Elemental Composition of HULIS in the Pearl River Delta Region, China: Results Inferred from Positive and Negative Electrospray High Resolution Mass Spectrometric Data

Abstract

The HUmic-LIke Substances (HULIS) fraction isolated from aerosol samples collected at a rural location of the Pearl River Delta Region (PRD), China, during the harvest season was analyzed by both positive and negative mode electrospray ionization (ESI) coupled with an ultrahigh resolution mass spectrometer (UHRMS). With the remarkable resolving power and mass accuracy of ESI-UHRMS, thousands of elemental formulas were identified. Formulas detected in the positive (ESI+) and the negative (ESI-) mode complement each other due to differences in the ionization mechanism, and the use of both provides a more complete characterization of HULIS. Compounds composed of C, H, and O atoms were preferentially detected in ESI- by deprotonation, implying their acidic properties. Tandem MS and Kendrick Mass Defect analysis implies that carboxyl groups are abundant in the CHO compounds. This feature is similar to those of natural fulvic acids, but relatively smaller molecular weights are observed in the HULIS samples. A greater number of reduced nitrogen organic compounds were observed in the ESI+ compared to ESI-. Compounds with biomass burning origin including alkaloids, amino acids, and their derivatives are their probable constituents. Sulfur-containing species were dominantly detected in ESI-. The presence of sulfate fragments in the MS/MS spectra of these species and their high O/S ratios implies that they are mainly organosulfates. Organosulfates and nitrooxy-organosulfates were often the most intensive peaks in the ESI- spectra. They are believed to be products of reactive uptake of photooxidation products of reactive volatile organic compounds by acidic sulfate particles. The elemental compositions deduced from the UHRMS analysis confirm the conclusion from our previous study that biomass burning and SOA formation are both important sources of HULIS in the PRD region.