The Ozonolysis of Methylated Selenide Compounds in the Atmosphere: Isotopes, Kinetics, Products, and Mechanisms.

Selenium (Se) is an essential micronutrient with an important atmospheric component in its biogeochemical cycle. In this cycle, phytoplankton form volatile organic Se species, such as dimethyl selenide (CH3SeCH3) and dimethyl diselenide (CH3SeSeCH3), which are emitted into the atmosphere. To predict the atmospheric fate of these methylated Se compounds, we investigated their ozonolysis reaction. We used proton-transfer-reaction time-of-flight mass spectrometry to quantify atmospheric Se and its isotopes, and used this method in kinetic and product studies. The ozonolysis of CH3SeCH3 proceeded with a rate constant of (7.4 ± 2.2) × 10-17 cm3 molec-1 s-1 at 26 ± 1 °C with an activation energy of 50 ± 14 kJ mol-1 forming dimethyl selenoxide (CH3Se(O)CH3). Comparatively, CH3SeSeCH3 reacted with O3 at (2.6 ± 0.9) × 10-17 cm3 molec-1 s-1 at 27 ± 1 °C with an activation energy of 56 ± 5 kJ mol-1 forming methylselinic acid (CH3Se(O)OH). At 20 ppbv of O3, the atmospheric lifetimes of CH3SeCH3 and CH3SeSeCH3 are 7.6 and 22 h, respectively. The Se oxidation products were confirmed by synthesis and can serve as new atmospheric tracers of methylated Se compounds. Overall, we measured Se isotopes in real time and determined the rate constants, activation energies, and oxidation products. These mechanisms can now be used to determine the quantitative atmospheric fate of Se toward O3, and thus its distribution within a changing climate.

Regional Sources and Sinks of Atmospheric Particulate Selenium in the United States Based on Seasonality Profiles.

Selenium (Se) is an essential nutrient for humans and enters our food chain through bioavailable Se in soil. Atmospheric deposition is a major source of Se to soils, driving the need to investigate the sources and sinks of atmospheric Se. Here, we used Se concentrations from PM2.5 data at 82 sites from 1988 to 2010 from the Interagency Monitoring of Protected Visual Environments (IMPROVE) network in the US to identify the sources and sinks of particulate Se. We identified 6 distinct seasonal profiles of atmospheric Se, grouped by geographical location: West, Southwest, Midwest, Southeast, Northeast, and North Northeast. Across most of the regions, coal combustion is the largest Se source, with a terrestrial source dominating in the West. We also found evidence for gas-to-particle partitioning in the wintertime in the Northeast. Wet deposition is an important sink of particulate Se, as determined by Se/PM2.5 ratios. The Se concentrations from the IMPROVE network compare well to modeled output from a global chemistry-climate model, SOCOL-AER, except in the Southeast US. Our analysis constrains the sources and sinks of atmospheric Se, thereby improving the predictions of Se distribution under climate change.

Tracking the Photomineralization Mechanism in Irradiated Lab-Generated and Field-Collected Brown Carbon Samples and Its Effect on Cloud Condensation Nuclei Abilities.

Organic aerosols affect the planet's radiative balance by absorbing and scattering light as well as by activating cloud droplets. These organic aerosols contain chromophores, termed brown carbon (BrC), and can undergo indirect photochemistry, affecting their ability to act as cloud condensation nuclei (CCN). Here, we investigated the effect of photochemical aging by tracking the conversion of organic carbon into inorganic carbon, termed the photomineralization mechanism, and its effect on the CCN abilities in four different types of BrC samples: (1) laboratory-generated (NH4)2SO4-methylglyoxal solutions, (2) dissolved organic matter isolate from Suwannee River fulvic acid (SRFA), (3) ambient firewood smoke aerosols, and (4) ambient urban wintertime particulate matter in Padua, Italy. Photomineralization occurred in all BrC samples albeit at different rates, evidenced by photobleaching and by loss of organic carbon up to 23% over a simulated 17.6 h of sunlight exposure. These losses were correlated with the production of CO up to 4% and of CO2 up to 54% of the initial organic carbon mass, monitored by gas chromatography. Photoproducts of formic, acetic, oxalic and pyruvic acids were also produced during irradiation of the BrC solutions, but at different yields depending on the sample. Despite these chemical changes, CCN abilities did not change substantially for the BrC samples. In fact, the CCN abilities were dictated by the salt content of the BrC solution, trumping a photomineralization effect on the CCN abilities for the hygroscopic BrC samples. Solutions of (NH4)2SO4-methylglyoxal, SRFA, firewood smoke, and ambient Padua samples had hygroscopicity parameters κ of 0.6, 0.1, 0.3, and 0.6, respectively. As expected, the SRFA solution with a κ of 0.1 was most impacted by the photomineralization mechanism. Overall, our results suggest that the photomineralization mechanism is expected in all BrC samples and can drive changes in the optical properties and chemical composition of aging organic aerosols.

Singlet Oxygen Seasonality in Aqueous PM10 is Driven by Biomass Burning and Anthropogenic Secondary Organic Aerosol.

The first excited state of molecular oxygen is singlet-state oxygen (1O2), formed by indirect photochemistry of chromophoric organic matter. To determine whether 1O2 can be a competitive atmospheric oxidant, we must first quantify its production in organic aerosols (OA). Here, we report the spatiotemporal distribution of 1O2 over a 1-year dataset of PM10 extracts at two locations in Switzerland, representing a rural and suburban site. Using a chemical probe technique, we measured 1O2 steady-state concentrations with a seasonality over an order of magnitude peaking in wintertime at 4.59 ± 0.01 × 10-13 M and with a quantum yield of up to 2%. Next, we identified biomass burning and anthropogenic secondary OA (SOA) as the drivers for 1O2 formation in the PM10 aqueous extracts using source apportionment data. Importantly, the quantity, the amount of brown carbon present in PM10, and the quality, the chemical composition of the brown carbon present, influence the concentration of 1O2 sensitized in each extract. Anthropogenic SOA in the extracts were 4 times more efficient in sensitizing 1O2 than primary biomass burning aerosols. Last, we developed an empirical fit to estimate 1O2 concentrations based on PM10 components, unlocking the ability to estimate 1O2 from existing source apportionment data. Overall, 1O2 is likely a competitive photo-oxidant in PM10 since 1O2 is sensitized by ubiquitous biomass burning OA and anthropogenic SOA.

UVB-irradiated Laboratory-generated Secondary Organic Aerosol Extracts Have Increased Cloud Condensation Nuclei Abilities: Comparison with Dissolved Organic Matter and Implications for the Photomineralization Mechanism.

During their atmospheric lifetime, organic compounds within aerosols are exposed to sunlight and undergo photochemical processing. This atmospheric aging process changes the ability of organic aerosols to form cloud droplets and consequently impacts aerosol-cloud interactions. We recently reported changes in the cloud forming properties of aerosolized dissolved organic matter (DOM) due to a photomineralization mechanism, transforming high-molecular weight compounds in DOM into organic acids, CO and CO2. To strengthen the implications of this mechanism to atmospheric aerosols, we now extend our previous dataset and report identical cloud activation experiments with laboratory-generated secondary organic aerosol (SOA) extracts. The SOA was produced from the oxidation of α-pinene and naphthalene, a representative biogenic and anthropogenic source of SOA, respectively. Exposure of aqueous solutions of SOA to UVB irradiation increased the dried organic material's hygroscopicity and thus its ability to form cloud droplets, consistent with our previous observations for DOM. We propose that a photomineralization mechanism is also at play in these SOA extracts. These results help to bridge the gap between DOM and SOA photochemistry by submitting two differently-sourced organic matter materials to identical experimental conditions for optimal comparison.

Reactive Oxygen Species Production from Secondary Organic Aerosols: The Importance of Singlet Oxygen.

Organic aerosols are subjected to atmospheric processes driven by sunlight, including the production of reactive oxygen species (ROS) capable of transforming their physicochemical properties. In this study, secondary organic aerosols (SOA) generated from aromatic precursors were found to sensitize singlet oxygen (1O2), an arguably underappreciated atmospheric ROS. Specifically, we quantified 1O2, OH radical, and H2O2 quantum yields within photoirradiated solutions of laboratory-generated SOA from toluene, biphenyl, naphthalene, and 1,8-dimethylnaphthalene. At 5 mgC L-1 of SOA extracts, the average steady-state concentrations of 1O2 and of OH radicals in irradiated solutions were 3 ± 1 × 10-14 M and 3.6 ± 0.9 × 10-17 M, respectively. Furthermore, ROS quantum yields of irradiated ambient PM10 extracts were comparable to those from laboratory-generated SOA, suggesting a similarity in ROS production from both types of samples. Finally, by using our measured ROS concentrations, we predict that certain organic compounds found in aerosols, such as amino acids, organo-nitrogen compounds, and phenolic compounds have shortened lifetimes by more than a factor of 2 when 1O2 is considered as an additional sink. Overall, our findings highlight the importance of SOA as a source of 1O2 and its potential as a competitive ROS species in photooxidation processes.

Sources of isocyanic acid (HNCO) indoors: a focus on cigarette smoke.

The sources and sinks of isocyanic acid (HNCO), a toxic gas, in indoor environments are largely uncharacterized. In particular, cigarette smoke has been identified as a significant source. In this study, controlled smoking of tobacco cigarettes was investigated in both an environmental chamber and a residence in Toronto, Canada using an acetate-CIMS. The HNCO emission ratio from side-stream cigarette smoke was determined to be 2.7 (±1.1) × 10-3 ppb HNCO/ppb CO. Side-stream smoke from a single cigarette introduced a large pulse of HNCO to the indoor environment, increasing the HNCO mixing ratio by up to a factor of ten from background conditions of 0.15 ppb. Although there was no evidence for photochemical production of HNCO from cigarette smoke in the residence, it was observed in the environmental chamber via oxidation by the hydroxyl radical (1.1 × 107 molecules per cm3), approximately doubling the HNCO mixing ratio after 30 minutes of oxidation. Oxidation of cigarette smoke by O3 (15 ppb = 4.0 × 1017 molecules per cm3) and photo-reaction with indoor fluorescent lights did not produce HNCO. By studying the temporal profiles of both HNCO and CO after smoking, it is inferred that gas-to-surface partitioning of HNCO acts as an indoor loss pathway. Even in the absence of smoking, the indoor HNCO mixing ratios in the Toronto residence were elevated compared to concurrent outdoor measurements by approximately a factor of two.

Isocyanic acid (HNCO) and its fate in the atmosphere: a review.

Isocyanic acid (HNCO) has recently been identified in ambient air at potentially concerning concentrations for human health. Since its first atmospheric detection, significant progress has been made in understanding its sources and sinks. The chemistry of HNCO is governed by its partitioning between the gas and liquid phases, its weak acidity, its high solubility at pH above 5, and its electrophilic chemical behaviour. The online measurement of HNCO in ambient air is possible due to recent advances in mass spectrometry techniques, including chemical ionization mass spectrometry for the detection of weak acids. To date, HNCO has been measured in North America, Europe and South Asia as well as outdoors and indoors, with mixing ratios up to 10s of ppbv. The sources of HNCO include: (1) fossil fuel combustion such as coal, gasoline and diesel, (2) biomass burning such as wildfires and crop residue burning, (3) secondary photochemical production from amines and amides, (4) cigarette smoke, and (5) combustion of materials in the built environment. Then, three losses processes can occur: (1) gas phase photochemistry, (2) heterogenous uptake and hydrolysis, and (3) dry deposition. HNCO lifetimes with respect to photolysis and OH radical oxidation are on the order of months to decades. Consequently, the removal of HNCO from the atmosphere is thought to occur predominantly by dry deposition and by heterogeneous uptake followed by hydrolysis to NH3 and CO2. A back of the envelope calculation reveals that HNCO is an insignificant global source of NH3, contributing only around 1%, but could be important for local environments. Furthermore, HNCO can react due to its electrophilic behaviour with various nucleophilic functionalities, including those present in the human body through a reaction called protein carbamoylation. This protein modification can lead to toxicity, and thus exposure to high concentrations of HNCO can lead to cardiovascular and respiratory diseases, as well as cataracts. In this critical review, we outline our current understanding of the atmospheric fate of HNCO and its potential impacts on outdoor and indoor air quality. We also call attention to the need for toxicology studies linking HNCO exposure to health effects.

Singlet Oxygen Photooxidation of Peptidic Oxazoles and Thiazoles.

Oxazoles and thiazoles are commonly found moieties in nonribosomal peptides (NRPs) and ribosomally synthesized post-translationally modified peptides (RiPPs), which are important biomolecules present in the environment and in natural waters. From previous studies, they seem susceptible to oxidation by singlet oxygen (1O2); therefore, we designed and synthesized model oxazole- and thiazole-peptides and measured their 1O2 bimolecular reaction rate constants, showing slow photooxidation under environmental conditions. We reasoned their stability through the electron-withdrawing effect of the carboxamide substituent. Reaction products were elucidated and support a reaction mechanism involving cycloaddition followed by a series of rearrangements. The first 1O2 bimolecular reaction rate constant for a RiPP, the thiazole-containing peptide Aerucyclamide A, was measured and found in good agreement with the model peptide's rate constant, highlighting the potential of using model peptides to study the transformations of other environmentally relevant NRPs and RiPPs.

Seasonal influences on surface ozone variability in continental South Africa and implications for air quality.

Although elevated surface ozone (O3) concentrations are observed in many areas within southern Africa, few studies have investigated the regional atmospheric chemistry and dominant atmospheric processes driving surface O3 formation in this region. Therefore, an assessment of comprehensive continuous surface O3 measurements performed at four sites in continental South Africa was conducted. The regional O3 problem was evident, with O3 concentrations regularly exceeding the South African air quality standard limit, while O3 levels were higher compared to other background sites in the Southern Hemisphere. The temporal O3 patterns observed at the four sites resembled typical trends for O3 in continental South Africa, with O3 concentrations peaking in late winter and early spring. Increased O3 concentrations in winter were indicative of increased emissions of O3 precursors from household combustion and other low-level sources, while a spring maximum observed at all the sites was attributed to increased regional biomass burning. Source area maps of O3 and CO indicated significantly higher O3 and CO concentrations associated with air masses passing over a region with increased seasonal open biomass burning, which indicated CO associated with open biomass burning as a major source of O3 in continental South Africa. A strong correlation between O3 on CO was observed, while O3 levels remained relatively constant or decreased with increasing NO x , which supports a VOC-limited regime. The instantaneous production rate of O3 calculated at Welgegund indicated that ~ 40 % of O3 production occurred in the VOC-limited regime. The relationship between O3 and precursor species suggests that continental South Africa can be considered VOC limited, which can be attributed to high anthropogenic emissions of NO x in the interior of South Africa. The study indicated that the most effective emission control strategy to reduce O3 levels in continental South Africa should be CO and VOC reduction, mainly associated with household combustion and regional open biomass burning.