Real-time measurements of product compounds formed through the reaction of ozone with breath exhaled VOCs.

Human presence can affect indoor air quality because of secondary organic compounds formed upon reactions between gaseous oxidant species, e.g., ozone (O3), hydroxyl radicals (OH), and chemical compounds from skin, exhaled breath, hair and clothes. We assess the gas-phase product compounds generated by reactions of gaseous O3 with volatile organic compounds (VOCs) from exhaled human breath by real time analysis using a high-resolution quadrupole-orbitrap mass spectrometer (HRMS) coupled to a secondary electrospray ionization (SESI) source. Based on the product compounds identified we propose a reaction mechanism initiated by O3 oxidation of the most common breath constituents, isoprene, α-terpinene and ammonia (NH3). The reaction of O3 with isoprene and α-terpinene generates ketones and aldehydes such as 3,4-dihydroxy-2-butanone, methyl vinyl ketone, 3-carbonyl butyraldehyde, formaldehyde and toxic compounds such as 3-methyl furan. Formation of compounds with reduced nitrogen containing functional groups such as amines, imines and imides is highly plausible through NH3 initiated cleavage of the C-O bond. The detected gas-phase product compounds suggest that human breath can additionally affect indoor air quality through the formation of harmful secondary products and future epidemiological studies should evaluate the potential health effects of these compounds.

The Effect of Human Occupancy on Indoor Air Quality through Real-Time Measurements of Key Pollutants.

The primarily emitted compounds by human presence, e.g., skin and volatile organic compounds (VOCs) in breath, can react with typical indoor air oxidants, ozone (O3), and hydroxyl radicals (OH), leading to secondary organic compounds. Nevertheless, our understanding about the formation processes of the compounds through reactions of indoor air oxidants with primary emitted pollutants is still incomplete. In this study we performed real-time measurements of nitrous acid (HONO), nitrogen oxides (NOx = NO + NO2), O3, and VOCs to investigate the contribution of human presence and human activity, e.g., mopping the floor, to secondary organic compounds. During human occupancy a significant increase was observed of 1-butene, isoprene, and d-limonene exhaled by the four adults in the room and an increase of methyl vinyl ketone/methacrolein, methylglyoxal, and 3-methylfuran, formed as secondary compounds through reactions of OH radicals with isoprene. Intriguingly, the level of some compounds (e.g., m/z 126, 6-methyl-5-hepten-2-one, m/z 152, dihydrocarvone, and m/z 194, geranyl acetone) formed through reactions of O3 with the primary compounds was higher in the presence of four adults than during the period of mopping the floor with commercial detergent. These results indicate that human presence can additionally degrade the indoor air quality.

Inorganic Ions Enhance the Number of Product Compounds through Heterogeneous Processing of Gaseous NO2 on an Aqueous Layer of Acetosyringone.

Methoxyphenols represent important pollutants that can participate in the formation of secondary organic aerosols (SOAs) through chemical reactions with atmospheric oxidants. In this study, we determine the influence of ionic strength, pH, and temperature on the heterogeneous reaction of NO2 with an aqueous film consisting of acetosyringone (ACS), as a proxy for methoxyphenols. The uptake coefficient of NO2 (50 ppb) on ACS (1 × 10-5 mol L-1) is γ = (9.3 ± 0.09) × 10-8 at pH 5, and increases by one order of magnitude to γ = (8.6 ± 0.5) × 10-7 at pH 11. The lifetime of ACS due to its reaction with NO2 is largely affected by the presence of nitrate ions and sulfate ions encountered in aqueous aerosols. The analysis performed by membrane inlet single-photon ionization-time-of-flight mass spectrometry (MI-SPI-TOFMS) reveals an increase in the number of product compounds and a change of their chemical composition upon addition of nitrate ions and sulfate ions to the aqueous thin layer consisting of ACS. These outcomes indicate that inorganic ions can play an important role during the heterogeneous oxidation processes in aqueous aerosol particles.

A Novel Insight into the Ozone-Skin Lipid Oxidation Products Observed by Secondary Electrospray Ionization High-Resolution Mass Spectrometry.

Emissions of secondary products through reactions of oxidants, ozone (O3), and hydroxyl radical (·OH) with human skin lipids have become increasingly important in indoor environments. Here, we evaluate the secondary organic compounds formed through heterogeneous reactions of gaseous O3 with hand skin lipids by using a high-resolution quadrupole Orbitrap mass spectrometer coupled to a commercial secondary electrospray ionization (SESI) source. More than 600 ions were detected over a period of less than 40 min real-time measurements, among which 53 ions were characterized with a significant increasing trend in signal intensity at the presence of O3. Based on the detected ions, we suggest detailed reaction pathways initiated by ozone oxidation of squalene that results in primary and secondary ozonides; we noticed for the first time that these products may be further cleaved by direct reaction of nucleophilic ammonia (NH3), emitted from human skin. Finally, we estimate the fate of secondarily formed carbonyl compounds with respect to their gas-phase reactions with ·OH, O3, and NO3 and compared with their removal by air exchange rate (AER) with outdoors. The obtained results suggest that human presence is a source of an important number of organic compounds, which can significantly influence the air quality in indoor environments.

Ionic Strength Effect Alters the Heterogeneous Ozone Oxidation of Methoxyphenols in Going from Cloud Droplets to Aerosol Deliquescent Particles.

Methoxyphenols are one of the most abundant classes of biomarker tracers for atmospheric wood smoke pollution. The reactions of atmospheric oxidants (ozone, OH) with methoxyphenols can contribute to the formation of secondary organic aerosols (SOA). Here, for the first time, we use the well-established vertical wetted wall flow tube (VWWFT) reactor to assess the effect of ionic strength (I), pH, temperature, and ozone concentration on the reaction kinetics of ozone with acetosyringone (ACS), as a representative methoxyphenol compound. At fixed pH 3, typical for acidic atmospheric deliquescent particles, and at I = 0.9 M adjusted by Na2SO4, the uptake coefficient (γ) of O3 increases by 2 orders of magnitude from γ = (5.0 ± 0.8) × 10-8 on neat salt solution (Na2SO4) to γ = (6.0 ± 0.01) × 10-6 on a mixture of ACS and Na2SO4. The comparison of the uptake coefficients of O3 at different pH values indicates that the reaction kinetics strongly depends on the acidity of the phenolic group of ACS. The observed different reactivity of gas-phase ozone with ACS has implications for ozone uptake by the dilute aqueous phase of cloud droplets and by aerosol deliquescent particles loaded with inorganic salts, and it can affect the formation of SOA in the atmosphere.

Light-Enhanced Heterogeneous Conversion of NO2 to HONO on Solid Films Consisting of Fluorene and Fluorene/Na2SO4: An Impact on Urban and Indoor Atmosphere.

Polycyclic aromatic hydrocarbons (PAHs) as constituents of urban grime and indoor surfaces can impact the photochemical conversion of nitrogen dioxide (NO2) to nitrous acid (HONO) thereby impacting the oxidation capacity of the atmosphere. In this study we investigate the effect of relative humidity (RH%), light intensity, and NO2 concentrations on uptake coefficients (γ) of NO2 on solid film consisting of fluorene (FL) and a mixture of FL and Na2SO4 as a proxy for urban and indoor grime at ambient pressure and temperature. γ(NO2) on solid FL increased markedly from (5.7 ± 1.7) × 10-7 at 0% RH to (4.6 ± 1.0) × 10-6 at 90% RH. The NO2 to HONO conversion yield, (ΔHONO/ΔNO2)%, increases with RH from 40% at 0% RH up to 80% at 60-90% RH, indicating that the water molecules favor the formation of HONO up to 60% RH. These results suggest that the heterogeneous photochemical reaction of NO2 on FL and FL/Na2SO4 can be an important source of HONO in the urban environment and indoor atmosphere and should be considered in photochemical models.

Assessing indoor gas phase oxidation capacity through real-time measurements of HONO and NOx in Guangzhou, China.

The hydroxyl radical (OH) is one of the most important oxidants controlling the oxidation capacity of the indoor atmosphere. One of the main OH sources indoors is the photolysis of nitrous acid (HONO). In this study, real-time measurements of HONO, nitrogen oxides (NOx) and ozone (O3) in an indoor environment in Guangzhou, China, were performed under two different conditions: (1) in the absence of any human activity and (2) in the presence of cooking. The maximum NOx and HONO levels drastically increased from 15 and 4 ppb in the absence of human activity to 135 and 40 ppb during the cooking event, respectively. The photon flux was determined for the sunlit room, which has a closed south-east oriented window. The photon flux was used to estimate the photolysis rate constants of NO2, J(NO2), and HONO, J(HONO), which span the range between 8 × 10-5 and 1.5 × 10-5 s-1 in the morning from 9:30 to 11:45, and 8.5 × 10-4 and 1.5 × 10-4 s-1 at noon, respectively. The OH concentrations calculated by photostationary state (PSS) approach, observed around noon, are very similar, i.e., 2.4 × 106 and 3.1 × 106 cm-3 in the absence of human activity and during cooking, respectively. These results suggest that under "high NOx" conditions (NOx higher than a few ppb) and with direct sunlight in the room, the NOx and HONO chemistry would be similar, independent of the geographic location of the indoor environment, which facilitates future modeling studies focused on indoor gas phase oxidation capacity.

Ionic-Strength Effects on the Reactive Uptake of Ozone on Aqueous Pyruvic Acid: Implications for Air-Sea Ozone Deposition.

A vertical wetted-wall flow-tube technique was used to explore the ionic strength effects at the air-water interface in mediating the sea-surface reaction between ozone (O3) and pyruvic acid (PA). The uptake coefficients of ozone on aqueous PA increase substantially with the concentrations of bromide (Br-) ions, clearly indicating that the dry deposition of ozone could be significantly enhanced due to the presence of carbonyl compounds such as PA at the bromide-rich sea surface. Based on the observed uptake coefficients, the estimated deposition velocity of ozone (100 ppb) for a nanomolar range of PA concentrations is ∼1 × 10-3 m s-1, which represents a significant contribution to the known deposition velocity of ozone at the sea surface. The analysis of reaction products by ultra-high-resolution Fourier transform-ion cyclotron resonance mass spectrometry suggests the formation of oligomers during both the dark and light-induced heterogeneous reactions between gaseous O3 and PA occurring at the surface of a dilute aqueous phase (representative of cloud droplets). The detected high-molecular-weight compounds are much more complex than the oligomeric species identified during the photolytic degradation of bulk aqueous PA alone.