Lab-In-Syringe automation of stirring-assisted room-temperature headspace extraction coupled online to gas chromatography with flame ionization detection for determination of benzene, toluene, ethylbenzene, and xylenes in surface waters.

Online coupling of Lab-In-Syringe automated headspace extraction to gas chromatography has been studied. The developed methodology was successfully applied to surface water analysis using benzene, toluene, ethylbenzene, and xylenes as model analytes. The extraction system consisted of an automatic syringe pump with a 5 mL syringe into which all solutions and air for headspace formation were aspirated. The syringe piston featured a longitudinal channel, which allowed connecting the syringe void directly to a gas chromatograph with flame ionization detector via a transfer capillary. Gas injection was achieved via opening a computer-controlled pinch valve and compressing the headspace, upon which separation was initialized. Extractions were performed at room temperature; yet sensitivity comparable to previous work was obtained by high headspace to sample ratio V/V of 1.6:1 and injection of about 77% of the headspace. Assistance by in-syringe magnetic stirring yielded an about threefold increase in extraction efficiency. Interferences were compensated by using chlorobenzene as an internal standard. Syringe cleaning and extraction lasting over 10 min was carried out in parallel to the chromatographic run enabling a time of analysis of <19 min. Excellent peak area repeatabilities with RSD of <4% when omitting and <2% RSD when using internal standard corrections on 100 μg L level were achieved. An average recovery of 97.7% and limit of detection of 1-2 μg L were obtained in analyses of surface water.