scholarly journals On the fate of oxygenated organic molecules in atmospheric aerosol particles

2020 ◽  
Vol 6 (11) ◽  
pp. eaax8922 ◽  
Author(s):  
V. Pospisilova ◽  
F. D. Lopez-Hilfiker ◽  
D. M. Bell ◽  
I. El Haddad ◽  
C. Mohr ◽  
...  
Keyword(s):  
Organic Molecules ◽  
Measurement Techniques ◽  
Organic Aerosol ◽  
Particle Phase ◽  
Ionization Time ◽  
Global Carbon Budget ◽  
Atmospheric Fate ◽  
Condensed Phase Reactions ◽  
Earth’S Climate ◽  
Global Carbon

Highly oxygenated organic molecules (HOMs) are formed from the oxidation of biogenic and anthropogenic gases and affect Earth’s climate and air quality by their key role in particle formation and growth. While the formation of these molecules in the gas phase has been extensively studied, the complexity of organic aerosol (OA) and lack of suitable measurement techniques have hindered the investigation of their fate post-condensation, although further reactions have been proposed. We report here novel real-time measurements of these species in the particle phase, achieved using our recently developed extractive electrospray ionization time-of-flight mass spectrometer (EESI-TOF). Our results reveal that condensed-phase reactions rapidly alter OA composition and the contribution of HOMs to the particle mass. In consequence, the atmospheric fate of HOMs cannot be described solely in terms of volatility, but particle-phase reactions must be considered to describe HOM effects on the overall particle life cycle and global carbon budget.

scholarly journals Organic aerosol source apportionment in Zurich using extractive electrospray ionization time-of-flight mass spectrometry (EESI-TOF): Part I, biogenic influences and day/night chemistry in summer

2019 ◽  
Author(s):  
Giulia Stefenelli ◽  
Veronika Pospisilova ◽  
Felipe D. Lopez-Hilfiker ◽  
Kaspar R. Daellenbach ◽  
Christoph Hüglin ◽  
...  
Keyword(s):  
Electrospray Ionization ◽  
Source Apportionment ◽  
Mass Spectrometer ◽  
Measurement Techniques ◽  
Time Of Flight ◽  
Organic Aerosol ◽  
Climate Impacts ◽  
Oxidation Products ◽  
Ionization Time ◽  
Two Factors

Abstract. Improving the understanding of the health and climate impacts of PM1 remains challenging and is restricted by the limitations of current measurement techniques. Detailed investigation of secondary organic aerosol (SOA), which is typically the dominating fraction of the organic aerosol (OA), requires instrumentation capable of real-time, in situ measurements of molecular composition. In this study, we present the first ambient measurements by a novel extractive electrospray ionization time-of-flight mass spectrometer (EESI-TOF). The EESI-TOF was deployed along with a high resolution time of flight aerosol mass spectrometer (HR-ToF-AMS) during summer 2016 at an urban location (Zurich, Switzerland). Positive matrix factorization (PMF), implemented within the Multilinear Engine (ME-2), was applied to the data from both instruments to quantify the primary and secondary contributions to OA. From the EESI-TOF analysis, a 6-factor solution was selected as the most representative and interpretable solution for the investigated dataset, including two primary and four secondary factors. The primary factors are dominated by cooking and cigarette smoke signatures while the secondary factors are discriminated according to their daytime (two factors) and nighttime (two factors) chemistry. All four factors showed strong influence by biogenic emissions but exhibited significant day/night differences. Factors dominating during daytime showed predominantly ions characteristic of monoterpene and sesquiterpene oxidation while the nighttime factors included less oxygenated terpene oxidation products, as well as organonitrates which were likely derived from NO3 radical oxidation of monoterpenes. Overall, the signal measured by the EESI-TOF and AMS showed a good correlation. Further, the two instruments were in excellent agreement in terms of both the mass contribution apportioned to the sum of POA and SOA factors and the total SOA signal. However, while the OOA factors separated by AMS analysis exhibited a flat diurnal pattern, the EESI-TOF factors illustrated significant chemical variation throughout the day. The captured variability, inaccessible from AMS PMF analysis, was shown to be consistent with the variations in the physiochemical processes influencing chemical composition and SOA formation. The improved source separation and interpretability of EESI-TOF results suggest it to be a promising approach to source apportionment and atmospheric composition research.

Using the “3Es” Method to Evaluate REDD+ Project in Nepal

2017 ◽  
Vol 1 (1) ◽  
pp. 1-5
Author(s):  
Doma Tshering Sherpa
Keyword(s):  
Forest Degradation ◽  
Benefit Distribution ◽  
Global Carbon Budget ◽  
Efficiency And Effectiveness ◽  
User Groups ◽  
And Performance ◽  
Community Forest User Groups ◽  
Global Carbon ◽  
Fundamental Requirement ◽  
Forest User

This case demonstrates the utility of the 3Es (effectiveness, efficiency, and equity) in examining Reducing Emissions from Deforestation and Forest Degradation (REDD+) project in Nepal. REDD+ offers results-based payments for conserving and managing forests sustainably and enhancing forest carbon stocks. This will benefit communities’ efforts to conserve forest resources and prevent deforestation; conserving integrity of forests in turn benefits the global carbon budget. This case uses the 3Es to examine one case in Nepal of distributing the REDD+ funds among local participants. Of the 3Es, equity is getting attention worldwide but there is still debate on which principle of 3Es should be given priority to achieve overall effectiveness of REDD+. This case finds that equity is a fundamental requirement to achieve the other Es (efficiency and effectiveness) in REDD+ implementation. Further, I find that distributive equity is the most important and understood in three different ways in Nepal: rights, needs, and performance. There is an argument between communities and experts on which equity should be given priority. I recommend that the issue of needs based equity vs. performance-based equity should be solved by formation of guidelines of sharing benefits at two levels. First, the benefit distribution from international sources/markets to community forest user groups should be based on the ownership of carbon and performance of communities participating in REDD+. Second, at community level, communities should decide on the form of benefit distribution according to their needs. The primacy of equity in this case will likely find international echoes in other environmental policies and in other countries.

scholarly journals Characterization of Aerosol Composition, Aerosol Acidity and Organic Acid Partitioning at an Agriculture-Intensive Rural Southeastern U.S. Site

2018 ◽  
Author(s):  
Theodora Nah ◽  
Hongyu Guo ◽  
Amy P. Sullivan ◽  
Yunle Chen ◽  
David J. Tanner ◽  
...  
Keyword(s):  
Oxalic Acid ◽  
Organic Acids ◽  
Organic Acid ◽  
Organic Aerosol ◽  
Water Soluble ◽  
Molar Concentration ◽  
Particle Phase ◽  
Aerosol Composition ◽  
Phase Water ◽  
Acetic Acids

Abstract. The implementation of stringent emission regulations has resulted in the decline of anthropogenic pollutants including sulfur dioxide (SO2), nitrogen oxides (NOx) and carbon monoxide (CO). In contrast, ammonia (NH3) emissions are largely unregulated, with emissions projected to increase in the future. We present real-time aerosol and gas measurements from a field study conducted in an agricultural-intensive region in the southeastern U.S. during the fall of 2016 to investigate how NH3 affects particle acidity and SOA formation via the gas-particle partitioning of semi-volatile organic acids. Particle water and pH were determined using the ISORROPIA-II thermodynamic model and validated by comparing predicted inorganic HNO3-NO3− and NH3-NH4+ gas-particle partitioning ratios with measured values. Our results showed that despite the high NH3 concentrations (study average 8.1 ± 5.2 ppb), PM1 were highly acidic with pH values ranging from 0.9 to 3.8, and a study-averaged pH of 2.2 ± 0.6. PM1 pH varied by approximately 1.4 units diurnally. Formic and acetic acids were the most abundant gas-phase organic acids, and oxalate was the most abundant particle-phase water-soluble organic acid anion. Measured particle-phase water-soluble organic acids were on average 6 % of the total non-refractory PM1 organic aerosol mass. The measured molar fraction of oxalic acid in the particle phase (i.e., particle-phase oxalic acid molar concentration divided by the total oxalic acid molar concentration) ranged between 47 and 90 % for PM1 pH 1.2 to 3.4. The measured oxalic acid gas-particle partitioning ratios were in good agreement with their corresponding thermodynamic predictions, calculated based on oxalic acid’s physicochemical properties, ambient temperature, particle water and pH. In contrast, gas-particle partitioning of formic and acetic acids were not well predicted for reasons currently unknown. For this study, higher NH3 concentrations relative to what has been measured in the region in previous studies had minor effects on PM1 organic acids and their influence on the overall organic aerosol and PM1 mass concentrations.

scholarly journals Enhanced SOA formation from mixed anthropogenic and biogenic emissions during the CARES campaign

2013 ◽  
Vol 13 (4) ◽  
pp. 2091-2113 ◽  
Author(s):  
J. E. Shilling ◽  
R. A. Zaveri ◽  
J. D. Fast ◽  
L. Kleinman ◽  
M. L. Alexander ◽  
...  
Keyword(s):  
Mass Spectrometer ◽  
Organic Aerosol ◽  
Proton Transfer Reaction ◽  
Chemical Mechanism ◽  
Biogenic Emissions ◽  
Anthropogenic Emissions ◽  
Radiation Balance ◽  
Particle Phase ◽  
Aerosol Formation ◽  
Research Aircraft

Abstract. The CARES campaign was conducted during June, 2010 in the vicinity of Sacramento, California to study aerosol formation and aging in a region where anthropogenic and biogenic emissions regularly mix. Here, we describe measurements from an Aerodyne High Resolution Aerosol Mass Spectrometer (AMS), an Ionicon Proton Transfer Reaction Mass Spectrometer (PTR-MS), and trace gas detectors (CO, NO, NOx) deployed on the G-1 research aircraft to investigate ambient gas- and particle-phase chemical composition. AMS measurements showed that the particle phase is dominated by organic aerosol (OA) (85% on average) with smaller concentrations of sulfate (5%), nitrate (6%) and ammonium (3%) observed. PTR-MS data showed that isoprene dominated the biogenic volatile organic compound concentrations (BVOCs), with monoterpene concentrations generally below the detection limit. Using two different metrics, median OA concentrations and the slope of plots of OA vs. CO concentrations (i.e., ΔOA/ΔCO), we contrast organic aerosol evolution on flight days with different prevailing meteorological conditions to elucidate the role of anthropogenic and biogenic emissions on OA formation. Airmasses influenced predominantly by biogenic emissions had median OA concentrations of 2.2 μg m−3 and near zero ΔOA/ΔCO. Those influenced predominantly by anthropogenic emissions had median OA concentrations of 4.7 μg m−3 and ΔOA/ΔCO ratios of 35–44 μg m−3 ppmv. But, when biogenic and anthropogenic emissions mixed, OA levels were enhanced, with median OA concentrations of 11.4 μg m−3 and ΔOA/ΔCO ratios of 77–157 μg m−3 ppmv. Taken together, our observations show that production of OA was enhanced when anthropogenic emissions from Sacramento mixed with isoprene-rich air from the foothills. After considering several anthropogenic/biogenic interaction mechanisms, we conclude that NOx concentrations play a strong role in enhancing SOA formation from isoprene, though the chemical mechanism for the enhancement remains unclear. If these observations are found to be robust in other seasons and in areas outside of Sacramento, regional and global aerosol modules will need to incorporate more complex representations of NOx-dependent SOA mechanisms and yields into their algorithms. Ultimately, accurately predicting OA mass concentrations and their effect on radiation balance will require a mechanistically-based treatment of the interactions of biogenic and anthropogenic emissions.

scholarly journals Evaluation of Anthropogenic Secondary Organic Aerosol Tracers

2016 ◽  
Author(s):  
Ibrahim M. Al-Naiema ◽  
Elizabeth A. Stone
Keyword(s):  
Phthalic Acid ◽  
Secondary Organic Aerosol ◽  
Dicarboxylic Acids ◽  
Organic Aerosol ◽  
Secondary Source ◽  
Particle Phase ◽  
Water Sensitivity ◽  
Nitrobenzyl Alcohol ◽  
Ambient Concentrations ◽  
Highly Correlated

Abstract. Products of secondary organic aerosol (SOA) from aromatic volatile organic compounds (VOC) – 2,3-dihydroxy-4-oxopentanoic acid, dicarboxylic acids, nitromonoaromatics, and furandiones – were evaluated for their potential to serve as anthropogenic SOA tracers with respect to their 1) ambient concentrations and detectability in PM2.5 in Iowa City, IA, USA, 2) gas-particle partitioning behaviour, and 3) source specificity by way of correlations with primary and secondary source tracers and literature review. A widely used tracer for toluene-derived SOA, 2,3-dihydroxy-4-oxopentanoic acid was only detected in the particle phase (Fp = 1) at low, but consistently measureable ambient concentrations (averaging 0.3 ng m−3). Four aromatic dicarboxylic acids were detected at relatively higher concentrations (9.1–34.5 ng m−3), of which phthalic acid was the most abundant. Phthalic acid had a low particle-phase fraction (Fp = 0.26) likely due to quantitation interferences from phthalic anhydride, while 4-methylphthalic acid was predominantly in the particle phase (Fp = 0.82). Phthalic acid and 4-methyl phthalic acid were both highly correlated with 2,3-dihydroxy-4-oxopentanoic acid (rs = 0.73, p = 0.003; rs = 0.80, p < 0.001, respectively), suggesting that they were derived from aromatic VOC. Isophthalic and terephthalic acids, however, were detected only in the particle phase (Fp = 1) and correlations suggested association with primary emission sources. Nitromonoaromatics were dominated by particle-phase concentrations of 4-nitrocatechol (1.6 ng m−3) and 4-methyl-5-nitrocatechol (1.6 ng m−3) that were associated with biomass burning. Meanwhile, 4-hydroxy-3-nitrobenzyl alcohol was detected in a lower concentration (0.06 ng m−3) in the particle phase only (Fp = 1), and is known as a product of toluene photooxidation. Furandiones in the atmosphere have only been attributed to the photooxidation of aromatic hydrocarbons, however the substantial partitioning toward the gas phase (Fp ≤ 0.16) and their water sensitivity limit their application as tracers. The outcome of this study is the demonstration that 2,3-dihydroxy-4-oxopentanoic acid, phthalic acid, 4-methylphthalic acid, and 4-hydroxy-3-nitrobenzyl alcohol are good candidates for tracing SOA from aromatic VOC.

scholarly journals The global carbon budget: a conflicting claims problem

2016 ◽  
Vol 136 (3-4) ◽  
pp. 693-703 ◽  
Author(s):  
José-Manuel Giménez-Gómez ◽  
Jordi Teixidó-Figueras ◽  
Cori Vilella
Keyword(s):  
Carbon Budget ◽  
Global Carbon Budget ◽  
Claims Problem ◽  
Global Carbon

scholarly journals Molecular characterization of gaseous and particulate oxygenated compounds at a remote site in Cape Corsica in the western Mediterranean Basin

2021 ◽  
Vol 21 (10) ◽  
pp. 8067-8088
Author(s):  
Vincent Michoud ◽  
Elise Hallemans ◽  
Laura Chiappini ◽  
Eva Leoz-Garziandia ◽  
Aurélie Colomb ◽  
...  
Keyword(s):  
Organic Carbon ◽  
Carboxylic Acids ◽  
Organic Aerosol ◽  
Western Mediterranean ◽  
Water Soluble ◽  
Molecular Composition ◽  
Particle Phase ◽  
Western Mediterranean Basin ◽  
Partitioning Coefficients

Abstract. The characterization of the molecular composition of organic carbon in both gaseous and aerosol is key to understanding the processes involved in the formation and aging of secondary organic aerosol. Therefore a technique using active sampling on cartridges and filters and derivatization followed by analysis using a thermal desorption–gas chromatography–mass spectrometer (TD–GC–MS) has been used. It is aimed at studying the molecular composition of organic carbon in both gaseous and aerosol phases (PM2.5) during an intensive field campaign which took place in Corsica (France) during the summer of 2013: the ChArMEx (Chemistry and Aerosol Mediterranean Experiment) SOP1b (Special Observation Period 1B) campaign. These measurements led to the identification of 51 oxygenated (carbonyl and or hydroxyl) compounds in the gaseous phase with concentrations between 21 and 3900 ng m−3 and of 85 compounds in the particulate phase with concentrations between 0.3 and 277 ng m−3. Comparisons of these measurements with collocated data using other techniques have been conducted, showing fair agreement in general for most species except for glyoxal in the gas phase and malonic, tartaric, malic and succinic acids in the particle phase, with disagreements that can reach up to a factor of 8 and 20 on average, respectively, for the latter two acids. Comparison between the sum of all compounds identified by TD–GC–MS in the particle phase and the total organic matter (OM) mass reveals that on average 18 % of the total OM mass can be explained by the compounds measured by TD–GC–MS. This number increases to 24 % of the total water-soluble OM (WSOM) measured by coupling the Particle Into Liquid Sampler (PILS)-TOC (total organic carbon) if we consider only the sum of the soluble compounds measured by TD–GC–MS. This highlights the important fraction of the OM mass identified by these measurements but also the relative important fraction of OM mass remaining unidentified during the campaign and therefore the complexity of characterizing exhaustively the organic aerosol (OA) molecular chemical composition. The fraction of OM measured by TD–GC–MS is largely dominated by di-carboxylic acids, which represent 49 % of the PM2.5 content detected and quantified by this technique. Other contributions to PM2.5 composition measured by TD–GC–MS are then represented by tri-carboxylic acids (15 %), alcohols (13 %), aldehydes (10 %), di-hydroxy-carboxylic acids (5 %), monocarboxylic acids and ketones (3 % each), and hydroxyl-carboxylic acids (2 %). These results highlight the importance of polyfunctionalized carboxylic acids for OM, while the chemical processes responsible for their formation in both phases remain uncertain. While not measured by the TD–GC–MS technique, humic-like substances (HULISs) represent the most abundant identified species in the aerosol, contributing for 59 % of the total OM mass on average during the campaign. A total of 14 compounds were detected and quantified in both phases, allowing the calculation of experimental partitioning coefficients for these species. The comparison of these experimental partitioning coefficients with theoretical ones, estimated by three different models, reveals large discrepancies varying from 2 to 7 orders of magnitude. These results suggest that the supposed instantaneous equilibrium being established between gaseous and particulate phases assuming a homogeneous non-viscous particle phase is questionable.

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