Effect of Pellet Boiler Exhaust on Secondary Organic Aerosol Formation from α-Pinene.

Interactions between anthropogenic and biogenic emissions, and implications for aerosol production, have raised particular scientific interest. Despite active research in this area, real anthropogenic emission sources have not been exploited for anthropogenic-biogenic interaction studies until now. This work examines these interactions using α-pinene and pellet boiler emissions as a model test system. The impact of pellet boiler emissions on secondary organic aerosol (SOA) formation from α-pinene photo-oxidation was studied under atmospherically relevant conditions in an environmental chamber. The aim of this study was to identify which of the major pellet exhaust components (including high nitrogen oxide (NOx), primary particles, or a combination of the two) affected SOA formation from α-pinene. Results demonstrated that high NOx concentrations emitted by the pellet boiler reduced SOA yields from α-pinene, whereas the chemical properties of the primary particles emitted by the pellet boiler had no effect on observed SOA yields. The maximum SOA yield of α-pinene in the presence of pellet boiler exhaust (under high-NOx conditions) was 18.7% and in the absence of pellet boiler exhaust (under low-NOx conditions) was 34.1%. The reduced SOA yield under high-NOx conditions was caused by changes in gas-phase chemistry that led to the formation of organonitrate compounds.

Factors controlling the evaporation of secondary organic aerosol from α-pinene ozonolysis.

Secondary organic aerosols (SOA) forms a major fraction of organic aerosols in the atmosphere. Knowledge of SOA properties that affect their dynamics in the atmosphere is needed for improving climate models. By combining experimental and modeling techniques, we investigated the factors controlling SOA evaporation under different humidity conditions. Our experiments support the conclusion of particle phase diffusivity limiting the evaporation under dry conditions. Viscosity of particles at dry conditions was estimated to increase several orders of magnitude during evaporation, up to 109 Pa s. However, at atmospherically relevant relative humidity and time scales, our results show that diffusion limitations may have a minor effect on evaporation of the studied α-pinene SOA particles. Based on previous studies and our model simulations, we suggest that, in warm environments dominated by biogenic emissions, the major uncertainty in models describing the SOA particle evaporation is related to the volatility of SOA constituents.

Multiphase Photochemistry of Pyruvic Acid under Atmospheric Conditions.

Aerosol and molecular processing in the atmosphere occurs in a complex and variable environment consisting of multiple phases and interfacial regions. To explore the effects of such conditions on the reactivity of chemical systems, we employ an environmental simulation chamber to investigate the multiphase photolysis of pyruvic acid, which photoreacts in the troposphere in aqueous particles and in the gas phase. Upon irradiation of nebulized pyruvic acid, acetic acid and carbon dioxide are rapidly generated, which is consistent with previous literature on the bulk phase photolysis reactions. Additionally, we identify a new C6 product, zymonic acid, a species that has not previously been reported from pyruvic acid photolysis under any conditions. Its observation here, and corresponding spectroscopic signatures, indicates it could be formed by heterogeneous reactions at the droplet surface. Prior studies of the aqueous photolysis of pyruvic acid have shown that high-molecular-weight compounds are formed via radical reactions; however, they are inhibited by the presence of oxygen, leading to doubt as to whether the chemistry would occur in the atmosphere. Identification of dimethyltartaric acid from the photolysis of multiphase pyruvic acid in air confirms radical polymerization chemistry can compete with oxygen reactions to some extent under aerobic conditions. Evidence of additional polymerization within the particles during irradiation is suggested by the increasing viscosity and organic content of the particles. The implications of multiphase specific processes are then discussed within the broader scope of atmospheric science.

Herbivory by an Outbreaking Moth Increases Emissions of Biogenic Volatiles and Leads to Enhanced Secondary Organic Aerosol Formation Capacity.

In addition to climate warming, greater herbivore pressure is anticipated to enhance the emissions of climate-relevant biogenic volatile organic compounds (VOCs) from boreal and subarctic forests and promote the formation of secondary aerosols (SOA) in the atmosphere. We evaluated the effects of Epirrita autumnata, an outbreaking geometrid moth, feeding and larval density on herbivore-induced VOC emissions from mountain birch in laboratory experiments and assessed the impact of these emissions on SOA formation via ozonolysis in chamber experiments. The results show that herbivore-induced VOC emissions were strongly dependent on larval density. Compared to controls without larval feeding, clear new particle formation by nucleation in the reaction chamber was observed, and the SOA mass loadings in the insect-infested samples were significantly higher (up to 150-fold). To our knowledge, this study provides the first controlled documentation of SOA formation from direct VOC emission of deciduous trees damaged by known defoliating herbivores and suggests that chewing damage on mountain birch foliage could significantly increase reactive VOC emissions that can importantly contribute to SOA formation in subarctic forests. Additional feeding experiments on related silver birch confirmed the SOA results. Thus, herbivory-driven volatiles are likely to play a major role in future biosphere-vegetation feedbacks such as sun-screening under daily 24 h sunshine in the subarctic.

An amorphous solid state of biogenic secondary organic aerosol particles.

Secondary organic aerosol (SOA) particles are formed in the atmosphere from condensable oxidation products of anthropogenic and biogenic volatile organic compounds (VOCs). On a global scale, biogenic VOCs account for about 90% of VOC emissions and of SOA formation (90 billion kilograms of carbon per year). SOA particles can scatter radiation and act as cloud condensation or ice nuclei, and thereby influence the Earth's radiation balance and climate. They consist of a myriad of different compounds with varying physicochemical properties, and little information is available on the phase state of SOA particles. Gas-particle partitioning models usually assume that SOA particles are liquid, but here we present experimental evidence that they can be solid under ambient conditions. We investigated biogenic SOA particles formed from oxidation products of VOCs in plant chamber experiments and in boreal forests within a few hours after atmospheric nucleation events. On the basis of observed particle bouncing in an aerosol impactor and of electron microscopy we conclude that biogenic SOA particles can adopt an amorphous solid-most probably glassy-state. This amorphous solid state should provoke a rethinking of SOA processes because it may influence the partitioning of semi-volatile compounds, reduce the rate of heterogeneous chemical reactions, affect the particles' ability to accommodate water and act as cloud condensation or ice nuclei, and change the atmospheric lifetime of the particles. Thus, the results of this study challenge traditional views of the kinetics and thermodynamics of SOA formation and transformation in the atmosphere and their implications for air quality and climate.

Effective density and morphology of particles emitted from small-scale combustion of various wood fuels.

The effective density of fine particles emitted from small-scale wood combustion of various fuels were determined with a system consisting of an aerosol particle mass analyzer and a scanning mobility particle sizer (APM-SMPS). A novel sampling chamber was combined to the system to enable measurements of highly fluctuating combustion processes. In addition, mass-mobility exponents (relates mass and mobility size) were determined from the density data to describe the shape of the particles. Particle size, type of fuel, combustion phase, and combustion conditions were found to have an effect on the effective density and the particle shape. For example, steady combustion phase produced agglomerates with effective density of roughly 1 g cm(-3) for small particles, decreasing to 0.25 g cm(-3) for 400 nm particles. The effective density was higher for particles emitted from glowing embers phase (ca. 1-2 g cm(-3)), and a clear size dependency was not observed as the particles were nearly spherical in shape. This study shows that a single value cannot be used for the effective density of particles emitted from wood combustion.

Insight into acid-base nucleation experiments by comparison of the chemical composition of positive, negative, and neutral clusters.

We investigated the nucleation of sulfuric acid together with two bases (ammonia and dimethylamine), at the CLOUD chamber at CERN. The chemical composition of positive, negative, and neutral clusters was studied using three Atmospheric Pressure interface-Time Of Flight (APi-TOF) mass spectrometers: two were operated in positive and negative mode to detect the chamber ions, while the third was equipped with a nitrate ion chemical ionization source allowing detection of neutral clusters. Taking into account the possible fragmentation that can happen during the charging of the ions or within the first stage of the mass spectrometer, the cluster formation proceeded via essentially one-to-one acid-base addition for all of the clusters, independent of the type of the base. For the positive clusters, the charge is carried by one excess protonated base, while for the negative clusters it is carried by a deprotonated acid; the same is true for the neutral clusters after these have been ionized. During the experiments involving sulfuric acid and dimethylamine, it was possible to study the appearance time for all the clusters (positive, negative, and neutral). It appeared that, after the formation of the clusters containing three molecules of sulfuric acid, the clusters grow at a similar speed, independent of their charge. The growth rate is then probably limited by the arrival rate of sulfuric acid or cluster-cluster collision.

Biogenic secondary organic aerosol participates in plant interactions and herbivory defense.

Biogenic secondary organic aerosols (SOAs) can be formed from the oxidation of plant volatiles in the atmosphere. Herbivore-induced plant volatiles (HIPVs) can elicit plant defenses, but whether such ecological functions persist after they form SOAs was previously unknown. Here we show that Scots pine seedlings damaged by large pine weevils feeding on their roots release HIPVs that trigger defenses in neighboring conspecific plants. The biological activity persisted after HIPVs had been oxidized to form SOAs, which was indicated by receivers displaying enhanced photosynthesis, primed volatile defenses, and reduced weevil damage. The elemental composition and quantity of SOAs likely determines their biological functions. This work demonstrates that plant-derived SOAs can mediate interactions between plants, highlighting their ecological significance in ecosystems.

Direct mitigation of secondary organic aerosol particulate pollutants by multiphase photocatalysis.

Particulate matter represents one of the most severe air pollutants globally. Organic aerosol (OA) comprises 30-70 % of submicron particle mass in urban areas. An effective way to mitigate OA particulate pollutants is to reduce the formation of secondary organic aerosol (SOA). Here, we studied the effect of titanium dioxide (TiO2) photocatalytic seeds on the formation and mitigation of SOA particles from α-pinene or toluene oxidation in chamber. For the first time, we discovered that under ultraviolet (UV) irradiation, the presence of TiO2 directly removed internally mixed α-pinene SOA mass by 53.7 % within 200 mins, and also directly removed SOA matter in an externally mixed state that is not in direct contact with TiO2 surface: the mass of externally mixed α-pinene SOA was reduced by 21.9 % within 81 mins, and the toluene SOA mass was reduced by 46.6 % in 145mins. In addition, the presence of TiO2 effectively inhibited the formation of SOA particles with a SOA mass yield of zero. This study brings up an innovative concept for air pollution control - the direct photocatalytic degradation of OA with aid of TiO2-based photocatalysts. Our novel findings will potentially bring practical applications in air pollution abatement and regional, even global aerosol-climate interactions.

Impact of Biomass Burning on Arctic Aerosol Composition.

Emissions from biomass burning (BB) occurring at midlatitudes can reach the Arctic, where they influence the remote aerosol population. By using measurements of levoglucosan and black carbon, we identify seven BB events reaching Svalbard in 2020. We find that most of the BB events are significantly different to the rest of the year (nonevents) for most of the chemical and physical properties. Aerosol mass and number concentrations are enhanced by up to 1 order of magnitude during the BB events. During BB events, the submicrometer aerosol bulk composition changes from an organic- and sulfate-dominated regime to a clearly organic-dominated regime. This results in a significantly lower hygroscopicity parameter κ for BB aerosol (0.4 ± 0.2) compared to nonevents (0.5 ± 0.2), calculated from the nonrefractory aerosol composition. The organic fraction in the BB aerosol showed no significant difference for the O:C ratios (0.9 ± 0.3) compared to the year (0.9 ± 0.6). Accumulation mode particles were present during all BB events, while in the summer an additional Aitken mode was observed, indicating a mixture of the advected air mass with locally produced particles. BB tracers (vanillic, homovanillic, and hydroxybenzoic acid, nitrophenol, methylnitrophenol, and nitrocatechol) were significantly higher when air mass back trajectories passed over active fire regions in Eastern Europe, indicating agricultural and wildfires as sources. Our results suggest that the impact of BB on the Arctic aerosol depends on the season in which they occur, and agricultural and wildfires from Eastern Europe have the potential to disturb the background conditions the most.

Process-evaluation of forest aerosol-cloud-climate feedback shows clear evidence from observations and large uncertainty in models.

Natural aerosol feedbacks are expected to become more important in the future, as anthropogenic aerosol emissions decrease due to air quality policy. One such feedback is initiated by the increase in biogenic volatile organic compound (BVOC) emissions with higher temperatures, leading to higher secondary organic aerosol (SOA) production and a cooling of the surface via impacts on cloud radiative properties. Motivated by the considerable spread in feedback strength in Earth System Models (ESMs), we here use two long-term observational datasets from boreal and tropical forests, together with satellite data, for a process-based evaluation of the BVOC-aerosol-cloud feedback in four ESMs. The model evaluation shows that the weakest modelled feedback estimates can likely be excluded, but highlights compensating errors making it difficult to draw conclusions of the strongest estimates. Overall, the method of evaluating along process chains shows promise in pin-pointing sources of uncertainty and constraining modelled aerosol feedbacks.

Aerosol chemical composition in cloud events by high resolution time-of-flight aerosol mass spectrometry.

This study presents results of direct observations of aerosol chemical composition in clouds. A high-resolution time-of-flight aerosol mass spectrometer was used to make measurements of cloud interstitial particles (INT) and mixed cloud interstitial and droplet residual particles (TOT). The differences between these two are the cloud droplet residuals (RES). Positive matrix factorization analysis of high-resolution mass spectral data sets and theoretical calculations were performed to yield distributions of chemical composition of the INT and RES particles. We observed that less oxidized hydrocarbon-like organic aerosols (HOA) were mainly distributed into the INT particles, whereas more oxidized low-volatile oxygenated OA (LVOOA) mainly in the RES particles. Nitrates existed as organic nitrate and in chemical form of NH(4)NO(3). Organic nitrates accounted for 45% of total nitrates in the INT particles, in clear contrast to 26% in the RES particles. Meanwhile, sulfates coexist in forms of acidic NH(4)HSO(4) and neutralized (NH(4))(2)SO(4). Acidic sulfate made up 64.8% of total sulfates in the INT particles, much higher than 10.7% in the RES particles. The results indicate a possible joint effect of activation ability of aerosol particles, cloud processing, and particle size effects on cloud formation.

Emissions of biogenic volatile organic compounds from adjacent boreal fen and bog as impacted by vegetation composition.

Peatland ecosystems emit biogenic volatile organic compounds (BVOC), which have a net cooling impact on the climate. However, the quality and quantity of BVOC emissions, and how they are regulated by vegetation and peatland type remain poorly understood. Here we measured BVOC emissions with dynamic enclosures from two major boreal peatland types, a minerotrophic fen and an ombrotrophic bog situated in Siikaneva, southern Finland and experimentally assessed the role of vegetation by removing vascular vegetation with or without the moss layer. Our measurements from four campaigns during growing seasons in 2017 and 2018 identified emissions of 59 compounds from nine different chemical groups. Isoprene accounted for 81 % of BVOC emissions. Measurements also revealed uptake of dichloromethane. Total BVOC emissions and the emissions of isoprene, monoterpenoids, sesquiterpenes, homoterpenes, and green leaf volatiles were tightly connected to vascular plants. Isoprene and sesquiterpene emissions were associated with sedges, whereas monoterpenoids and homoterpenes were associated with shrubs. Additionally, isoprene and alkane emissions were higher in the fen than in the bog and they significantly contributed to the higher BVOC emissions from intact vegetation in the fen. During an extreme drought event in 2018, emissions of organic halides were absent. Our results indicate that climate change with an increase in shrub cover and increased frequency of extreme weather events may have a negative impact on total BVOC emissions that otherwise are predicted to increase in warmer temperatures. However, these changes also accompanied a change in BVOC emission quality. As different compounds differ in their capacity to form secondary organic aerosols, the ultimate climate impact of peatland BVOC emissions may be altered.

Reductions in particulate and NO(x) emissions by diesel engine parameter adjustments with HVO fuel.

Hydrotreated vegetable oil (HVO) diesel fuel is a promising biofuel candidate that can complement or substitute traditional diesel fuel in engines. It has been already reported that by changing the fuel from conventional EN590 diesel to HVO decreases exhaust emissions. However, as the fuels have certain chemical and physical differences, it is clear that the full advantage of HVO cannot be realized unless the engine is optimized for the new fuel. In this article, we studied how much exhaust emissions can be reduced by adjusting engine parameters for HVO. The results indicate that, with all the studied loads (50%, 75%, and 100%), particulate mass and NO(x) can both be reduced over 25% by engine parameter adjustments. Further, the emission reduction was even higher when the target for adjusting engine parameters was to exclusively reduce either particulates or NO(x). In addition to particulate mass, different indicators of particulate emissions were also compared. These indicators included filter smoke number (FSN), total particle number, total particle surface area, and geometric mean diameter of the emitted particle size distribution. As a result of this comparison, a linear correlation between FSN and total particulate surface area at low FSN region was found.

Study of Miller timing on exhaust emissions of a hydrotreated vegetable oil (HVO)-fueled diesel engine.

The effect of intake valve closure (IVC) timing by utilizing Miller cycle and start of injection (SOI) on particulate matter (PM), particle number and nitrogen oxide (NOx) emissions was studied with a hydrotreated vegetable oil (HVO)-fueled nonroad diesel engine. HVO-fueled engine emissions, including aldehyde and polyaromatic hydrocarbon (PAH) emissions, were also compared with those emitted with fossil EN590 diesel fuel. At the engine standard settings, particle number and NOx emissions decreased at all the studied load points (50%, 75%, and 100%) when the fuel was changed from EN590 to HVO. Adjusting IVC timing enabled a substantial decrease in NOx emission and combined with SOI timing adjustment somewhat smaller decrease in both NOx and particle emissions at IVC -50 and -70 degrees CA points. The HVO fuel decreased PAH emissions mainly due to the absence of aromatics. Aldehyde emissions were lower with the HVO fuel with medium (50%) load. At higher loads (75% and 100%), aldehyde emissions were slightly higher with the HVO fuel. However, the aldehyde emission levels were quite low, so no clear conclusions on the effect of fuel can be made. Overall, the study indicates that paraffinic HVO fuels are suitable for emission reduction with valve and injection timing adjustment and thus provide possibilities for engine manufacturers to meet the strictening emission limits.

Effect of fuel injection pressure on a heavy-duty diesel engine nonvolatile particle emission.

The effects of the fuel injection pressure on a heavy-duty diesel engine exhaust particle emissions were studied. Nonvolatile particle size distributions and gaseous emissions were measured at steady-state engine conditions while the fuel injection pressure was changed. An increase in the injection pressure resulted in an increase in the nonvolatile nucleation mode (core) emission at medium and at high loads. At low loads, the core was not detected. Simultaneously, a decrease in soot mode number concentration and size and an increase in the soot mode distribution width were detected at all loads. Interestingly, the emission of the core was independent of the soot mode concentration at load conditions below 50%. Depending on engine load conditions, growth of the geometric mean diameter of the core mode was also detected with increasing injection pressure. The core mode emission and also the size of the mode increased with increasing NOx emission while the soot mode size and emission decreased simultaneously.

Significance of the organic aerosol driven climate feedback in the boreal area.

Aerosol particles cool the climate by scattering solar radiation and by acting as cloud condensation nuclei. Higher temperatures resulting from increased greenhouse gas levels have been suggested to lead to increased biogenic secondary organic aerosol and cloud condensation nuclei concentrations creating a negative climate feedback mechanism. Here, we present direct observations on this feedback mechanism utilizing collocated long term aerosol chemical composition measurements and remote sensing observations on aerosol and cloud properties. Summer time organic aerosol loadings showed a clear increase with temperature, with simultaneous increase in cloud condensation nuclei concentration in a boreal forest environment. Remote sensing observations revealed a change in cloud properties with an increase in cloud reflectivity in concert with increasing organic aerosol loadings in the area. The results provide direct observational evidence on the significance of this negative climate feedback mechanism.

Ion mobility distributions during the initial stages of new particle formation by the ozonolysis of α-pinene.

An ion mobility spectrometer (IMS) was used to study gas phase compounds during nucleation and growth of secondary organic aerosols (SOA). In this study SOA particles were generated by oxidizing α-pinene with O(3) and OH in a 6 m(3) reaction chamber. Positive ion peaks with reduced mobilities of 1.59 cm(2)(Vs)(-1) and 1.05 cm(2)(Vs)(-1) were observed 7 min after α-pinene and ozone were added to the chamber. The detected compounds can be associated with low volatility oxidation products of α-pinene, which have been suggested to participate in new particle formation. This is the first time that IMS has been applied to laboratory studies of SOA formation. IMS was found suitable for continuous online monitoring of the SOA formation process, allowing for highly sensitive detection of gas phase species that are thought to initiate new particle formation.

Deposition of α-pinene oxidation products on plant surfaces affects plant VOC emission and herbivore feeding and oviposition.

White cabbage, Brassica oleracea, plants and artificial leaves covered with B. oleracea epicuticular wax were exposed to α-pinene and α-pinene oxidation products formed through the oxidation of α-pinene by ozone (O3) and hydroxyl (OH) radicals. O3 and OH-induced oxidation of α-pinene led to the formation of oxygenated volatile organic compounds (OVOCs) and secondary organic aerosol particles (SOA), referred to together as oxidation products (OP). Exposure of cabbage plants to O3 and OH-induced α-pinene OP led to the deposition and re-emission of gas-phase OP by exposed cabbage plants. In a series of 2-choice bioassays, the specialist cruciferous herbivore, Plutella xylostella adults deposited less eggs on artificial leaves exposed to α-pinene OP than on control plants exposed to clean filtered air. P. xylostella larvae did not show a specific feeding preference when offered leaves from different exposure treatments. However, the generalist Indian stick insect, Carausius morosus, fed more on control filtered air-exposed plants than on those exposed to α-pinene OP. Taken together, our results show that exposure to α-pinene oxidation products affects VOC emissions of B. oleracea and alters P. xylostella oviposition and C. morosus feeding responses.

Resolving ambient organic aerosol formation and aging pathways with simultaneous molecular composition and volatility observations.

Organic aerosol (OA) constitutes a significant fraction of atmospheric fine particle mass. However, the precursors and chemical processes responsible for a majority of OA are rarely conclusively identified. We use online observations of hundreds of simultaneously measured molecular components obtained from 15 laboratory OA formation experiments with constraints on their effective saturation vapor concentrations to attribute the VOC precursors and subsequent chemical pathways giving rise to the vast majority of OA mass measured in two forested regions. We find that precursors and chemical pathways regulating OA composition and volatility are dynamic over hours to days, with their variations driven by coupled interactions between multiple oxidants. The extent of physical and photochemical aging, and its modulation by NOx, were key to a uniquely comprehensive combined composition-volatility description of OA. Our findings thus provide some of the most complete mechanistic-level guidance to the development of OA descriptions in air quality and Earth system models.