Elemental composition of HULIS in the Pearl River Delta Region, China: results inferred from positive and negative electrospray high resolution mass spectrometric data.

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.

[1]  M. Claeys,et al.  Characterisation of tracers for aging of α-pinene secondary organic aerosol using liquid chromatography/negative ion electrospray ionisation mass spectrometry , 2012 .

[2]  J. Yu,et al.  Generation of reactive oxygen species mediated by humic-like substances in atmospheric aerosols. , 2011, Environmental science & technology.

[3]  G. Bernhard,et al.  Humic acid model substances with pronounced redox functionality for the study of environmentally relevant interaction processes of metal ions in the presence of humic acid , 2011 .

[4]  A. Laskin,et al.  Molecular chemistry of organic aerosols through the application of high resolution mass spectrometry. , 2011, Physical chemistry chemical physics : PCCP.

[5]  Luisa T. M. Profeta,et al.  Case study of water-soluble metal containing organic constituents of biomass burning aerosol. , 2011, Environmental science & technology.

[6]  M. Claeys,et al.  Terpenylic acid and related compounds: precursors for dimers in secondary organic aerosol from the ozonolysis of α- and β-pinene , 2010 .

[7]  E. Da̧bek-Złotorzyńska,et al.  Analysis of the unresolved organic fraction in atmospheric aerosols with ultrahigh-resolution mass spectrometry and nuclear magnetic resonance spectroscopy: organosulfates as photochemical smog constituents. , 2010, Analytical chemistry.

[8]  J. Yu,et al.  Humic-like substances in fresh emissions of rice straw burning and in ambient aerosols in the Pearl River Delta Region, China , 2010 .

[9]  Brandie M. Ehrmann,et al.  Water-soluble atmospheric organic matter in fog: exact masses and chemical formula identification by ultrahigh-resolution fourier transform ion cyclotron resonance mass spectrometry. , 2010, Environmental science & technology.

[10]  J. Schauer,et al.  Reactive oxygen species activity and chemical speciation of size-fractionated atmospheric particulate matter from Lahore, Pakistan: an important role for transition metals. , 2010, Journal of environmental monitoring : JEM.

[11]  M. Oss,et al.  Electrospray ionization efficiency scale of organic compounds. , 2010, Analytical chemistry.

[12]  A. Laskin,et al.  High-resolution mass spectrometry analysis of secondary organic aerosol generated by ozonolysis of isoprene , 2010 .

[13]  Xiao-Feng Huang,et al.  Abundance and size distribution of HULIS in ambient aerosols at a rural site in South China , 2009 .

[14]  M. Johnston,et al.  Composition domains in monoterpene secondary organic aerosol. , 2009, Environmental science & technology.

[15]  B. Turpin,et al.  Composition of dissolved organic nitrogen in continental precipitation investigated by ultra-high resolution FT-ICR mass spectrometry. , 2009, Environmental science & technology.

[16]  Thorsten Reemtsma,et al.  Determination of molecular formulas of natural organic matter molecules by (ultra-) high-resolution mass spectrometry: status and needs. , 2009, Journal of chromatography. A.

[17]  A. Laskin,et al.  Molecular characterization of nitrogen-containing organic compounds in biomass burning aerosols using high-resolution mass spectrometry. , 2009, Environmental science & technology.

[18]  M. Witt,et al.  Fragmentation studies of fulvic acids using collision induced dissociation fourier transform ion cyclotron resonance mass spectrometry. , 2009, Analytical chemistry.

[19]  A. Laskin,et al.  Molecular characterization of biomass burning aerosols using high-resolution mass spectrometry. , 2009, Analytical chemistry.

[20]  Y. Rudich,et al.  Atmospheric HULIS enhance pollutant degradation by promoting the dark Fenton reaction , 2008 .

[21]  M. Hannigan,et al.  Source apportionment of in vitro reactive oxygen species bioassay activity from atmospheric particulate matter. , 2008, Environmental science & technology.

[22]  Barbara J. Turpin,et al.  Oligomers, organosulfates, and nitrooxy organosulfates in rainwater identified by ultra-high resolution electrospray ionization FT-ICR mass spectrometry , 2008 .

[23]  R. Sleighter,et al.  Technical Note: Molecular characterization of aerosol-derived water soluble organic carbon using ultrahigh resolution electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry , 2008 .

[24]  A. Laskin,et al.  The effect of solvent on the analysis of secondary organic aerosol using electrospray ionization mass spectrometry. , 2008, Environmental science & technology.

[25]  John H Seinfeld,et al.  Organosulfate formation in biogenic secondary organic aerosol. , 2008, The journal of physical chemistry. A.

[26]  G. Láng,et al.  Properties of atmospheric humic-like substances – water system , 2008 .

[27]  Allen V. Barker,et al.  Natural Products from Plants, Second Edition , 2008 .

[28]  I. Leito,et al.  Towards the electrospray ionization mass spectrometry ionization efficiency scale of organic compounds. , 2008, Rapid communications in mass spectrometry : RCM.

[29]  Julia Laskin,et al.  High-resolution mass spectrometric analysis of secondary organic aerosol produced by ozonation of limonene. , 2008, Physical chemistry chemical physics : PCCP.

[30]  B. Spengler,et al.  Oligomer formation during gas-phase ozonolysis of small alkenes and enol ethers: new evidence for the central role of the Criegee Intermediate as oligomer chain unit , 2007 .

[31]  T. Hoffmann,et al.  Unambiguous identification of esters as oligomers in secondary organic aerosol formed from cyclohexene and cyclohexene/α-pinene ozonolysis , 2007 .

[32]  Herbert Thiele,et al.  Even-electron ions: a systematic study of the neutral species lost in the dissociation of quasi-molecular ions. , 2007, Journal of mass spectrometry : JMS.

[33]  R. Zenobi,et al.  Functional group analysis of high-molecular weight compounds in the water-soluble fraction of organic aerosols , 2007 .

[34]  Christian Panse,et al.  Ultrahigh mass resolution and accurate mass measurements as a tool to characterize oligomers in secondary organic aerosols. , 2007, Analytical chemistry.

[35]  R. Sleighter,et al.  The application of electrospray ionization coupled to ultrahigh resolution mass spectrometry for the molecular characterization of natural organic matter. , 2007, Journal of mass spectrometry : JMS.

[36]  Gerhard Kattner,et al.  Fundamentals of molecular formula assignment to ultrahigh resolution mass data of natural organic matter. , 2007, Analytical chemistry.

[37]  Armin Sorooshian,et al.  Characterization of 2-methylglyceric acid oligomers in secondary organic aerosol formed from the photooxidation of isoprene using trimethylsilylation and gas chromatography/ion trap mass spectrometry. , 2007, Journal of mass spectrometry : JMS.

[38]  Oliver Fiehn,et al.  Seven Golden Rules for heuristic filtering of molecular formulas obtained by accurate mass spectrometry , 2007, BMC Bioinformatics.

[39]  Andreas Springer,et al.  Identification of fulvic acids and sulfated and nitrated analogues in atmospheric aerosol by electrospray ionization fourier transform ion cyclotron resonance mass spectrometry. , 2006, Analytical chemistry.

[40]  Sunghwan Kim,et al.  Direct molecular evidence for the degradation and mobility of black carbon in soils from ultrahigh-resolution mass spectral analysis of dissolved organic matter from a fire-impacted forest soil , 2006 .

[41]  Yinon Rudich,et al.  Atmospheric HULIS : how humic-like are they ? A comprehensive and critical review , 2005 .

[42]  Fabio Moretti,et al.  Functional group analysis by H NMR/chemical derivatization for the characterization of organic aerosol from the SMOCC field campaign , 2005 .

[43]  Gilles Mailhot,et al.  Transition metals in atmospheric liquid phases: sources, reactivity, and sensitive parameters. , 2005, Chemical reviews.

[44]  Meinrat O. Andreae,et al.  Optical properties of humic-like substances (HULIS) in biomass-burning aerosols , 2005 .

[45]  Hans-Christen Hansson,et al.  Surface Tension Effects of Humic-Like Substances in the Aqueous Extract of Tropospheric Fine Aerosol , 2005 .

[46]  R. Olariu,et al.  Nitrated phenols in the atmosphere: a review , 2005 .

[47]  P. Hatcher,et al.  Identification of black carbon derived structures in a volcanic ash soil humic acid by Fourier transform ion cyclotron resonance mass spectrometry. , 2004, Environmental science & technology.

[48]  F. J. Cox,et al.  Formation of oligomers in secondary organic aerosol. , 2004, Environmental science & technology.

[49]  A. Marshall,et al.  Two- and Three-Dimensional van Krevelen Diagrams: A Graphical Analysis Complementary to the Kendrick Mass Plot for Sorting Elemental Compositions . . , 2004 .

[50]  Martin Gysel,et al.  Hygroscopic properties of water-soluble matter and humic-like organics in atmospheric fine aerosol , 2003 .

[51]  Sunghwan Kim,et al.  Graphical method for analysis of ultrahigh-resolution broadband mass spectra of natural organic matter, the van Krevelen diagram. , 2003, Analytical chemistry.

[52]  P. Artaxo,et al.  Water‐soluble organic nitrogen in Amazon Basin aerosols during the dry (biomass burning) and wet seasons , 2003 .

[53]  A. Marshall,et al.  Ionization and fragmentation of humic substances in electrospray ionization Fourier transform-ion cyclotron resonance mass spectrometry. , 2002, Analytical chemistry.

[54]  Qi Zhang,et al.  Water‐soluble organic nitrogen in atmospheric fine particles (PM2.5) from northern California , 2002 .

[55]  M. Facchini,et al.  Water soluble organic compounds formed by oxidation of soot , 2002 .

[56]  A G Marshall,et al.  Kendrick mass defect spectrum: a compact visual analysis for ultrahigh-resolution broadband mass spectra. , 2001, Analytical chemistry.

[57]  C. Enke,et al.  Practical implications of some recent studies in electrospray ionization fundamentals. , 2001, Mass spectrometry reviews.

[58]  M. Facchini,et al.  Surface tension of atmospheric wet aerosol and cloud/fog droplets in relation to their organic carbon content and chemical composition , 2000 .

[59]  E. Kendrick.  A Mass Scale Based on CH2 = 14.0000 for High Resolution Mass Spectrometry of Organic Compounds. , 1963 .