Anthropogenic Sulfur Perturbations on Biogenic Oxidation: SO2 Additions Impact Gas-Phase OH Oxidation Products of α- and β-Pinene

Friedman, Beth; Brophy, Patrick D.; Brune, William H.; Farmer, Delphine K.

doi:10.1021/acs.est.5b05010

Cited by 53 publications

(42 citation statements)

References 81 publications

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“…In our experiment, the decrease in the SOA yield with SO 2 addition might then not be attributed to its reaction with OH. It is also possible that the SO 2 addition could change the chemistry of the photooxidation process and suppress the oxygenation of products (Friedman et al, 2016;Liu et al, 2015). Comparing the MS results at different initial SO 2 concentrations, the proportion of low molecular weight components increases with increasing SO 2 concentration.…”

Section: Effect Of So 2 On Soa Yieldsmentioning

confidence: 99%

Photooxidation of cyclohexene in the presence of SO2: SOA yield and chemical composition

Liu

Jia

et al. 2017

Atmos. Chem. Phys.

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Abstract. Secondary organic aerosol (SOA) formation from a cyclohexene / NO x system with various SO 2 concentrations under UV light was investigated to study the effects of cyclic alkenes on the atmospheric environment in polluted urban areas. A clear decrease at first and then an increase in the SOA yield was found with increasing SO 2 concentrations. The lowest SOA yield was obtained when the initial SO 2 concentration was in the range of 30-40 ppb, while higher SOA yield compared to that without SO 2 could not be obtained until the initial SO 2 concentration was higher than 85 ppb. The decreasing SOA yield might be due to the fact that the promoting effect of acid-catalysed reactions on SOA formation was less important than the inhibiting effect of decreasing OH concentration at low initial SO 2 concentrations, caused by the competition reactions of OH with SO 2 and cyclohexene. The competitive reaction was an important factor for SOA yield and it should not be neglected in photooxidation reactions. The composition of organic compounds in SOA was measured using several complementary techniques including Fourier transform infrared (FTIR) spectroscopy, ion chromatography (IC), and Exactive Plus Orbitrap mass spectrometer equipped with electrospray interface (ESI). We present new evidence that organosulfates were produced from the photooxidation of cyclohexene in the presence of SO 2 .

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Section: Effect Of So 2 On Soa Yieldsmentioning

confidence: 99%

Photooxidation of cyclohexene in the presence of SO2: SOA yield and chemical composition

Liu

Jia

et al. 2017

Atmos. Chem. Phys.

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“…Similarly, at low NO x (initial NO < 0.3, α-pinene ∼ 20 ppb), Han et al (2016) found that the acidity of seed has no significant effect on SOA yield from α-pinene photooxidation. In addition, SO 2 was found to influence the gas-phase oxidation products from α-pinene and β-pinene photooxidation, which is possibly due to the change in the OH / HO 2 ratio caused by SO 2 oxidation or SO 3 directly reacting with organic molecules (Friedman et al, 2016).…”

Section: Introductionmentioning

confidence: 99%

Effects of NOx and SO2 on the secondary organic aerosol formation from photooxidation of α-pinene and limonene

et al. 2018

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Abstract. Anthropogenic emissions such as NO x and SO 2 influence the biogenic secondary organic aerosol (SOA) formation, but detailed mechanisms and effects are still elusive. We studied the effects of NO x and SO 2 on the SOA formation from the photooxidation of α-pinene and limonene at ambient relevant NO x and SO 2 concentrations (NO x : < 1to 20 ppb, SO 2 : < 0.05 to 15 ppb). In these experiments, monoterpene oxidation was dominated by OH oxidation. We found that SO 2 induced nucleation and enhanced SOA mass formation. NO x strongly suppressed not only new particle formation but also SOA mass yield. However, in the presence of SO 2 which induced a high number concentration of particles after oxidation to H 2 SO 4 , the suppression of the mass yield of SOA by NO x was completely or partly compensated for. This indicates that the suppression of SOA yield by NO x was largely due to the suppressed new particle formation, leading to a lack of particle surface for the organics to condense on and thus a significant influence of vapor wall loss on SOA mass yield. By compensating for the suppressing effect on nucleation of NO x , SO 2 also compensated for the suppressing effect on SOA yield. Aerosol mass spectrometer data show that increasing NO x enhanced nitrate formation. The majority of the nitrate was organic nitrate (57-77 %), even in low-NO x conditions (< ∼ 1 ppb). Organic nitrate contributed 7-26 % of total organics assuming a molecular weight of 200 g mol −1 . SOA from α-pinene photooxidation at high NO x had a generally lower hydrogen to carbon ratio (H / C), compared to low NO x . The NO x dependence of the chemical composition can be attributed to the NO x dependence of the branching ratio of the RO 2 loss reactions, leading to a lower fraction of organic hydroperoxides and higher fractions of organic nitrates at high NO x . While NO x suppressed new particle formation and SOA mass formation, SO 2 can compensate for such effects, and the combining effect of SO 2 and NO x may have an important influence on SOA formation affected by interactions of biogenic volatile organic compounds (VOCs) with anthropogenic emissions.

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“…In the presence of SO 2 , enhanced gas-phase products from a-pinene and b-pinene photooxidation were observed with a decreased oxidation state of gas-phase semivolatile species (Friedman et al, 2016). Liu et al (2017) demonstrated that SOA yields of cyclohexene photooxidation 55 were lower at atmospherically relevant concentrations of SO 2 , implying that SO 2 may indirectly decrease SOA formation when the acid-catalyzed SOA enhancement is insufficient to compensate for the loss of OH reactivity towards VOCs.…”

Section: Introduction 25mentioning

confidence: 99%

Novel Pathway of SO2 Oxidation in the Atmosphere: Reactions with Monoterpene Ozonolysis Intermediates and Secondary Organic Aerosol

Ye¹,

Abbatt²,

Chan³

2017

Preprint

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Abstract. Ozonolysis of monoterpenes is an important source of atmospheric biogenic secondary organic aerosol (BSOA). While enhanced BSOA formation has been associated with sulfate-rich conditions, the 10 underlying mechanisms remain poorly understood. In this work, the interactions between SO 2 and reactive intermediates from monoterpene ozonolysis were investigated under different humidity conditions (10% vs. 50%). Chamber experiments were conducted with ozonolysis of a-pinene or limonene in the presence of SO 2 . Limonene SOA formation was enhanced in the presence of SO 2 , while no significant changes in SOA yields were observed during a-pinene ozonolysis. Under dry conditions, SO 2 primarily reacted with 15 stabilized Criegee Intermediates (sCI) produced from ozonolysis, but at 50% RH, heterogeneous uptake of SO 2 onto organic aerosol was found to be the dominant sink of SO 2 , likely owing to reactions between SO 2 and organic peroxides. This SO 2 loss mechanism to organic peroxides in SOA has not previously been identified in experimental chamber study. Organosulfates were detected and identified using electrospray ionization-ion mobility time of flight mass spectrometer (ESI-IMS-TOF) when SO 2 was 20 present in the experiments. Our results demonstrate the synergistic effects between BSOA formation and SO 2 oxidation through sCI chemistry and SO 2 uptake onto organic aerosol and illustrate the importance of considering the chemistry of organic and sulfur-containing compounds holistically to properly account for their reactive sinks.Atmos. Chem. Phys. Discuss., https://doi

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Anthropogenic Sulfur Perturbations on Biogenic Oxidation: SO₂ Additions Impact Gas-Phase OH Oxidation Products of α- and β-Pinene

Cited by 53 publications

References 81 publications

Photooxidation of cyclohexene in the presence of SO<sub>2</sub>: SOA yield and chemical composition

Photooxidation of cyclohexene in the presence of SO<sub>2</sub>: SOA yield and chemical composition

Effects of NO<sub><i>x</i></sub> and SO<sub>2</sub> on the secondary organic aerosol formation from photooxidation of <i>α</i>-pinene and limonene

Novel Pathway of SO<sub>2</sub> Oxidation in the Atmosphere: Reactions with Monoterpene Ozonolysis Intermediates and Secondary Organic Aerosol

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Anthropogenic Sulfur Perturbations on Biogenic Oxidation: SO2 Additions Impact Gas-Phase OH Oxidation Products of α- and β-Pinene

Cited by 53 publications

References 81 publications

Photooxidation of cyclohexene in the presence of SO&lt;sub&gt;2&lt;/sub&gt;: SOA yield and chemical composition

Photooxidation of cyclohexene in the presence of SO&lt;sub&gt;2&lt;/sub&gt;: SOA yield and chemical composition

Effects of NO&lt;sub&gt;&lt;i&gt;x&lt;/i&gt;&lt;/sub&gt; and SO&lt;sub&gt;2&lt;/sub&gt; on the secondary organic aerosol formation from photooxidation of &lt;i&gt;α&lt;/i&gt;-pinene and limonene

Novel Pathway of SO&lt;sub&gt;2&lt;/sub&gt; Oxidation in the Atmosphere: Reactions with Monoterpene Ozonolysis Intermediates and Secondary Organic Aerosol

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Anthropogenic Sulfur Perturbations on Biogenic Oxidation: SO₂ Additions Impact Gas-Phase OH Oxidation Products of α- and β-Pinene

Photooxidation of cyclohexene in the presence of SO<sub>2</sub>: SOA yield and chemical composition

Photooxidation of cyclohexene in the presence of SO<sub>2</sub>: SOA yield and chemical composition

Effects of NO<sub><i>x</i></sub> and SO<sub>2</sub> on the secondary organic aerosol formation from photooxidation of <i>α</i>-pinene and limonene

Novel Pathway of SO<sub>2</sub> Oxidation in the Atmosphere: Reactions with Monoterpene Ozonolysis Intermediates and Secondary Organic Aerosol