LC/TOF-MS Identification of Organic Components in Cloud and Fog Water Samples

The nature and identity of organic compounds in cloud and fog droplets are not well understood. Approximately 80 percent of the total organic carbon remains unidentified due to several confounding factors. Traditionally, many of the organic compound analyses have been accomplished by the use of gas chromatography (GC) / mass spectrometry (MS) methods. These methods require analytes to be extracted from water and introduced into the GC by the use of organic solvents. Extraction efficiencies of the water- soluble organic components vary widely depending upon molecular size and polarity. Additionally, many polar compounds are thermally labile and require derivatization to make them more amenable for GC/MS analysis. Liquid chromatography (LC) methods which allow for sample introduction in water have also been used widely for organic analyses. However, commonly used detection methods such as conductivity, UV absorbance, and fluorescence limit the identification of organic components based on detection specific associated physical properties. Recently, electrospray ionization has allowed for MS detection to be paired with LC. There exist several types of MS each with their own specific advantages and disadvantages. In this study, we used LC with accurate mass time of flight (TOF) MS. The distinct advantage of accurate mass TOF is that it may be used to identify unknown organic compounds. Here we present results from our search for novel organic components (including organic nitrogen and organosulfates) in a variety of cloud and fog water samples from polluted and rural environments. These results are paired with established measurement methods for liquid water content, pH, and concentrations of total organic carbon (TOC), dissolved organic carbon (DOC), carbohydrates, formaldehyde, low molecular weight organic acids, carbonyls, and organic nitrogen.