Fragmentation Analysis of Water-Soluble Atmospheric Organic Matter Using Ultrahigh-Resolution FT-ICR Mass Spectrometry

2012 ◽  
Vol 46 (8) ◽  
pp. 4312-4322 ◽  
Author(s):  
Jeffrey P. LeClair ◽  
Jeffrey L. Collett ◽  
Lynn R. Mazzoleni
Keyword(s):  
Mass Spectrometry ◽  
Organic Matter ◽  
Water Soluble ◽  
Ultrahigh Resolution ◽  
Atmospheric Organic Matter ◽  
Ft Icr

scholarly journals Atmospheric organic matter in clouds: exact masses and molecular formula identification using ultrahigh-resolution FT-ICR mass spectrometry

2013 ◽  
Vol 13 (24) ◽  
pp. 12343-12362 ◽  
Author(s):  
Y. Zhao ◽  
A. G. Hallar ◽  
L. R. Mazzoleni
Keyword(s):  
Mass Spectrometry ◽  
Organic Matter ◽  
Cloud Water ◽  
Wood Combustion ◽  
Ultrahigh Resolution ◽  
Reduced Sulfur ◽  
Atmospheric Organic Matter ◽  
Sulfur Containing ◽  
Sulfur Containing Compounds ◽  
Ft Icr

Abstract. Clouds alter the composition of atmospheric aerosol by acting as a medium for interactions between gas- and particulate-phase substances. To determine the cloud water atmospheric organic matter (AOM) composition and study the cloud processing of aerosols, two samples of supercooled clouds were collected at the Storm Peak Laboratory near Steamboat Springs, Colorado (3220 m a.s.l.). Approximately 3000 molecular formulas were assigned to ultrahigh-resolution mass spectra of the samples after using a reversed-phase extraction procedure to isolate the AOM components from the cloud water. Nitrogen-containing compounds (CHNO compounds), sulfur-containing compounds (CHOS and CHNOS compounds) and other oxygen-containing compounds (CHO compounds) with molecular weights up to 700 Da were observed. Average oxygen-to-carbon ratios of ∼0.6 indicate a slightly more oxidized composition than most water-soluble organic carbon identified in aerosol studies, which may result from aqueous oxidation in the clouds. The AOM composition indicates significant influences from biogenic secondary organic aerosol (SOA) and residential wood combustion. We observed 60% of the cloud water CHO molecular formulas to be identical to SOA samples of α-pinene, β-pinene, d-limonene, and β-caryophyllene ozonolysis. CHNO compounds had the highest number frequency and relative abundances and are associated with residential wood combustion and NOx oxidation. Multiple nitrogen atoms in the assigned molecular formulas for the nighttime cloud sample composite were observed, indicating the significance of nitrate radical reactions on the AOM composition. Several CHOS and CHNOS compounds with reduced sulfur (in addition to the commonly observed oxidized sulfur-containing compounds) were also observed; however further investigation is needed to determine the origin of the reduced sulfur-containing compounds. Overall, the molecular composition determined using ultrahigh-resolution Fourier-transform ion cyclotron resonance (FT-ICR) mass spectrometry provides an unambiguous identification of the cloud water organic anion composition in the Rocky Mountain area that could help to improve the understanding of aqueous-phase processes.

scholarly journals Atmospheric organic matter in clouds: exact masses and molecular formula identification using ultrahigh resolution FT-ICR mass spectrometry

2013 ◽  
Vol 13 (8) ◽  
pp. 20561-20610 ◽  
Author(s):  
Y. Zhao ◽  
A. G. Hallar ◽  
L. R. Mazzoleni
Keyword(s):  
Mass Spectrometry ◽  
Organic Matter ◽  
Cloud Water ◽  
Wood Combustion ◽  
Ultrahigh Resolution ◽  
Reduced Sulfur ◽  
Atmospheric Organic Matter ◽  
Sulfur Containing ◽  
Sulfur Containing Compounds ◽  
Ft Icr

Abstract. Clouds alter the composition of atmospheric aerosol by acting as a medium for interactions between gaseous and particulate phase substances. To determine the cloud water atmospheric organic matter (AOM) composition and study the cloud processing of aerosols, two samples of supercooled clouds were collected at Storm Peak Laboratory near Steamboat Spring, Colorado (3220 m a.s.l.). Approximately 3000 molecular formulas were assigned to ultrahigh resolution mass spectra of the samples after using a reverse phase extraction procedure to isolate the AOM components from the cloud water. Nitrogen containing compounds (CHNO compounds), sulfur containing compounds (CHOS and CHNOS compounds) and other oxygen containing compounds (CHO compounds) with molecular weights up to 700 Da were observed. Average oxygen-to-carbon ratios of ~0.6 indicate a slightly more oxidized composition than most water-soluble organic carbon identified in aerosol studies, which may result from aqueous oxidation in the clouds. The AOM composition indicates significant influences from biogenic secondary organic aerosol (SOA) and residential wood combustion. We observed 60% of the cloud water CHO molecular formulas to be identical to SOA samples of α-pinene, β-pinene, d-limonene, and β-caryophyllene ozonolysis. CHNO compounds had the highest number frequency and relative abundances and are associated with residential wood combustion and NOx oxidation. We observed multiple nitrogen atoms in the assigned molecular formulas for the nighttime cloud sample composite indicating the significance of nighttime emissions or NOx oxidation on the AOM composition. Several CHOS and CHNOS compounds with reduced sulfur (in addition to the commonly observed oxidized sulfur containing compounds) were also observed, however further investigation is needed to determine the origin of the reduced sulfur containing compounds. Overall, the molecular composition determined using ultrahigh resolution Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry provides an unambiguous identification of the cloud water organic composition in the Rocky Mountain area which could help to improve the understanding of aqueous phase processes.

scholarly journals Oligomers, organosulfates, and nitrooxy organosulfates in rainwater identified by ultra-high resolution electrospray ionization FT-ICR mass spectrometry

2009 ◽  
Vol 9 (7) ◽  
pp. 2533-2542 ◽  
Author(s):  
K. E. Altieri ◽  
B. J. Turpin ◽  
S. P. Seitzinger
Keyword(s):  
Mass Spectrometry ◽  
Organic Matter ◽  
High Resolution ◽  
Electrospray Ionization ◽  
Mass Range ◽  
Negative Ion ◽  
Ion Cyclotron Resonance ◽  
Important Input ◽  
Atmospheric Organic Matter ◽  
Ft Icr

Abstract. Wet deposition is an important removal mechanism for atmospheric organic matter, and a potentially important input for receiving ecosystems, yet less than 50% of rainwater organic matter is considered chemically characterized. Precipitation samples collected in New Jersey, USA, were analyzed by negative ion ultra-high resolution electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS). Elemental compositions of 552 unique molecular species were determined in the mass range 50–500 Da in the rainwater. Four main groups of organic compounds were identified: compounds containing carbon, hydrogen, and oxygen (CHO) only, sulfur (S) containing CHOS compounds, nitrogen (N) containing CHON compounds, and S- and N- containing CHONS compounds. Organic acids commonly identified in precipitation were detected in the rainwater. Within the four main groups of compounds detected in the rainwater, oligomers, organosulfates, and nitrooxy-organosulfates were assigned based on elemental formula comparisons. The majority of the compounds identified are products of atmospheric reactions and are known contributors to secondary organic aerosol (SOA) formed from gas phase, aerosol phase, and in-cloud reactions in the atmosphere. It is suggested that the large uncharacterized component of SOA is the main contributor to the large uncharacterized component of rainwater organic matter.

Identification of water-soluble organic carbon in non-urban aerosols using ultrahigh-resolution FT-ICR mass spectrometry: organic anions

2012 ◽  
Vol 9 (3) ◽  
pp. 285 ◽  
Author(s):  
Lynn R. Mazzoleni ◽  
Parichehr Saranjampour ◽  
Megan M. Dalbec ◽  
Vera Samburova ◽  
A. Gannet Hallar ◽  
...  
Keyword(s):  
Mass Spectrometry ◽  
Organic Carbon ◽  
Significant Influence ◽  
Atmospheric Aerosols ◽  
Complex Mixture ◽  
Water Soluble ◽  
Ultrahigh Resolution ◽  
Water Soluble Organic Carbon ◽  
Soluble Organic Carbon ◽  
Ft Icr

Environmental contextAerosol water-soluble organic carbon is a complex mixture of thousands of organic compounds which may have a significant influence on the climate-relevant properties of atmospheric aerosols. Using ultrahigh resolution mass spectrometry, more than 4000 individual molecular formulas were identified in non-urban aerosol water-soluble organic carbon. A significant fraction of the assigned molecular formulas were matched to assigned molecular formulas of laboratory generated secondary organic aerosols. AbstractWater-soluble organic carbon (WSOC) is a complex mixture of thousands of organic compounds which may have significant influence on the climate-relevant properties of atmospheric aerosols. An improved understanding of the molecular composition of WSOC is needed to evaluate the effect of aerosol composition upon aerosol physical properties. In this work, ultrahigh-resolution Fourier transform–ion cyclotron resonance mass spectrometry (FT-ICR MS) was used to characterise aerosol WSOC collected during the summer of 2010 at the Storm Peak Laboratory (3210 m ASL) near Steamboat Springs, CO. Approximately 4000 molecular formulas were assigned in the mass range of 100–800 Da after negative-ion electrospray ionisation and more than 50 % of them contained nitrogen or sulfur. The double bond equivalents (DBEs) of the molecular formulas were inversely proportional to the O : C ratio, despite a relatively constant H : C ratio of ~1.5. Despite the range of DBE values, the elemental ratios and the high number of oxygen atoms per formula indicate that a majority of the compounds are aliphatic to olefinic in nature. These trends indicate significant non-oxidative accretion reaction pathways for the formation of high molecular weight WSOC components. In addition, a significant number of molecular formulas assigned in this work matched those previously identified as secondary organic aerosol components of monoterpene and sesquiterpene ozonolysis.

scholarly journals Molecular insights on aging and aqueous phase processing from ambient biomass burning emissions-influenced Po Valley fog and aerosol

2018 ◽  
Author(s):  
Matthew Brege ◽  
Marco Paglione ◽  
Stefania Gilardoni ◽  
Stefano Decesari ◽  
Maria Cristina Facchini ◽  
...  
Keyword(s):  
Mass Spectrometry ◽  
Organic Matter ◽  
Biomass Burning ◽  
Nmr Analysis ◽  
Fog Water ◽  
Po Valley ◽  
Two Samples ◽  
Atmospheric Organic Matter ◽  
Ft Icr Ms ◽  
Ft Icr

Abstract. Atmospheric organic matter is a complex mixture of thousands of individual organic compounds originating from a combination of primary emissions and secondary processes. To study the influence of regional biomass burning emissions and secondary processes, ambient samples of fog and aerosol were collected in the Po Valley (Italy) during the 2013 Supersito field campaign. After the extent of fresh vs. aged biomass burning influence was estimated from proton nuclear magnetic resonance (1H-NMR) and high resolution time of flight aerosol mass spectrometry (HR-TOF-AMS) observations, two samples of fog water and two samples of PM1 aerosol were selected for ultrahigh resolution Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) analysis. Over 4300 distinct molecular formulas were assigned to electrospray ionization FT-ICR MS anions and were sorted into four elemental groups (CHO, CHNO, CHOS and CHNOS) and 64 subclasses. Molecular weight distributions indicated that the water-soluble organic matter was largely non-polymeric without clearly repeating units, although some evidence of dimerization was observed for C10 compounds and especially for C8–9 CHNO species in the aged aerosol. The selected samples had an atypically large frequency of molecular formulas containing nitrogen and sulfur (not evident in the NMR composition) attributed to multifunctional organonitrates and organosulfates. While higher numbers of organonitrates were observed in aerosol (dry or deliquesced particles), higher numbers of organosulfates were mostly found in fog water and so chemical reactions promoted by liquid water must be postulated for their formation. Consistent with the observation of an enhanced aromatic proton signature in the 1H-NMR analysis, the average molecular formula double bond equivalents and carbon numbers were higher in the fresh biomass burning influenced samples, whereas the average O : C and H : C values from FT-ICR MS were higher in the samples with an aged influence (O : C > 0.6 and H : C > 1.2). The aged fog had a large set of unique highly oxygenated CHO fragments in HR-TOF-AMS mass spectra, which reflects an enrichment of carboxylic acids and other compounds carrying acyl groups as highlighted by the NMR analysis. Fog compositions were more SOA-like than aerosols as indicated by the observed similarity between the aged aerosol and fresh fog, implying that fog nuclei must be somewhat aged. Overall, functionalization with nitrate and sulfate moieties in addition to aqueous oxidation trigger an increase in the molecular complexity in this environment, which is apparent in the FT-ICR MS results. This study demonstrates the significance of the aqueous phase to transform the molecular chemistry of atmospheric organic matter and contribute to secondary organic aerosol.

Ultrahigh-resolution FT-ICR mass spectrometry for molecular characterisation of pressurised hot water-extractable organic matter in soils

2016 ◽  
Vol 128 (3) ◽  
pp. 307-326 ◽  
Author(s):  
Julien Guigue ◽  
Mourad Harir ◽  
Olivier Mathieu ◽  
Marianna Lucio ◽  
Lionel Ranjard ◽  
...  
Keyword(s):  
Mass Spectrometry ◽  
Organic Matter ◽  
Hot Water ◽  
Molecular Characterisation ◽  
Ultrahigh Resolution ◽  
Extractable Organic Matter ◽  
Water Extractable ◽  
Ft Icr

Unprecedented Ultrahigh Resolution FT-ICR Mass Spectrometry and Parts-Per-Billion Mass Accuracy Enable Direct Characterization of Nickel and Vanadyl Porphyrins in Petroleum from Natural Seeps

2014 ◽  
Vol 28 (4) ◽  
pp. 2454-2464 ◽  
Author(s):  
Amy M. McKenna ◽  
Jeffrey T. Williams ◽  
Jonathan C. Putman ◽  
Christoph Aeppli ◽  
Christopher M. Reddy ◽  
...  
Keyword(s):  
Mass Spectrometry ◽  
Mass Accuracy ◽  
Ultrahigh Resolution ◽  
Ft Icr
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