Automatic pressure-assisted dual-headspace gas-liquid microextraction. Lab-in-syringe platform for membraneless gas separation of ammonia coupled with fluorimetric sequential injection analysis.

A novel pressure-assisted dual-headspace lab-in-syringe microextraction technique is presented as an alternative approach for automatic on-line membraneless gas separation of volatile compounds. The developed gas-liquid microextraction procedure is based on the lab-in-syringe (LIS) concept by using two independent micro-syringe pumps which are connected to each other for the application of negative and positive pressure inside the common headspace area of the syringe barrels. The adoption of reduced and increased pressure conditions is facilitated by the programmable LIS strategy resulting in increased extraction rates. The analytical process includes the in-situ ammonia vapor generation in the headspace of the first microsyringe, under reduced pressure environment, and its subsequent transportation into the headspace of the second microsyringe. Then, positive pressure is applied inside the second microsyringe enabling the ammonia vapor dissolution into the extraction solution to produce a fluorescent product (isoindol-1-sulfonat). The reaction is time and temperature affected, thus after an optimized time of delay inside the thermostated syringe barrel at 60 °C, it is delivered into the flow-cell of the miniSIA system where it is quantified at 425 nm (excitation wavelength, 365 nm). The proposed preconcentration system has been fully tested and optimized regarding the relevant parameters affecting the generation of gaseous ammonia, its effective transportation into the headspace of the second syringe barrel and its quantitative dissolution and reaction with the extraction solution. For a sample volume of 3000 μL, the sample frequency is 8 h, the precision expressed as relative standard deviation (RSD) is 3.6 (at 5.0 μg L) and a detection limit (3s) of 0.05 μg L for ammonium is obtained. The detection is linear in the concentration range of 0.15 and 10.0 μg L with a correlation coefficient of 0.9987. The accuracy of the proposed method has been evaluated by analyzing a standard reference material (relative error: 3.8%) as well as using the Certified Method (relative error < 5.5%) for ammonium determination. The potential of this novel schema has been demonstrated for ammonia determination in natural water samples.