On the growth of atmospheric nanoparticles by organic vapors

Atmospheric aerosol particles affect the visibility, damage human health and influence the Earth's climate by scattering and absorbing radiation and acting as cloud condensation nuclei (CCN). Considerable uncertainties are associated with the estimates of aerosol climatic effects and the extent of these effects depends on the particles size, composition, concentration and location in the atmosphere. Improved knowledge on the processes affecting these properties is of great importance in predicting future climate. Significant fraction of the atmospheric aerosol particles are formed in the atmosphere from trace gases through a phase change, i.e. nucleation. The freshly nucleated secondary aerosol particles are about a nanometer in diameter, and they need to grow tens of nanometers by condensation of vapors before they affect the climate. During the growth, the nanoparticles are subject to coagulational losses, and their survival to CCN sizes is greatly dependent on their growth rate. Therefore, capturing the nanoparticle growth correctly is crucial for representing aerosol effects in climate models. A large fraction of nanoparticle growth in many environments is expected to be due to organic compounds. However a full identification of the compounds and processes involved in the growth is lacking to date. In this thesis the variability in atmospheric nanoparticle growth rates with particle size and ambient conditions was studied based on observations at two locations, a boreal forest and a Central European rural site. The importance of various organic vapor uptake mechanisms and particle phase processes was evaluated, and two nanoparticle growth models were developed to study the effect of acid-base chemistry in the uptake of organic compounds by nanoparticles. Further, the effect of inorganic solutes on the partitioning of organic aerosol constituents between gas and particle phase was studied based on laboratory experiments. Observations of the atmospheric nanoparticle growth rates supported the hypothesis of organic compounds controlling the particle growth. The growth rates of particles with diameter PIENEMPI 20 nm vary with particle size, and the processes covering the uptake of organic vapors and limiting the nanoparticle growth were concluded to be size dependent. Formation of organic salts in the particle phase is likely to play a role in nanoparticle growth, however, according to the model predictions, it does not explain the uptake of semi-volatile organic compounds entirely. Small amount of inorganic salt does not seem to affect the volatility of organic acids, however with an increased inorganic content the case is not as clear.Ilmakehän pienhiukkaset, aerosolihiukkaset, vaikuttavat näkyvyyteen, aiheuttavat epäsuotuisia terveysvaikutuksia ja vaikuttavat ilmastoon. Nämä vaikutukset riippuvat pienhiukkasten koosta, koostumuksesta, pitoisuudesta sekä sijainnista ilmakehässä. Pienhiukkasten ominaisuuksiin vaikuttavien tekijöiden parempi tuntemus on tärkeää kehitettäessä ilmastomalleja. Merkittävä osa ilmakehän pienhiukkasista muodostuu ilmakehässä olomuodonmuutoksella kaasusta nesteeksi tai kiinteäksi aineeksi. Näiden nanohiukkasten selviytyminen tarpeeksi suuriin kokoihin vaikuttaakseen ilmastoon riippuu vahvasti hiukkasten kasvunopeudesta. Useissa ympäristöissä suuri osa nanohiukkasten kasvusta tapahtuu ilmassa olevien orgaanisten hivenkaasujen tiivistymisellä hiukkaseen. Tähän tiivistymiskasvuun osallistuvia orgaanisia aineita ja hiukkasten kasvuun liittyviä prosesseja ei kuitenkaan tunneta vielä hyvin. Tässä väitöskirjassa tarkasteltiin ilmakehän noin 1-20 nm kokoluokkaa halkaisijaltaan olevien pienhiukkasten kasvua. Näiden nanohiukkasten kasvunopeuksia määritettiin hiukkaskokojakaumamittausten avulla kahdessa ympäristössä: boreaalisella metsäalueella Hyytiälässä, Suomessa, sekä maaseudulla Keski-Euroopassa. Mittausten perusteella tutkittiin nanohiukkasten kasvunopeuden vaihtelua hiukkasen koon ja ilmakehän olosuhteiden muuttuessa. Tutkimuksessa arvioitiin myös kaasufaasin ja hiukkasen sisäisten prosessien merkitystä nanohiukkasen kasvulle sekä kehitettiin kaksi laskennallista kasvumallia kuvaamaan happo-emäs-kemian roolia nanohiukkasten kasvussa. Lisäksi tutkittiin hiukkasessa olevan epäorgaanisen aineen vaikutusta orgaanisen aineen tiivistymisominaisuuksiin. Tulokset tukevat oletusta orgaanisten kaasujen tärkeästä roolista nanohiukkasten kasvussa. Työssä määritetyt kasvunopeuden arvot, erityisesti Hyytiälässä määritetyt, tarjoavat hyvän mahdollisuuden kehittää ilmastomalleihin tarkempia parametrisaatioita kuvaamaan nanohiukkasten kasvua. Erilaisten hiukkasen kasvuun liittyvien prosessien merkitys nanohiukkasen kasvun kannalta riippuu tulosten valossa hiukkasen koosta. Happo-emäs-kemialla on merkitystä nanohiukkasten kasvun kannalta, mutta mallisimulaatioiden perusteella tämä yksinään ei selitä orgaanisten höyryjen tiivistymistä hiukkaseen. Väitöskirjan tuloksia voidaan käyttää arvioimaan prosesseja, joita ilmastomalleihin tulisi sisällyttää kuvaamaan nanohiukkasten kasvua

Analysis of sub-3 nm particle growth in connection with sulfuric acid in a boreal forest

We analyzed nanoparticle growth during new-particle-formation events based on ten years of measurements carried out at a boreal forest site in Hyytiala, Finland, concentrating on the sub-3 nm particles and the role of sulfuric acid in their growth. Growth rates of 1.5-3 nm diameter particles were determined from ion spectrometer measurements and compared with parameterized sulfuric acid concentration and other atmospheric parameters. The calculated growth rates from sulfuric acid condensation were on average 7.4% of the observed growth rates and the two did not correlate. These suggest that neither sulfuric acid monomer condensation nor coagulation of small sulfuric acid clusters was the primary growth mechanism in these atmospheric conditions. Also no clear sign of organic condensation being the single main growth mechanism was seen. These observations are consistent with the hypothesis that several factors have comparative roles in the sub-3 nm growth.Peer reviewe

Comparing secondary organic aerosol (SOA) volatility distributions derived from isothermal SOA particle evaporation data and FIGAERO-CIMS measurements

The volatility distribution of the organic compounds present in secondary organic aerosol (SOA) at different conditions is a key quantity that has to be captured in order to describe SOA dynamics accurately. The development of the Filter Inlet for Gases and AEROsols (FIGAERO) and its coupling to a chemical ionization mass spectrometer (CIMS; collectively FIGAERO-CIMS) has enabled near-simultaneous sampling of the gas and particle phases of SOA through thermal desorption of the particles. The thermal desorption data have been recently shown to be interpretable as a volatility distribution with the use of the positive matrix factorization (PMF) method. Similarly, volatility distributions can be inferred from isothermal particle evaporation experiments when the particle size change measurements are analyzed with process-modeling techniques. In this study, we compare the volatility distributions that are retrieved from FIGAERO-CIMS and particle size change measurements during isothermal particle evaporation with process-modeling techniques. We compare the volatility distributions at two different relative humidities (RHs) and two oxidation conditions. In high-RH conditions, where particles are in a liquid state, we show that the volatility distributions derived via the two ways are similar within a reasonable assumption of uncertainty in the effective saturation mass concentrations that are derived from FIGAERO-CIMS data. In dry conditions, we demonstrate that the volatility distributions are comparable in one oxidation condition, and in the other oxidation condition, the volatility distribution derived from the PMF analysis shows considerably more high-volatility matter than the volatility distribution inferred from particle size change measurements. We also show that the Vogel-Tammann-Fulcher equation together with a recent glass transition temperature parametrization for organic compounds and PMF-derived volatility distribution estimates are consistent with the observed isothermal evaporation under dry conditions within the reported uncertainties. We conclude that the FIGAERO-CIMS measurements analyzed with the PMF method are a promising method for inferring the volatility distribution of organic compounds, but care has to be taken when the PMF factors are analyzed. Future process-modeling studies about SOA dynamics and properties could benefit from simultaneous FIGAERO-CIMS measurements.Peer reviewe

Effects of oligomerization and decomposition on the nanoparticle growth : a model study

The rate at which freshly formed secondary aerosol particles grow is an important factor in determining their climate impacts. The growth rate of atmospheric nanoparticles may be affected by particle-phase oligomerization and decomposition of condensing organic molecules. We used the Model for Oligomerization and Decomposition in Nanoparticle Growth (MODNAG) to investigate the potential atmospheric significance of these effects. This was done by conducting multiple simulations with varying reaction-related parameters (volatilities of the involved compounds and reaction rates) using both artificial and ambient measured gas-phase concentrations of organic vapors to define the condensing vapors. While our study does not aim at providing information on any specific reaction, our results indicate that particle-phase reactions have significant potential to affect the nanoparticle growth. In simulations in which one-third of a volatility basis set bin was allowed to go through particle-phase reactions, the maximum increase in growth rates was 71% and the decrease 26% compared to the base case in which no particle-phase reactions were assumed to take place. These results highlight the importance of investigating and increasing our understanding of particle-phase reactions.Peer reviewe

Secondary Organic Aerosol Formation from Healthy and Aphid-Stressed Scots Pine Emissions.

One barrier to predicting biogenic secondary organic aerosol (SOA) formation in a changing climate can be attributed to the complex nature of plant volatile emissions. Plant volatile emissions are dynamic over space and time, and change in response to environmental stressors. This study investigated SOA production from emissions of healthy and aphid-stressed Scots pine saplings via dark ozonolysis and photooxidation chemistry. Laboratory experiments using a batch reaction chamber were used to investigate SOA production from different plant volatile mixtures. The volatile mixture from healthy plants included monoterpenes, aromatics, and a small amount of sesquiterpenes. The biggest change in the volatile mixture for aphid-stressed plants was a large increase (from 1.4 to 7.9 ppb) in sesquiterpenes-particularly acyclic sesquiterpenes, such as the farnesene isomers. Acyclic sesquiterpenes had different effects on SOA production depending on the chemical mechanism. Farnesenes suppressed SOA formation from ozonolysis with a 9.7-14.6% SOA mass yield from healthy plant emissions and a 6.9-10.4% SOA mass yield from aphid-stressed plant emissions. Ozonolysis of volatile mixtures containing more farnesenes promoted fragmentation reactions, which produced higher volatility oxidation products. In contrast, plant volatile mixtures containing more farnesenes did not appreciably change SOA production from photooxidation. SOA mass yields ranged from 10.8 to 23.2% from healthy plant emissions and 17.8-26.8% for aphid-stressed plant emissions. This study highlights the potential importance of acyclic terpene chemistry in a future climate regime with an increased presence of plant stress volatiles

Optimization of process models for determining volatility distribution and viscosity of organic aerosols from isothermal particle evaporation data

The composition of organic aerosol under different ambient conditions as well as their phase state have been a subject of intense study in recent years. One way to study particle properties is to measure the particle size shrinkage in a diluted environment at isothermal conditions. From these measurements it is possible to separate the fraction of low-volatility compounds from high-volatility compounds. In this work, we analyse and evaluate a method for obtaining particle composition and viscosity from measurements using process models coupled with input optimization algorithms. Two optimization methods, the Monte Carlo genetic algorithm and Bayesian inference, are used together with process models describing the dynamics of particle evaporation. The process model optimization scheme in inferring particle composition in a volatility-basis-set sense and composition-dependent particle viscosity is tested with artificially generated data sets and real experimental data. Optimizing model input so that the output matches these data yields a good match for the estimated quantities. Both optimization methods give equally good results when they are used to estimate particle composition to artificially test data. The timescale of the experiments and the initial particle size are found to be important in defining the range of values that can be identified for the properties from the optimization

The effect of clouds and precipitation on the aerosol concentrations and composition in a boreal forest environment

Atmospheric aerosol particle concentrations are strongly affected by various wet processes, including below and in-cloud wet scavenging and in-cloud aqueous-phase oxidation. We studied how wet scavenging and cloud processes affect particle concentrations and composition during transport to a rural boreal forest site in northern Europe. For this investigation, we employed air mass history analysis and observational data. Long-term particle number size distribution (similar to 15 years) and composition measurements (similar to 8 years) were combined with air mass trajectories with relevant variables from reanalysis data. Some such variables were rainfall rate, relative humidity, and mixing layer height. Additional observational datasets, such as temperature and trace gases, helped further evaluate wet processes along trajectories with mixed effects models. All chemical species investigated (sulfate, black carbon, and organics) exponentially decreased in particle mass concentration as a function of accumulated precipitation along the air mass route. In sulfate (SO4) aerosols, clear seasonal differences in wet removal emerged, whereas organics (Org) and equivalent black carbon (eBC) exhibited only minor differences. The removal efficiency varied slightly among the different reanalysis datasets (ERA-Interim and Global Data Assimilation System; GDAS) used for the trajectory calculations due to the difference in the average occurrence of precipitation events along the air mass trajectories between the reanalysis datasets. Aqueous-phase processes were investigated by using a proxy for air masses travelling inside clouds. We compared air masses with no experience of approximated in-cloud conditions or precipitation during the past 24 h to air masses recently inside non-precipitating clouds before they entered SMEAR II (Station for Measuring Ecosystem-Atmosphere Relations). Significant increases in SO4 mass concentration were observed for the latter air masses (recently experienced non-precipitating clouds). Our mixed effects model considered other contributing factors affecting particle mass concentrations in SMEAR II: examples were trace gases, local meteorology, and diurnal variation. This model also indicated in-cloud SO4 production. Despite the reanalysis dataset used in the trajectory calculations, aqueous-phase SO4 formation was observed. Particle number size distribution measurements revealed that most of the in-cloud SO4 formed can be attributed to particle sizes larger than 200 nm (electrical mobility diameter). Aqueous-phase secondary organic aerosol (aqSOA) formation was non-significant.Peer reviewe

Multivariate model-based investigation of the temperature dependence of ozone concentration in Finnish boreal forest

Tropospheric ozone (O-3) concentrations are observed to increase with temperature in urban and rural locations. We investigated the apparent temperature dependency of daytime ozone concentration in the Finnish boreal forest in summertime based on long-term measurements. We used statistical mixed effects models to separate the direct effects of temperature from other factors influencing this dependency, such as weather conditions, long-range transport of precursors, and concentration of various hydrocarbons. The apparent temperature dependency of 1.16 ppb ?(-1) based on a simple linear regression was reduced to 0.87 ppb ?(-1) within the canopy for summer daytime data after considering these factors. In addition, our results indicated that small oxygenated volatile organic compounds may play an important role in the temperature dependence of O-3 concentrations in this dataset from a low-NOx environment. Summertime observations and daytime data were selected for this analysis to focus on an environment that is significantly affected by biogenic emissions. Despite limitations due to selection of the data, these results highlight the importance of considering factors contributing to the apparent temperature dependence of the O-3 concentration. In addition, our results show that a mixed effects model achieves relatively good predictive accuracy for this dataset without explicitly calculating all processes involved in O-3 formation and removal.Peer reviewe