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GC-FID has been effectively used as a universal quantification technique for volatile organic compounds for a long time. In most cases, the use of the ECN allows for quantification by GC-FID without external calibration using only the response of a single internal standard. In this paper we compare the performance characteristics of GC-FID with those of post-column (13)C Isotope Dilution GC-Combustion-MS for the absolute quantification of organic compounds without the need for individual standards. For this comparison we have selected the quantification of FAMEs in biodiesel. The selection of the right internal standard was critical for GC-FID even when ECN were considered. On the other hand, the nature of the internal standard was not relevant when GC-Combustion-MS was employed. The proposed method was validated with the analysis of the certified reference material SRM 2772 and comparative data was obtained on real biodiesel samples. The analysis of the SRM 2772 biodiesel provided recoveries in the range 100.6-103.5% and 96.4-103.6% for GC-combustion-MS and GC-FID, respectively. The detection limit for GC-combustion-MS was found to be 4.2ng compound/g of injected sample. In conclusion, the quantitative performance of GC-Combustion-MS compared satisfactorily with that of GC-FID constituting a viable alternative for the quantification of organic compounds without the need for individual standards.

Seven β2-agonist (clenproperol, clenbuterol, salbutamol, bronbuterol, ractopamine, clenpenterol and clencyclohexerol) were determined simultaneously in human and bovine urine by isotope dilution LC-ESI-MS/MS in a triple quadrupole instrument. The method is based on the application of multiple linear regression in combination with compound-specific minimally 13C-labelled analogues. Additionally, the increase of the bandpass of the first quadrupole during the selected reaction monitoring (SRM) measurement procedure allowed the simultaneous quantification of the seven compounds at sub ngg-1 levels in a single chromatogram without resorting to a methodological calibration graph. Recovery values at concentration levels between 5.0 and 0.05ngg-1 ranged from 95 to 110% in fortified bovine urine and from 91 to 108% in human urine, with relative standard deviations lower than 5% except for salbutamol and ractopamine. The proposed methodology was validated by analyzing the certified reference material BCR-503 (lyophilized bovine urine) certified for clenbuterol and salbutamol. The limits of detection (LOD) for a sample volume of 10mL of both human and bovine urine was found to be lower than 0.012ngg-1 for all compounds, except to salbutamol in bovine urine which was of 0.029ngg-1. The use of compound-specific isotopically labelled analogues minimally labelled in 13C minimized the occurrence of isotope effects and corrected for matrix effects during ESI ionization and can be efficiently applied for the quantification of ultra-trace concentrations of β2-agonists in human and bovine urine.

In this work, the implementation of isotope dilution mass spectrometry (IDMS) using minimal labeling and isotope pattern deconvolution (IPD) is evaluated as a strategy for the minimization of matrix effects during trace determination of β 2 -agonists in complex matrices by liquid chromatography electrospray ionization mass spectrometry (LC–ESI-MS). First, the parameters affecting the measurement of isotopic composition of organic compounds by liquid chromatography electrospray ionization high resolution mass spectrometry with a time-of-flight analyzer were evaluated using as a case of study three different β 2 -agonists: clenbuterol, clenproperol and brombuterol. Then, a calibration graph-free IDMS methodology was evaluated in order to overcome matrix effects in LC–ESI-MS in complex samples. In this procedure singly 13 C-labeled analogues of clenbuterol, clenproperol and brombuterol were employed in combination with IPD. Using this approach accurate and precise results were obtained in the simultaneous quantification of β 2 -agonists in human urine and bovine liver, even at the sub ng g −1 and particularly in spite of the previously reported matrix effects. Recovery rates in the range of 97–114% in fortified human urine and from 95% to 111% in fortified bovine liver were obtained with RSD (%) of independent recovery experiments always lower than 6%. These results demonstrate that the proposed methodology based on the use of 13 C 1 -labeled standards and IPD is a reliable approach for accurate LC–MS quantitation of small molecules and compatible with full-scan high-resolution mass spectrometry.

Rare earth elements (REEs) form anionic complexes which can be separated isocratically by anion-exchange chromatography using ethylenediaminetetraacetic acid (EDTA) as the mobile phase. For easy detection and identification, inductively coupled plasma (ICP) MS was used as detection method. From pH 3.5 to 7.5, retention increases from La to Sm and then decreases again up to Lu. Above pH 8.5, the retention of the light lanthanides increased drastically. It seems that the stoichiometry and the charge of the REE-EDTA complexes change with the elution pH. This strange elution behaviour can be easily tuned for particular applications by selecting the elution pH. For example, at pH values between 5.5 and 7.5 most isobaric and polyatomic interferences which occur in ICP-MS detection of the lanthanides are eliminated. A mechanism for the stepwise formation of the REE-EDTA complexes as a function of pH is proposed.

Large volume injection, up to 5 mL, was evaluated and optimised for the on-line ion chromatographic separation of Rb and Sr before ICP-MS measurement of Sr isotope ratios. Flat-topped chromatographic peaks, ideally suited for multicollector ICP-MS isotope ratio measurements, could be obtained when the composition of the mobile phase (nitric acid and 18-crown-6 ether) was identical to the matrix of the sample. Under those conditions rubidium eluted at the dead volume of the column while strontium produced a flat-topped transient signal with several minutes of stable plateau. On-line data acquisition during several minutes at the plateau of Sr signal allowed high precision Sr isotope ratio measurement. The developed procedure was evaluated for Sr isotope ratio measurements on different types of samples, including cider, apples, apple leaves, and soil extracts, in the frame of a long-term project aiming at origin authentication using strontium isotope ratio measurements. It was observed that sample matrix caused broadening of the strontium chromatographic peak and loss of flat-topped peak profile. Under those circumstances the addition of the complexing crown-ether 18-crown-6 both to samples and chromatographic eluent provided two distinct advantages. First, a drastic increase in the retention of strontium was observed which could be modulated by increasing the concentration of nitric acid in the eluent up to 900 mM. This increase in the eluent HNO3 concentration allowed the application of the method to acid soil digests and other high acidity samples. Second, the matrix of the sample did not affect any more the chromatographic peak profile and similar chromatographic separations could be obtained for samples and standards maintaining the flat-topped Sr peak profile. Sample preparation consisted of a simple 1:10 dilution of the cider or pre-treated solid samples by adding HNO3 (900 mM) and 18-crown-6 ether (5 mM) to obtain similar composition in the sample solution and the HPLC eluent.

A study of the separation of trace uranium from multi element mixtures using high-performance chelating ion chromatography (HPCIC) is described. Three different chelating columns were compared in the investigations and the results are discussed. Two types of neutral polystyrene substrates were used for forming the chelating surfaces, a hypercrosslinked macronet and a standard low crosslinked polymer. Calmagite, 4-(2-pyridyl) azoresorcinol (PAR) and dipicolinic acid were the chelating compounds selected to impregnate or coat the resins. One unusual finding was the different retention orders for uranium(VI) and thorium(IV) on the three columns. The best separation of uranium(VI) was obtained on the macronet resin dynamically coated with dipicolinic acid. The column gave a uranium peak of good symmetry well separated from thorium(IV), lanthanum(III) and iron(II). The reproducibility of retention and quantitative performance for uranium(VI) was evaluated using arsenazo III post-column reaction detection.