Improved time-resolved measurements of inorganic ions in particulate matter by PILS-IC integrated with a sample pre-concentration system

A particle-into-liquid sampler coupled with ion chromatograph (PILS-IC) for the on-line measurement of inorganic ions has been modified by the insertion of two ion-exchange pre-concentration cartridges that enrich the sample during the period of the IC analysis. The limits of detection of the modified instrument were 10-15 times lower and the time coverage 24 times higher (from 2 to 48 min per hour) than those of the original PILS-IC setup. The instrumental performance in terms of recovery and break-through volume from the cartridges was satisfactory. The modified PILS-IC was operated in comparison with a diffusion denuder line and with a high-resolution time-of-flight aerosol mass spectrometer (HR-TOF-AMS) during a short intensive measurement period organized in the framework of the European Monitoring and Evaluation Programme (EMEP), a co-operative program for monitoring and evaluation of the long-range transmission of the air pollutants in Europe. The instrument showed a quantitative response in agreement with the results of the diffusion lines, and an ability to trace fine concentration variations not so different from the performance of the much more complex HR-TOF-AMS. From the time patterns of the ion concentrations measured by the modified PILS-IC, it was possible to obtain useful information about the variations in the air quality and in the strength of the particulate matter sources.