt reactors exhibit highest activity and energy efficiency among the reactors tested. Higher yields of hydrogen are achieved at higher input voltages, low flow rates, and low concentrations of water (Y_H = 78 % at U_in of 3.75 kV, F_He of 20 mL/min, and C_W of 0.86 %). The energy efficiency exhibits an opposite trend (E_e = 6.1 % at U_in of 1.25 kV, F_He of 60 mL/min and C_W of 3.1 %).     

Thermal decomposition of liebigite

Summary A combination of high resolution thermogravimetric analysis coupled to a gas evolution mass spectrometer has been used to study the thermal decomposition of liebigite. Water is lost in two steps at 44 and 302°C. Two mass loss steps are observed for carbon dioxide evolution at 456 and 686°C. The product of the thermal decomposition was found to be a mixture of CaUO₄ and Ca₃UO₆. The thermal decomposition of liebigite was followed by hot-stage Raman spectroscopy. Two Raman bands are observed in the 50°C spectrum at 3504 and 3318 cm^-1 and shift to higher wavenumbers upon thermal treatment; no intensity remains in the bands above 300°C. Three bands assigned to the υ₁ symmetric stretching modes of the (CO₃)^2- units are observed at 1094, 1087 and 1075 cm^-1 in agreement with three structurally distinct (CO₃)^2- units. At 100°C, two bands are found at 1089 and 1078 cm^-1. Thermogravimetric analysis is undertaken as dynamic experiment with a constant heating rate whereas the hot-stage Raman spectroscopic experiment occurs as a staged experiment. Hot stage Raman spectroscopy supports the changes in molecular structure of liebigite during the proposed stages of thermal decomposition as observed in the TG-MS experiment.     

Analysis of Spectinomycin by HPLC with Evaporative Light-Scattering Detection

A high-performance liquid chromatographic method with evaporative light-scattering detection (ELSD) has been developed for analysis of spectinomycin and related impurities. Separation of spectinomycin from structurally related impurities was achieved on a C₁₈ column. The optimized mobile phase was 25 mmol L⁻¹ ammonium acetate (pH 7.5)-methanol, 90:10 (v/v), at a flow rate of 0.6 mL min⁻¹. The temperature of the drift tube of the ELSD was 95°C and the flow rate of carrier gas was 2.2 L min⁻¹. The accuracy, specificity, precision, linearity, sensitivity, and robustness of the method were validated in accordance with ICH guidelines. In addition to determination of spectinomycin and related impurities, the method is also ideal for determination of the salts spectinomycin hydrochloride and spectinomycin sulfate.     

Sorbent separation and enrichment method for cobalt ions determination by graphite furnace atomic absorption spectrometry in water and urine samples using multiwall carbon nanotubes

A new cobalt ions pre-concentration method, optimised by fractional factorial design, using multiwall carbon nanotubes (MWCNTs) with further Graphite Furnace Atomic Absorption Spectrometry (GFAAS) quantification is described. The method explores the high chemical and physical stability of MWCNTs for improving the detectability of GFAAS. It is based on off-line pre-concentration of 20.0 mL of sample previously buffered (pH 8.82) on MWCNTs at a flow rate of 10.0 mL min^?1. After the pre-concentration procedure, the elution step was carried out with 500 µL of 0.524 mol L^?1 HNO₃ solution at a flow rate of 2.0 mL min^?1. Fractional factorial designs and response surface methodology were employed for optimisation of all chemical parameters involved in the pre-concentration procedure, including pre-concentration flow rate, buffer and eluent concentration, sample pH and elution volume. The method provides a linear calibration range from 0.03 up to 7.00 µg L^?1 with linear correlation coefficient higher than 0.9994 and limits of detection and quantification of 0.01 and 0.03 µg L^?1, respectively. Repeatability of the six measurements was found to be 2.38 and 1.84% for 0.3 and 4.5 µg L^?1 cobalt concentration, respectively. By pre-concentrating 20.0 mL of sample, a pre-concentration factor (PF) of 19.10-fold and a consumption index of 1.05 mL were obtained. The pre-concentration efficiency (PE) was found to be 9.55 min^?1. The proposed method was successfully applied for the pre-concentration and determination of cobalt in water and urine samples with satisfactory recovery values.     

Determination of inorganic and total mercury by vapor generation atomic absorption spectrometry using different temperatures of the measurement cell

A simple and inexpensive laboratory-built flow injection vapor generation system coupled to atomic absorption spectrometry (FI-VG AAS) for inorganic and total mercury determination has been developed. It is based on the vapor generation of total mercury and a selective detection of Hg^2 + or total mercury by varying the temperature of the measurement cell. Only the inorganic mercury is measured when the quartz cell is at room temperature, and when the cell is heated to 650 °C or higher the total Hg concentration is measured. The organic Hg concentration in the sample is calculated from the difference between the total Hg and Hg^2 + concentrations. Parameters such as the type of acid (HCl or HNO₃) and its concentration, reductant (NaBH₄) concentration, carrier solution (HCl) flow rate, carrier gas flow rate, sample volume and quartz cell temperature, which influence FI-VG AAS system performance, were systematically investigated. The optimized conditions for Hg^2 + and total Hg determinations were: 1.0 mol l^− 1 HCl as carrier solution, carrier flow rate of 3.5 ml min^− 1, 0.1% (m/v) NaBH₄, reductant flow rate of 1.0 ml min^− 1 and carrier gas flow rate of 200 ml min^− 1. The relative standard deviation (RSD) is lower than 5.0% for a 1.0 μg l^− 1 Hg solution and the limit of quantification (LOQ, 10 s) is 55 ng g^− 1. Certified samples of dogfish muscle (DORM-1 and DORM-2) and non-certified fish samples were analyzed, using a 6.0 mol l^− 1 HCl solution for analyte extraction. The Hg^2 + and CH₃Hg⁺ concentrations found were in agreement with certified ones.     

Pyrolysis of pine needles: effects of process parameters on products yield and analysis of products

Pyrolysis of pine needles was carried out in a semi-batch reactor. The effects of pyrolysis parameters such as temperature (350–650 °C), heating rate (10 and 50 °C min^?1), nitrogen flow rate (50–200 cm³ min^?1) and biomass particle size (0.25–1.7 mm) were examined on products yield. Maximum bio-oil yield of 43.76% was obtained at pyrolysis temperature of 550 °C with a heating rate of 50 °C min^?1, nitrogen flow rate of 100 cm³ min^?1 for biomass particle size of 0.6 < d _p < 1 mm. The characterization of pyrolysis products (bio-oil, bio-char) has been made through different instrumental methods like Fourier transform infrared spectroscopy, gas chromatography–mass spectrometry, nuclear magnetic resonance spectroscopy (¹H NMR), X-ray powder diffraction, field emission scanning electron microscope and Brunauer–Emmett–Teller surface area analysis. The empirical formula of the bio-oil and bio-char was found as CH_1.47O_0.36N_0.005 and CH_0.56O_0.28N_0.013 with heating value of 26.25 and 25.50 MJ kg^?1, respectively. Results show that bio-oil can be potentially valuable as a renewable fuel after upgrading and can be used as a feedstock for valuable chemicals production. The properties of bio-char reveal that it can be used as solid fuels, as a cheap adsorbent and as a feedstock for activated carbon production.     

Detector Systems in Capillary Gas Chromatography

Expressions for the minimum detectable amount Q_o and the minimum analyte concentration C_o as functions of the chromatographic parameters are derived for both mass and concentration sensitive detectors. The effects of pressure drop, column inner diameter, and film thickness are given. The minimum analyte concentration for mass flow sensitive detectors, C_o^m, can be reduced considerably by selecting the carrier gas velocity well above its optimum value (related to H_min), however, at the cost of long columns and long analysis times. For Q_o the improvements can be neglected, and so the analysis can best be performed at u_opt. When the flow rate in the detector, F_d, is equal to the column flow rate F_c, the maximum permissible detector volume of concentration sensitive detectors is proportional to d_c² up to d_c³, and so narrow bore columns require detectors of extremely small volume. Make-up gas has to be added when the actual volume is too large, thus worsening the detectability. Another approach, vacuum operation of the detector cell, appears to be very attractive. On the other hand, when wide bore columns are used in combination with small volume concentration sensitive detectors, very small values of Q_o^c and C_o^c are obtainable when the abundant carrier gas can be removed before entering the detector cell. Digital noise filtering can further reduce the obtainable Q_o and C_o values, especially for broad peaks and thus for wide bore columns.     

Optimisation of a Flow Injection System with a Piezoelectric Quartz Crystal Detector for the Determination of Inorganic Mercury

ABSTRACT

A new method combining flow injection methodology with quartz crystal microbalance (QCM) detection is proposed for inorganic mercury analysis. A modified simplex method is used in order to maximise the observed analytical signals (crystal frequency decrease). Six parameters were optimised: the concentration of the acidic carrier solution, the lengths of the sample loop and mixing coil, and the flow rates of the sample carrier, the reductant stream (SnCl₂), and the carrier of the mercury vapour (N₂). An increase of 18% in the signal of the centroid of the calibration line was achieved, as well as an increase in the sensitivity from 290 Hz μg^? to 313 Hz μg^?. Following the proposed procedure, detection limits of 47 μg L^? of inorganic mercury were found for sample volumes of 0.5 mL.     

Linearization of calibration curves by aerosol carrier effect of CCl4 vapor in electrothermal vaporization inductively coupled plasma mass spectrometry

Carbon tetrachloride vapor as gaseous phase modifier in a graphite furnace electrothermal vaporizer (GFETV) converts heavy volatile analyte forms to volatile and medium volatile chlorides and produces aerosol carrier effect, the latter being a less generally recognized benefit. However, the possible increase of polyatomic interferences in inductively coupled plasma mass spectrometry (GFETV–ICP-MS) by chlorine and carbon containing species due to CCl₄ vapor introduction has been discouraging with the use of low resolution, quadrupole type MS equipment. Being aware of this possible handicap, it was aimed at to investigate the feasibility of the use of this halogenating agent in ICP-MS with regard of possible hazards to the instrument, and also to explore the advantages under these specific conditions. With sample gas flow (inner gas flow) rate not higher than 900 ml min⁻¹ Ar in the torch and 3 ml min⁻¹ CCl₄ vapor flow rate in the furnace, the long-term stability of the instrument was ensured and the following benefits by the halocarbon were observed. The non-linearity error (defined in the text) of the calibration curves (signal versus mass functions) with matrix-free solution standards was 30–70% without, and 1–5% with CCl₄ vapor introduction, respectively, at 1 ng mass of Cu, Fe, Mn and Pb analytes. The sensitivity for these elements increased by 2–4-fold with chlorination, while the relative standard deviation (RSD) was essentially the same (2–5%) for the two cases in comparison. A vaporization temperature of 2650 °C was required for Cr in Ar atmosphere, while 2200 °C was sufficient in Ar + CCl₄ atmosphere to attain complete vaporization. Improvements in linear response and sensitivity were the highest for this least volatile element. The pyrolytic graphite layer inside the graphite tube was protected by the halocarbon, and tube life time was further increased by using traces of hydrocarbon vapor in the external sheath gas of the graphite furnace. Details of the modification of the gas supply for HGA-600MS furnace and the design of the volatilization device are described.     

A novel 2-(2-methyl-2-nitrovinyl)-furan ectoparasitic drug: physicochemical characterization and determination of the raw material by gas chromatography mass spectrometry

2-(2-methyl-2-nitrovinyl)-furan (NVF) has recently been synthesized and the pharmaceutical industry interest in this compound has grown due to its antibacterial, fungicidal and anti-ectoparasitic activities. Therefore, the physicochemical characterization of new drug was conducted. In addition, two rapid, simple and suitable GC methods were developed for determination of NVF. Analyses were carried out with an Agilent DB-5ms capillary column (60 m × 0.25 mm i.d., 0.25 µm film thickness). The GC-FID analysis employed splitless mode of injection, oven/injector/detector temperature of 160/230/280°C and nitrogen carrier at the flow of 5.0 mL min^?1. The GC-MS analysis employed splitless mode of injection, helium carrier at the flow of 1.5 mL min^?1, column temperature program with 2 min at 100°C, ramp at 50°C min^?1 to 260°C and injector and detector temperature of 250 and 290°tC, respectively. The MS conditions were ionization voltage, 70 eV; mass range, m/z 40–350; and ion source temperature, 200°C. The analysis time took less than 6 min. The results obtained in the validation of the methods suggest that these methods are economic, precise, accurate and linear over the range of analysis. The methods were successfully employed during the synthesis of NVF in order to ensure the quality of the raw material.      

Quantification of dopant species using atom probe tomography for semiconductor application

Doping of semiconductors serve various purposes in metal-oxide-semiconductor (CMOS) technology, eg, increase carrier concentration and modify electric field distribution. With the scaling down of device and the introduction of three-dimensional fin field-effect transistors (FinFET), precise and reliable dopant quantification of concentration at the nano-scale is critical. Laser-assisted atom probe tomography (APT) provides a unique approach to characterize and quantify the dopant in three dimensions at sub-nanometer resolution. Nevertheless, quantification accuracy of APT is strongly influenced by the experimental conditions. Although B quantification has been widely studied, the correlation of B signal loss to B concentration is not yet established. In addition, no phosphorous quantification study has been reported. In this work, we found that, due to B multi-hit effect in APT, high B dose sample has larger B loading compared with low B dose sample. For standard calibration with minimized impact from multi-hit effect, we recommend B dose in the range of 1e14 atoms/cm². Despite the fact that B loading is dose dependent, APT quantification of B achieves precision within 2% to 6% relative standard deviation (RSD), which demonstrates that APT has good accuracy. On the other hand, P quantification suffers from mass interference of ³¹P⁺ and ³¹P₂²⁺ at 31 Da resulting in a large loading between APT and secondary ion mass spectrometry (SIMS). Nevertheless, we recommend that 31 Da to be labeled as ³¹P⁺ for smaller P variation for the APT analysis.     

Far-infrared spectrum,barrier to internal rotation,ro structure,and ab initio calculations for acetylacetylene

The far-infrared spectrum has been recorded from 50 to 360 cm^–1 at a resolution of 0.10 cm^–1 for acetyiacetylene (1-butyne-3-one], CH₃C(O)CCH. The fundamental methyl torsion has been observed at 117.94 cm^–1, from which a periodic barrier to internal rotation has been calculated to be 346 cm^–1 (989 cal mol^–1]. Infrared spectra (3500-50 cm^–1] of the gas and solid and the Raman spectra (3500-100 cm^–1) of the gas, liquid, and solid are reported. Utilizing previously reported rotational constants for three isotopic species,r _o structural parameters have been determined for the heavy-atom skeleton. The fundamental vibrational frequencies, barrier to internal rotation, and structural parameters that have been obtained experimentally are compared to those obtained from ab initio Hartree-Fock calculations employing 3-21G, 6-31G, and DZ basis sets and to the corresponding quantities for some similar molecules.     

Identification of Fe‐polycarboxylic complexes by electrospray ionization mass spectrometry and reduction of interferences by ion chromatography/inductively coupled plasma mass spectrometry with an octopole reaction system

Stable complexes are required during the ion chromatographic (IC) separation of Fe‐polycarboxylic acid complexes. Electrospray ionization mass spectrometry (ESI‐MS) was used to identify 1:1 stoichiometric complexes of Fe[HEDTA], Fe[EDTA]^1? and Fe[DTPA]^2?, and the spectra showed that these Fe complexes were stable in solution. Furthermore, inductively coupled plasma mass spectrometry (ICP‐MS) using an octopole reaction system (ORS) reduced polyatomic ion ⁴⁰Ar¹⁶O⁺ interference in the detection of ⁵⁶Fe via the addition of either H₂ or He to the ORS, with He at a flow rate 3.5 mL min^?1 being the optimum collision gas. Finally, IC/ICP‐MS was used for the separation and detection of Fe complexes with an eluent containing 30 mM (NH₄)₂HPO₄ at pH 8.0, but only Fe[HEDTA], Fe[EDTA]^1? and Fe[DTPA]^2? were observed within 10 min with reasonable resolution. Detection limits in the range of 10–13 µg L^?1 were achieved using He as the collision gas. The proposed method was used for the determination of Fe species in soil solutions. Copyright © 2010 John Wiley & Sons, Ltd.