An Observational Perspective on the Atmospheric Impacts of Alkyl and Multifunctional Nitrates on Ozone and Secondary Organic Aerosol

Perring, A. E.; Pusede, Sally E.; Cohen, R. C.

doi:10.1021/cr300520x

Cited by 249 publications

(321 citation statements)

References 240 publications

Supporting

Mentioning

303

Contrasting

Unclassified

Order By: Relevance

“…The HO 2 reaction pathway is important for the production of particulate matter through second-generation epoxydiol products (5,6). The NO pathway contributes to the transport of nitrogen beyond the isoprene source region through the formation of stable organic nitrogen compounds (20). The two pathways, to different extents, help to maintain the atmospheric oxidation cycle, including feedbacks on OH and O 3 concentrations (3,5,11).…”

mentioning

confidence: 99%

Isoprene photochemistry over the Amazon rainforest

Liu

Brito

Dorris

et al. 2016

Proc. Natl. Acad. Sci. U.S.A.

106

165

View full text Add to dashboard Cite

Isoprene photooxidation is a major driver of atmospheric chemistry over forested regions. Isoprene reacts with hydroxyl radicals (OH) and molecular oxygen to produce isoprene peroxy radicals (ISOPOO). These radicals can react with hydroperoxyl radicals (HO 2 ) to dominantly produce hydroxyhydroperoxides (ISOPOOH). They can also react with nitric oxide (NO) to largely produce methyl vinyl ketone (MVK) and methacrolein (MACR). Unimolecular isomerization and bimolecular reactions with organic peroxy radicals are also possible. There is uncertainty about the relative importance of each of these pathways in the atmosphere and possible changes because of anthropogenic pollution. Herein, measurements of ISOPOOH and MVK + MACR concentrations are reported over the central region of the Amazon basin during the wet season. The research site, downwind of an urban region, intercepted both background and polluted air masses during the GoAmazon2014/5 Experiment. Under background conditions, the confidence interval for the ratio of the ISOPOOH concentration to that of MVK + MACR spanned 0.4-0.6. This result implies a ratio of the reaction rate of ISOPOO with HO 2 to that with NO of approximately unity. A value of unity is significantly smaller than simulated at present by global chemical transport models for this important, nominally low-NO, forested region of Earth. Under polluted conditions, when the concentrations of reactive nitrogen compounds were high (>1 ppb), ISOPOOH concentrations dropped below the instrumental detection limit (<60 ppt). This abrupt shift in isoprene photooxidation, sparked by human activities, speaks to ongoing and possible future changes in the photochemistry active over the Amazon rainforest.isoprene photochemistry | Amazon | organic hydroperoxides

show abstract

mentioning

confidence: 99%

Isoprene photochemistry over the Amazon rainforest

Liu

Brito

Dorris

et al. 2016

Proc. Natl. Acad. Sci. U.S.A.

106

165

View full text Add to dashboard Cite

show abstract

“…Ambient air organic mixtures are observed to have average Reaction (R3') branching ratios in the range of 2-8 % (Perring et al, 2013). At low NO x , increasing NO drives Reaction (R3) and Reaction (R5), and therefore the oxidation of VOCs and P O 3 .…”

Section: S E Pusede Et Al: Temperature-dependent Impacts Of Emissimentioning

confidence: 99%

“…At peak P O 3 , the production of alkyl nitrates by Reaction (R3') and peroxy nitrates also reach a peak. The formation of these nitrates is important to the absolute P O 3 but has little effect on P O 3 's functional form Perring et al, 2013). When chemistry is VOC-limited, the impact of increasing the VOCR is twofold: (a) it increases the magnitude of P O 3 and (b) it shifts the position of peak P O 3 to higher NO x .…”

Section: S E Pusede Et Al: Temperature-dependent Impacts Of Emissimentioning

confidence: 99%

On the temperature dependence of organic reactivity, nitrogen oxides, ozone production, and the impact of emission controls in San Joaquin Valley, California

et al. 2014

Self Cite

View full text Add to dashboard Cite

Abstract. The San Joaquin Valley (SJV) experiences some of the worst ozone air quality in the US, frequently exceeding the California 8 h standard of 70.4 ppb. To improve our understanding of trends in the number of ozone violations in the SJV, we analyze observed relationships between organic reactivity, nitrogen oxides (NO x ), and daily maximum temperature in the southern SJV using measurements made as part of California at the Nexus of Air Quality and Climate Change in 2010 (CalNex-SJV). We find the daytime speciated organic reactivity with respect to OH during CalNex-SJV has a temperature-independent portion with molecules typically associated with motor vehicles being the major component.Published by Copernicus Publications on behalf of the European Geosciences Union. S. E. Pusede et al.: Temperature-dependent impacts of emission controlsAt high temperatures, characteristic of days with high ozone, the largest portion of the total organic reactivity increases exponentially with temperature and is dominated by small, oxygenated organics and molecules that are unidentified. We use this simple temperature classification to consider changes in organic emissions over the last and next decade. With the CalNex-SJV observations as constraints, we examine the sensitivity of ozone production (P O 3 ) to future NO x and organic reactivity controls. We find that P O 3 is NO x -limited at all temperatures on weekends and on weekdays when daily maximum temperatures are greater than 29 • C. As a consequence, NO x reductions are the most effective control option for reducing the frequency of future ozone violations in the southern SJV.

show abstract

“…ONs formed from isoprene oxidation alone are responsible for the export of 8-30% of anthropogenic NO x out of the US continental boundary layer (1,2). Regional NO x budgets and tropospheric ozone (O 3 ) production are, therefore, particularly sensitive to uncertainties in the yields and fates of ON (3)(4)(5)(6). The yields implemented in modeling studies are determined from laboratory experiments, in which only a few of the first generation gaseous ONs or the total gas-phase ONs and particle-phase organic nitrates (pONs) have been quantified, whereas production of highly functionalized ONs capable of strongly partitioning to the particle phase have been inferred (7)(8)(9)(10)(11) or directly measured in the gas phase (12).…”

mentioning

confidence: 99%

Highly functionalized organic nitrates in the southeast United States: Contribution to secondary organic aerosol and reactive nitrogen budgets

Lee

Mohr

Lopez‐Hilfiker

et al. 2016

Proc. Natl. Acad. Sci. U.S.A.

305

438

View full text Add to dashboard Cite

Speciated particle-phase organic nitrates (pONs) were quantified using online chemical ionization MS during June and July of 2013 in rural Alabama as part of the Southern Oxidant and Aerosol Study. A large fraction of pONs is highly functionalized, possessing between six and eight oxygen atoms within each carbon number group, and is not the common first generation alkyl nitrates previously reported. Using calibrations for isoprene hydroxynitrates and the measured molecular compositions, we estimate that pONs account for 3% and 8% of total submicrometer organic aerosol mass, on average, during the day and night, respectively. Each of the isoprene-and monoterpenes-derived groups exhibited a strong diel trend consistent with the emission patterns of likely biogenic hydrocarbon precursors. An observationally constrained diel box model can replicate the observed pON assuming that pONs (i) are produced in the gas phase and rapidly establish gasparticle equilibrium and (ii) have a short particle-phase lifetime (∼2-4 h). Such dynamic behavior has significant implications for the production and phase partitioning of pONs, organic aerosol mass, and reactive nitrogen speciation in a forested environment. O rganic nitrates (ONs; ON = RONO 2 + RO 2 NO 2 ) are an important reservoir, if not sink, of atmospheric nitrogen oxides (NO x = NO + NO 2 ). ONs formed from isoprene oxidation alone are responsible for the export of 8-30% of anthropogenic NO x out of the US continental boundary layer (1, 2). Regional NO x budgets and tropospheric ozone (O 3 ) production are, therefore, particularly sensitive to uncertainties in the yields and fates of ON (3-6). The yields implemented in modeling studies are determined from laboratory experiments, in which only a few of the first generation gaseous ONs or the total gas-phase ONs and particle-phase organic nitrates (pONs) have been quantified, whereas production of highly functionalized ONs capable of strongly partitioning to the particle phase have been inferred (7-11) or directly measured in the gas phase (12). Addition of a nitrate (-ONO 2 ) functional group to a hydrocarbon is estimated to lower the equilibrium saturation vapor pressure by 2.5-3 orders of magnitude (13). Thus, ON formation can enhance particle-phase partitioning of semivolatile species in regions with elevated levels of nitrogen oxides, contributing to secondary organic aerosol (SOA) growth (8). However, highly time-resolved measurements of speciated ON in the particle phase have been lacking.We use a recently developed high-resolution time-of-flight chemical ionization mass spectrometer (HRToF-CIMS) using iodide-adduct ionization (14) with a filter inlet for gases and aerosols (FIGAERO) (15) that allows alternating in situ measurements of the molecular SignificanceWe present online field observations of the speciated molecular composition of organic nitrates in ambient atmospheric particles utilizing recently developed high-resolution MS-based instrumentation. We find that never-before-identified low-volatility organi...

show abstract

An Observational Perspective on the Atmospheric Impacts of Alkyl and Multifunctional Nitrates on Ozone and Secondary Organic Aerosol

Cited by 249 publications

References 240 publications

Isoprene photochemistry over the Amazon rainforest

Isoprene photochemistry over the Amazon rainforest

On the temperature dependence of organic reactivity, nitrogen oxides, ozone production, and the impact of emission controls in San Joaquin Valley, California

Highly functionalized organic nitrates in the southeast United States: Contribution to secondary organic aerosol and reactive nitrogen budgets

Contact Info

Product

Resources

About