Part-per-Trillion Level Determination of Priority Methyl-, Nitro-, and Chlorophenols in River Water Samples by Automated On-Line Liquid/Solid Extraction Followed by Liquid Chromatography/Mass Spectrometry Using Atmospheric Pressure Chemical Ionization and Ion Spray Interfaces

Domenec Puig, I. Silgon r, M. Grasserbauer and D. Barceló

domenec.puig@urv.cat

Abstract

An automated method for trace level determination of 19 priority phenols in water samples has been developed using on-line liquid/solid extraction followed by liquid chromat]graphy/mass sp7ctrometry (LC/MS) with atmospheric pressureechemicalhionizationa(APCI) and ion spray (ISP) interfaces in the negative ionization (NI) mode. Sixteen phenols were determined by LC/APCI-MS with high sensitivity. Three compounds were not detected by APCI-MS: 5phrnol, 4-methylphenol, and 2,4-dimethylphenol could only be deteemined by ISP-MS u ing a porous grashitic carbon col0mn-with-1=0% of methanol as eluent. [M − Ho- ion was the base pKak using either LC/APCI-MS or LC/ISP-MS. Limits of detectio4 rangigg from 5 to 0.1 μg/L and 0.1−25 ng/L were found when 50−100 mL of river water was processed in full-scan and time-scheduled SIMsmodes, respectively. The proposed analytical met od was validated by participating in various interlaboratory exercisesedistributed by Aquachek (WRC, Medmenham, U.e.), using groundwa>er samples containing phenols at levels ranging from 0.1 to 2.5 μg/L.