Technical note: Conversion of isoprene hydroxy hydroperoxides (ISOPOOHs) on metal environmental simulation chamber walls

Bernhammer, Anne-Kathrin; Breitenlechner, Martin; Keutsch, Frank N.; Hansel, Armin

doi:10.5194/acp-17-4053-2017

Cited by 15 publications

(23 citation statements)

References 31 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…In both experimental configurations, we heated the passivated stainless steel transfer lines to reduce the loss of semivolatile vapors. However, metal throughout the experimental setup can convert gas‐phase species such as hydroperoxides, which are known to form from biomass burning, to more stable products [ Rivera‐Rios et al , ; Bernhammer et al , ]. This issue was not investigated in this study.…”

Section: Methodsmentioning

confidence: 99%

A dual‐chamber method for quantifying the effects of atmospheric perturbations on secondary organic aerosol formation from biomass burning emissions

et al. 2017

View full text Add to dashboard Cite

Biomass burning (BB) is a major source of atmospheric pollutants. Field and laboratory studies indicate that secondary organic aerosol (SOA) formation from BB emissions is highly variable. We investigated sources of this variability using a novel dual‐smog‐chamber method that directly compares the SOA formation from the same BB emissions under two different atmospheric conditions. During each experiment, we filled two identical Teflon smog chambers simultaneously with BB emissions from the same fire. We then perturbed the smoke with UV lights, UV lights plus nitrous acid (HONO), or dark ozone in one or both chambers. These perturbations caused SOA formation in nearly every experiment with an average organic aerosol (OA) mass enhancement ratio of 1.78 ± 0.91 (mean ± 1σ). However, the effects of the perturbations were highly variable ranging with OA mass enhancement ratios ranging from 0.7 (30% loss of OA mass) to 4.4 across the set of perturbation experiments. There was no apparent relationship between OA enhancement and perturbation type, fuel type, and modified combustion efficiency. To better isolate the effects of different perturbations, we report dual‐chamber enhancement (DUCE), which is the quantity of the effects of a perturbation relative to a reference condition. DUCE values were also highly variable, even for the same perturbation and fuel type. Gas measurements indicate substantial burn‐to‐burn variability in the magnitude and composition of SOA precursor emissions, even in repeated burns of the same fuel under nominally identical conditions. Therefore, the effects of different atmospheric perturbations on SOA formation from BB emissions appear to be less important than burn‐to‐burn variability.

show abstract

Section: Methodsmentioning

confidence: 99%

A dual‐chamber method for quantifying the effects of atmospheric perturbations on secondary organic aerosol formation from biomass burning emissions

et al. 2017

View full text Add to dashboard Cite

show abstract

“…During the fire events, an intricate myriad of chemical and physical processes occurs. The continuous increase in temperature of the fresh biomass caused by nearby fires can distill species absorbed by plants with low boiling point (e.g., T isoprene ∼ = 307 K), macromolecular bonds can be broken (i.e., low-temperature pyrolysis), gasification reactions converting carbon in the solid char to CO and CO 2 can occur and the flames efficiently oxidize the volatile gases to species such as H 2 O, CO 2 , and NO x (Bertschi et al, 2003;Longo et al, 2013). The release of isoprene and other BVOCs is dependent on the different phases of biomass combustion, and diverse vegetation communities affect the amount and diversity of VOCs released (Ciccioli et al, 2014).…”

Section: F C Dos Santos Et Al: Biomass Burning Emission Disturbancmentioning

confidence: 99%

Biomass burning emission disturbances of isoprene oxidation in a tropical forest

et al. 2018

View full text Add to dashboard Cite

Abstract. We present a characterization of the chemical composition of the atmosphere of the Brazilian Amazon rainforest based on trace gas measurements carried out during the South AMerican Biomass Burning Analysis (SAMBBA) airborne experiment in September 2012. We analyzed the observations of primary biomass burning emission tracers, i.e., carbon monoxide (CO), nitrogen oxides (NOx), ozone (O3), isoprene, and its main oxidation products, methyl vinyl ketone (MVK), methacrolein (MACR), and isoprene hydroxy hydroperoxide (ISOPOOH). The focus of SAMBBA was primarily on biomass burning emissions, but there were also several flights in areas of the Amazon forest not directly affected by biomass burning, revealing a background with a signature of biomass burning in the chemical composition due to long-range transport of biomass burning tracers from both Africa and the eastern part of Amazonia. We used the [MVK + MACR + ISOPOOH] ∕ [isoprene] ratio and the hydroxyl radical (OH) indirect calculation to assess the oxidative capacity of the Amazon forest atmosphere. We compared the background regions (CO < 150 ppbv), fresh and aged smoke plumes classified according to their photochemical age ([O3] ∕ [CO]), to evaluate the impact of biomass burning emissions on the oxidative capacity of the Amazon forest atmosphere. We observed that biomass burning emissions disturb the isoprene oxidation reactions, especially for fresh plumes ([MVK + MACR + ISOPOOH] ∕ [isoprene] = 7) downwind. The oxidation of isoprene is higher in fresh smoke plumes at lower altitudes (∼ 500 m) than in aged smoke plumes, anticipating near the surface a complex chain of oxidation reactions which may be related to secondary organic aerosol (SOA) formation. We proposed a refinement of the OH calculation based on the sequential reaction model, which considers vertical and horizontal transport for both biomass burning regimes and background environment. Our approach for the [OH] estimation resulted in values on the same order of magnitude of a recent observation in the Amazon rainforest [OH] ≅ 106 (molecules cm−3). During the fresh plume regime, the vertical profile of [OH] and the [MVK + MACR + ISOPOOH] ∕ [isoprene] ratio showed evidence of an increase in the oxidizing power in the transition from planetary boundary layer to cloud layer (1000–1500 m). These high values of [OH] (1.5 × 106 molecules cm−3) and [MVK + MACR + ISOPOOH] ∕ [isoprene] (7.5) indicate a significant change above and inside the cloud decks due to cloud edge effects on photolysis rates, which have a major impact on OH production rates.

show abstract

“…More-oxidized molecules have typically higher proton affinities; their concentrations are estimated by using the sensitivity of 3-hexanone. Oxidized organic compounds might undergo fragmentation in reactions with H 3 O(H 2 O) + n pri-mary ions, especially when containing hydroperoxide groups (Bernhammer et al, 2017). Therefore, concentrations are lower-limit estimates.…”

Section: Ptr3-tofmentioning

confidence: 99%

“…New-particle formation (NPF) is observed in many environments and under various conditions around the globe, from remote locations such as forested areas or marine and coastal regions to polluted urban areas; from warm environments, such as the tropics, to cold polar and alpine regions; and from Earth's surface to the free troposphere (Kulmala et al, 2004;Kerminen et al, 2018). Gaseous sulfuric acid (Ball et al, 1999;Kuang et al, 2008), ammonia (Kirkby et al, 2011;Kürten et al, 2016), amines (Kurtén et al, 2008;Almeida et al, 2013;Kürten et al, 2014), iodine (O'Dowd et al, 2002; and biogenic volatile organic compounds (BVOCs; Donahue et al, 2013;Riccobono et al, 2014;Kirkby et al, 2016;Bianchi et al, 2016) have been identified as key vapors involved in atmospheric NPF. The relative importance of each these precursors, however, depends on the particular ambient conditions.…”

Section: Introductionmentioning

confidence: 99%

Molecular understanding of new-particle formation from α-pinene between −50 and +25 °C

et al. 2020

Self Cite

View full text Add to dashboard Cite

Abstract. Highly oxygenated organic molecules (HOMs) contribute substantially to the formation and growth of atmospheric aerosol particles, which affect air quality, human health and Earth's climate. HOMs are formed by rapid, gas-phase autoxidation of volatile organic compounds (VOCs) such as α-pinene, the most abundant monoterpene in the atmosphere. Due to their abundance and low volatility, HOMs can play an important role in new-particle formation (NPF) and the early growth of atmospheric aerosols, even without any further assistance of other low-volatility compounds such as sulfuric acid. Both the autoxidation reaction forming HOMs and their NPF rates are expected to be strongly dependent on temperature. However, experimental data on both effects are limited. Dedicated experiments were performed at the CLOUD (Cosmics Leaving OUtdoor Droplets) chamber at CERN to address this question. In this study, we show that a decrease in temperature (from +25 to −50 ∘C) results in a reduced HOM yield and reduced oxidation state of the products, whereas the NPF rates (J1.7 nm) increase substantially. Measurements with two different chemical ionization mass spectrometers (using nitrate and protonated water as reagent ion, respectively) provide the molecular composition of the gaseous oxidation products, and a two-dimensional volatility basis set (2D VBS) model provides their volatility distribution. The HOM yield decreases with temperature from 6.2 % at 25 ∘C to 0.7 % at −50 ∘C. However, there is a strong reduction of the saturation vapor pressure of each oxidation state as the temperature is reduced. Overall, the reduction in volatility with temperature leads to an increase in the nucleation rates by up to 3 orders of magnitude at −50 ∘C compared with 25 ∘C. In addition, the enhancement of the nucleation rates by ions decreases with decreasing temperature, since the neutral molecular clusters have increased stability against evaporation. The resulting data quantify how the interplay between the temperature-dependent oxidation pathways and the associated vapor pressures affect biogenic NPF at the molecular level. Our measurements, therefore, improve our understanding of pure biogenic NPF for a wide range of tropospheric temperatures and precursor concentrations.

show abstract

Technical note: Conversion of isoprene hydroxy hydroperoxides (ISOPOOHs) on metal environmental simulation chamber walls

Cited by 15 publications

References 31 publications

A dual‐chamber method for quantifying the effects of atmospheric perturbations on secondary organic aerosol formation from biomass burning emissions

A dual‐chamber method for quantifying the effects of atmospheric perturbations on secondary organic aerosol formation from biomass burning emissions

Biomass burning emission disturbances of isoprene oxidation in a tropical forest

Molecular understanding of new-particle formation from α-pinene between −50 and +25 °C

Contact Info

Product

Resources

About