scholarly journals Isoprene oxidation by nitrate radical: alkyl nitrate and secondary organic aerosol yields

2009 ◽  
Vol 9 (2) ◽  
pp. 8857-8902 ◽  
Author(s):  
A. W. Rollins ◽  
A. Kiendler-Scharr ◽  
J. Fry ◽  
T. Brauers ◽  
S. S. Brown ◽  
...  
Keyword(s):  
First Generation ◽  
Secondary Organic Aerosol ◽  
Model Simulation ◽  
Effective Rate Constant ◽  
Organic Aerosol ◽  
Effective Rate ◽  
Oxidation Products ◽  
Alkyl Nitrates ◽  
Alkyl Nitrate ◽  
Isoprene Oxidation

Abstract. Alkyl nitrates and secondary organic aerosol (SOA) produced during the oxidation of isoprene by nitrate radicals has been observed in the SAPHIR chamber. We find the yield of nitrates is 70±8% from the isoprene+NO3 reaction, and the yield for secondary dinitrates produced in the reaction of primary isoprene nitrates with NO3 is 40±20%. We find an effective rate constant for reaction of NO3 with the group of first generation oxidation products to be 7×10−14 cm3 s−1. At the low total organic aerosol concentration in the chamber (max ≈0.6 μg m−3) we observed a mass yield (ΔSOA mass/Δisoprene mass) of 2% for the entire 16 h experiment. However a comparison of the timing of the observed SOA production to a box model simulation of first and second generation oxidation products shows that the yield from the first generation products was <0.2% while the further oxidation of the initial products leads to a yield of 10% (defined as ΔSOA/Δisoprene2x where Δisoprene2x is the mass of isoprene which reacted twice with NO3). The SOA yield of 10% is consistent with equilibrium partitioning of highly functionalized C5 products of isoprene oxidation.

scholarly journals Isoprene oxidation by nitrate radical: alkyl nitrate and secondary organic aerosol yields

2009 ◽  
Vol 9 (18) ◽  
pp. 6685-6703 ◽  
Author(s):  
A. W. Rollins ◽  
A. Kiendler-Scharr ◽  
J. L. Fry ◽  
T. Brauers ◽  
S. S. Brown ◽  
...  
Keyword(s):  
First Generation ◽  
Secondary Organic Aerosol ◽  
Model Simulation ◽  
Effective Rate Constant ◽  
Organic Aerosol ◽  
Effective Rate ◽  
Oxidation Products ◽  
Alkyl Nitrates ◽  
Alkyl Nitrate ◽  
Isoprene Oxidation

Abstract. Alkyl nitrates and secondary organic aerosol (SOA) produced during the oxidation of isoprene by nitrate radicals has been observed in the SAPHIR (Simulation of Atmospheric PHotochemistry In a large Reaction Chamber) chamber. A 16 h dark experiment was conducted with temperatures at 289–301 K, and maximum concentrations of 11 ppb isoprene, 62.4 ppb O3 and 31.1 ppb NOx. We find the yield of nitrates is 70±8% from the isoprene + NO3 reaction, and the yield for secondary dinitrates produced in the reaction of primary isoprene nitrates with NO3 is 40±20%. We find an effective rate constant for reaction of NO3 with the group of first generation oxidation products to be 7×10−14 molecule−1 cm3 s−1. At the low total organic aerosol concentration in the chamber (max=0.52 μg m−3) we observed a mass yield (ΔSOA mass/Δisoprene mass) of 2% for the entire 16 h experiment. However a comparison of the timing of the observed SOA production to a box model simulation of first and second generation oxidation products shows that the yield from the first generation products was <0.7% while the further oxidation of the initial products leads to a yield of 14% (defined as ΔSOA/Δisoprene2x where Δisoprene2x is the mass of isoprene which reacted twice with NO3). The SOA yield of 14% is consistent with equilibrium partitioning of highly functionalized C5 products of isoprene oxidation.

scholarly journals Secondary organic aerosol in the global aerosol – chemistry transport model Oslo CTM2

2007 ◽  
Vol 7 (3) ◽  
pp. 9053-9092 ◽  
Author(s):  
C. R. Hoyle ◽  
T. Berntsen ◽  
G. Myhre ◽  
I. S. A. Isaksen
Keyword(s):  
Ammonium Sulphate ◽  
Secondary Organic Aerosol ◽  
Transport Model ◽  
Model Simulation ◽  
Anthropogenic Activities ◽  
Organic Aerosol ◽  
Oxidation Products ◽  
Total Production ◽  
Chemical Transport Model ◽  
Sulphate Aerosol

Abstract. The global chemical transport model Oslo CTM2 has been extended to include the formation, transport and deposition of secondary organic aerosol (SOA). Precursor hydrocarbons which are oxidised to form condensible species include both biogenic species such as terpenes and isoprene, as well as species emitted predominantly by anthropogenic activities (toluene, m-xylene, methylbenzene and other aromatics). A model simulation for 2004 gives an annual global SOA production of approximately 55 Tg. Of this total, 2.5 Tg is found to consist of the oxidation products of anthropogenically emitted hydrocarbons, and about 15 Tg is formed by the oxidation products of isoprene. The global production of SOA is increased to about 76 Tg yr−1 by allowing semi-volatile species to condense on ammonium sulphate aerosol. This brings modelled organic aerosol values closer to those observed, however observations in Europe remain significantly underestimated, raising the possibility of an unaccounted for SOA source. Allowing SOA to form on ammonium sulphate aerosol increases the contribution of anthropogenic SOA from about 4.5% to almost 9% of the total production. The importance of NO3 as an oxidant of SOA precursors is found to vary regionally, causing up to 50%–60% of the total amount of SOA near the surface in polluted regions and less than 25% in more remote areas. This study underscores the need for SOA to be represented in a more realistic way in global aerosol models in order to better reproduce observations of organic aerosol burdens in industrialised and biomass burning regions.

Secondary organic aerosol yields from cloud-processing of isoprene oxidation products

2008 ◽  
Vol 35 (2) ◽  
Author(s):  
Barbara Ervens ◽  
Annmarie G. Carlton ◽  
Barbara J. Turpin ◽  
Katye E. Altieri ◽  
Sonia M. Kreidenweis ◽  
...  
Keyword(s):  
Secondary Organic Aerosol ◽  
Organic Aerosol ◽  
Oxidation Products ◽  
Cloud Processing ◽  
Isoprene Oxidation ◽  
Isoprene Oxidation Products

scholarly journals Evidence for a significant proportion of Secondary Organic Aerosol from isoprene above a maritime tropical forest

2011 ◽  
Vol 11 (3) ◽  
pp. 1039-1050 ◽  
Author(s):  
N. H. Robinson ◽  
J. F. Hamilton ◽  
J. D. Allan ◽  
B. Langford ◽  
D. E. Oram ◽  
...  
Keyword(s):  
Secondary Organic Aerosol ◽  
Significant Proportion ◽  
Organic Aerosol ◽  
Oxidation Products ◽  
Emission Region ◽  
Experimental Chamber ◽  
Mass Spectral ◽  
Aerosol Mass ◽  
Isoprene Oxidation ◽  
Highly Correlated

Abstract. Isoprene is the most abundant non-methane biogenic volatile organic compound (BVOC), but the processes governing secondary organic aerosol (SOA) formation from isoprene oxidation are only beginning to become understood and selective quantification of the atmospheric particulate burden remains difficult. Organic aerosol above a tropical rainforest located in Danum Valley, Borneo, Malaysia, a high isoprene emission region, was studied during Summer 2008 using Aerosol Mass Spectrometry and offline detailed characterisation using comprehensive two dimensional gas chromatography. Observations indicate that a substantial fraction (up to 15% by mass) of atmospheric sub-micron organic aerosol was observed as methylfuran (MF) after thermal desorption. This observation was associated with the simultaneous measurements of established gas-phase isoprene oxidation products methylvinylketone (MVK) and methacrolein (MACR). Observations of MF were also made during experimental chamber oxidation of isoprene. Positive matrix factorisation of the AMS organic mass spectral time series produced a robust factor which accounts for an average of 23% (0.18 μg m−3), reaching as much as 53% (0.50 μg m−3) of the total oraganic loading, identified by (and highly correlated with) a strong MF signal. Assuming that this factor is generally representative of isoprene SOA, isoprene derived aerosol plays a significant role in the region. Comparisons with measurements from other studies suggest this type of isoprene SOA plays a role in other isoprene dominated environments, albeit with varying significance.

scholarly journals Secondary organic aerosol production from pinanediol, a semi-volatile surrogate for first-generation oxidation products of monoterpenes

2018 ◽  
Vol 18 (9) ◽  
pp. 6171-6186 ◽  
Author(s):  
Penglin Ye ◽  
Yunliang Zhao ◽  
Wayne K. Chuang ◽  
Allen L. Robinson ◽  
Neil M. Donahue
Keyword(s):  
Organic Compounds ◽  
First Generation ◽  
Secondary Organic Aerosol ◽  
Organic Aerosol ◽  
Particle Formation ◽  
Oxidation Products ◽  
Basis Set ◽  
New Particle Formation ◽  
Aerosol Mass ◽  
Volatile Precursor

Abstract. We have investigated the production of secondary organic aerosol (SOA) from pinanediol (PD), a precursor chosen as a semi-volatile surrogate for first-generation oxidation products of monoterpenes. Observations at the CLOUD facility at CERN have shown that oxidation of organic compounds such as PD can be an important contributor to new-particle formation. Here we focus on SOA mass yields and chemical composition from PD photo-oxidation in the CMU smog chamber. To determine the SOA mass yields from this semi-volatile precursor, we had to address partitioning of both the PD and its oxidation products to the chamber walls. After correcting for these losses, we found OA loading dependent SOA mass yields from PD oxidation that ranged between 0.1 and 0.9 for SOA concentrations between 0.02 and 20 µg m−3, these mass yields are 2–3 times larger than typical of much more volatile monoterpenes. The average carbon oxidation state measured with an aerosol mass spectrometer was around −0.7. We modeled the chamber data using a dynamical two-dimensional volatility basis set and found that a significant fraction of the SOA comprises low-volatility organic compounds that could drive new-particle formation and growth, which is consistent with the CLOUD observations.

scholarly journals Global modelling of secondary organic aerosol in the troposphere: A sensitivity analysis

2003 ◽  
Vol 3 (3) ◽  
pp. 2879-2929 ◽  
Author(s):  
K. Tsigaridis ◽  
M. Kanakidou
Keyword(s):  
Organic Matter ◽  
First Generation ◽  
Secondary Organic Aerosol ◽  
Transport Model ◽  
Organic Aerosol ◽  
Oxidation Products ◽  
Carbonaceous Aerosols ◽  
Temporal And Spatial Distribution ◽  
Model Calculations ◽  
3 Dimensional

Abstract. A global 3-dimensional chemistry/transport model able to describe O3, NOx, Volatile Organic Compounds (VOC), sulphur and NH3 chemistry has been extended to simulate the temporal and spatial distribution of primary and secondary carbonaceous aerosols in the troposphere focusing on Secondary Organic Aerosol (SOA) formation. A number of global simulations have been performed to determine a possible range of annual global SOA production and investigate uncertainties associated with the model results. Uncertainties in the model calculations related to the enthalpy of vaporization, the solubility and the activity coefficient of the condensable species, the chemical fate of the first generation low volatility oxidation products, the ageing of particles with regard to their hydrophilic properties, the partitioning of SOA on various aerosol surfaces and the evaporation of semi-volatiles from aerosol surfaces have been evaluated. Although not all sources of uncertainties have been investigated, according to our calculations, the above factors within the experimental range of variations could result to an overall uncertainty of about a factor of 20 in the global SOA budget. The global annual SOA production from biogenic VOC might range from 2.5 to 44.5 Tg of organic matter per year, whereas that from anthropogenic VOC ranges from 0.05 to 2.62 Tg of organic matter per year. These estimates can be considered as a lower limit, since partitioning on coarse particles like nitrate, dust or sea-salt, together with the partitioning and the dissociation of the semi-volatile products in aerosol water has been neglected. The large uncertainties associated with the emissions of VOC have not been investigated in this study. Comparison of model results to observations, where available, shows a better agreement for the upper budget estimates than for the lower ones.

scholarly journals Characterisation of tracers for aging of α-pinene secondary organic aerosol using liquid chromatography/negative ion electrospray ionisation mass spectrometry

2012 ◽  
Vol 9 (3) ◽  
pp. 236 ◽  
Author(s):  
Farhat Yasmeen ◽  
Reinhilde Vermeylen ◽  
Nicolas Maurin ◽  
Emilie Perraudin ◽  
Jean-François Doussin ◽  
...  
Keyword(s):  
First Generation ◽  
Secondary Organic Aerosol ◽  
Organic Aerosol ◽  
Oxidation Products ◽  
Negative Ion ◽  
Subsequent Aging ◽  
Structural Characterisation ◽  
Spectrometric Data ◽  
Ionisation Mass Spectrometry ◽  
Biogenic Aerosols

Environmental contextAmbient fine aerosol from forested sites contains secondary organic aerosol from the oxidation of monoterpenes that are emitted by the vegetation, mainly by conifers. These biogenic aerosols can have varying lifetimes in the atmosphere because they contain first-generation oxidation products of α-pinene as well as aged products formed through further photooxidation, fragmentation, hydrolysis, and dimerisation reactions. We focus on the structural characterisation of secondary organic aerosol products that are simulated in a smog chamber experiment and can serve as potential tracers for aging processes in biogenic aerosols. AbstractSecondary organic aerosol (SOA) from the oxidation of α-pinene is a very complex and dynamic mixture containing products with a different chemical nature and physicochemical properties that are dependent on chemical evolution or aging processes. In this study, we focus on the chemical characterisation of major products that are formed upon α-pinene ozonolysis SOA and subsequent aging through OH-initiated reactions in the absence of NOx, which include known as well as unknown tracers. The mass spectrometric data obtained for selected unknown compounds that show an increased relative abundance upon aging are interpreted in detail and tentative structures for them are proposed taking into account their formation through photooxidation of α-pinene. Known tracers for α-pinene SOA aging that were identified include norpinic acid, 10-hydroxypinonic acid, diaterpenylic acid acetate, and diesters formed by esterification of pinic acid with terpenylic acid or 10-hydroxypinonic acid. Novel tracers for α-pinene SOA aging that were tentatively identified include dinorpinic acid and 8-hydroxypinonic acid. In addition, reaction mechanisms are proposed to explain the formation of the observed α-pinene SOA tracers.

scholarly journals Reactive oxidation products promote secondary organic aerosol formation from green leaf volatiles

2009 ◽  
Vol 9 (1) ◽  
pp. 3921-3943
Author(s):  
J. F. Hamilton ◽  
A. C. Lewis ◽  
T. J. Carey ◽  
J. C. Wenger ◽  
E. Borrás i Garcia ◽  
...  
Keyword(s):  
First Generation ◽  
Secondary Organic Aerosol ◽  
Chemical Species ◽  
Organic Aerosol ◽  
Green Leaf Volatiles ◽  
Oxidation Products ◽  
Atmospheric Oxidation ◽  
Green Leaf ◽  
Aerosol Formation ◽  
Leaf Volatiles

Abstract. Green leaf volatiles (GLVs) are an important group of chemicals released by vegetation which have emission fluxes that can be significantly increased when plants are damaged or stressed. A series of simulation chamber experiments has been conducted at the European Photoreactor in Valencia, Spain, to investigate secondary organic aerosol (SOA) formation from the atmospheric oxidation of the major GLVs cis-3-hexenylacetate and cis-3-hexen-1-ol. Liquid chromatography-ion trap mass spectrometry was used to identify chemical species present in the SOA. Cis-3-hexen-1-ol proved to be a more efficient SOA precursor due to the high reactivity of its first generation oxidation product, 3-hydroxypropanal, which can hydrate and undergo further reactions with other aldehydes resulting in SOA dominated by higher molecular weight oligomers. The lower SOA yields produced from cis-3-hexenylacetate are attributed to the acetate functionality, which inhibits oligomer formation in the particle phase. Based on observed SOA yields and best estimates of global emissions, these compounds may be calculated to be a substantial unidentified global source of SOA, contributing 1–5 TgC yr−1, equivalent to around a third of that predicted from isoprene. Molecular characterization of the SOA, combined with organic mechanistic information, has provided evidence that the formation of organic aerosols from GLVs is closely related to the reactivity of their first generation atmospheric oxidation products, and indicates that this may be a simple parameter that could be used in assessing the aerosol formation potential for other unstudied organic compounds in the atmosphere.

scholarly journals Secondary organic aerosol from chlorine-initiated oxidation of isoprene

2017 ◽  
Author(s):  
Dongyu S. Wang ◽  
Lea Hildebrandt Ruiz
Keyword(s):  
Secondary Organic Aerosol ◽  
Organic Aerosol ◽  
Oxidative Capacity ◽  
Oxidation Products ◽  
Ionization Mass ◽  
Photo Oxidation ◽  
Wide Range ◽  
Chlorine Radicals ◽  
Isoprene Oxidation ◽  
Isoprene Oxidation Products

Abstract. Recent studies have found inland concentrations of reactive chlorine species to be higher than expected, suggesting that atmospheric chlorine chemistry is more extensive than previously thought. Chlorine radicals can interact with HOx radicals and nitrogen oxides (NOx) to alter the oxidative capacity of the atmosphere. They are known to rapidly oxidize a wide range of volatile organic compounds (VOC) found in the atmosphere, yet little is known about secondary organic aerosol (SOA) formation from chlorine-initiated photo-oxidation and its atmospheric implications. Environmental chamber experiments were carried out under low-NOx conditions with isoprene and chlorine as primary VOC and oxidant sources. Upon complete isoprene consumption, observed SOA yields ranged from 8 % to 36 %, decreasing with extended photo-oxidation and SOA aging. A High-Resolution Time-of-Flight Chemical Ionization Mass Spectrometer was used to determine the molecular composition of gas-phase species using iodide-water and hydronium-water ionization. Ions consistent with isoprene-derived epoxydiol (IEPOX) and other common OH-isoprene oxidation products were observed, evident of secondary OH production and resulting chemistry from Cl-initiated reactions.

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