Direct quantification of inorganic iodine in seawater by mixed-mode liquid chromatography-electrospray ionization-mass spectrometry.

Atmospheric iodine plays a relevant role in climate change. Bearing in mind that most of this iodine comes from the oceans, analytical methods capable of determining iodine in a challenging matrix as seawater are necessary. In this work, the first method capable of direct determination of total inorganic iodine in seawater at subnanomolar level based on mixed-mode liquid chromatography-electrospray ionization-mass spectrometry (LC-ESI-MS) without any sample treatment is presented. Analytical characteristics of the developed method were studied in terms of linear range, limits of detection and quantification, precision, trueness, matrix effect, and robustness. The detection limit for iodide was as low as 0.16 nM, injecting 5 µL of seawater without any sample treatment and the working linear range of four orders of magnitude was wide enough to cover the broad concentration range observed in seawater samples. Average values for repeatability and intermediate precision were 4.1% and 8.1%, respectively. The suitability of the method was demonstrated through its application to the analysis of several types of samples, including seawater samples taken at different locations along the Spanish Mediterranean coast and some domestic iodized salts. According to the results obtained, the method developed is rapid, easy to apply and to be automated, avoids sample treatment and requires only few microliters of sample. Furthermore, it has a low detection limit and allows the quantification of inorganic iodine over a wide concentration range.

Characterization by the solvation parameter model of the retention properties of commercial ionic liquid columns for gas chromatography.

For the first time, four commercial ionic liquid columns (SLB-IL59, SLB-IL76, SLB-IL82 and SLB-IL100) for gas chromatography have been comprehensively evaluated in terms of efficiency, polarity and solvation properties. Grob tests and McReynolds constants showed that they were all high-efficiency columns of high polarity, but with low inertness to compounds with hydrogen bonding capabilities. The solvation parameter model was used to characterize the solvation interactions of the four columns in the 80-160°C temperature range. Results revealed that all the ionic liquids studied can be considered moderately hydrogen-bond acid and highly cohesive stationary phases, on which the dominant contributions to retention were the dipolar-type and hydrogen-bond base interactions, while π-π and n-π interactions were barely significant. The SLB-IL59 column provided the best separation of homologs, while the SLB-IL76 and SLB-IL100 columns had the most basic and the most acidic phases, respectively. A principal component analysis for the commonly used stationary phases in capillary GC showed that these commercial ionic liquid columns fill an empty area of the available selectivity space, which clearly enhances the separation capacity of this technique.