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Aromatic hydrocarbons contribute significantly to tropospheric ozone and secondary organic aerosols (SOA). Despite large efforts in elucidating the formation mechanism of aromatic-derived SOA, current models still substantially underestimate the SOA yields when comparing to field measurements. Here we present a new, up to now undiscovered pathway for the formation of highly oxidized products from the OH-initiated oxidation of alkyl benzenes based on theoretical and experimental investigations. We propose that unimolecular H-migration followed by O 2 -addition, a so-called autoxidation step, can take place in bicyclic peroxy radicals (BPRs), which are important intermediates of the OH-initiated oxidation of aromatic compounds. These autoxidation steps lead to the formation of highly oxidized multifunctional compounds (HOMs), which are able to form SOA. Our theoretical calculations suggest that the intramolecular H-migration in BPRs of substituted benzenes could be fast enough to compete with bimolecular reactions with HO 2 radicals or NO under atmospheric conditions. The theoretical findings are experimentally supported by flow tube studies using chemical ionization mass spectrometry to detect the highly oxidized peroxy radical intermediates and closed-shell products. This new unimolecular BPR route to form HOMs in the gas phase enhances our understanding of the aromatic oxidation mechanism, and contributes significantly to a better understanding of aromatic-derived SOA in urban areas.

Forests emit large quantities of volatile organic compounds (VOCs) to the atmosphere. Their condensable oxidation products can form secondary organic aerosol, a significant and ubiquitous component of atmospheric aerosol, which is known to affect the Earth's radiation balance by scattering solar radiation and by acting as cloud condensation nuclei. The quantitative assessment of such climate effects remains hampered by a number of factors, including an incomplete understanding of how biogenic VOCs contribute to the formation of atmospheric secondary organic aerosol. The growth of newly formed particles from sizes of less than three nanometres up to the sizes of cloud condensation nuclei (about one hundred nanometres) in many continental ecosystems requires abundant, essentially non-volatile organic vapours, but the sources and compositions of such vapours remain unknown. Here we investigate the oxidation of VOCs, in particular the terpene α-pinene, under atmospherically relevant conditions in chamber experiments. We find that a direct pathway leads from several biogenic VOCs, such as monoterpenes, to the formation of large amounts of extremely low-volatility vapours. These vapours form at significant mass yield in the gas phase and condense irreversibly onto aerosol surfaces to produce secondary organic aerosol, helping to explain the discrepancy between the observed atmospheric burden of secondary organic aerosol and that reported by many model studies. We further demonstrate how these low-volatility vapours can enhance, or even dominate, the formation and growth of aerosol particles over forested regions, providing a missing link between biogenic VOCs and their conversion to aerosol particles. Our findings could help to improve assessments of biosphere-aerosol-climate feedback mechanisms, and the air quality and climate effects of biogenic emissions generally.

The recent development in measurement techniques and theoretical understanding has enabled us to study atmospheric vapor, cluster and nanoparticle concentrations, dynamics, and their connection to atmospheric nucleation. Here we present a summary of the chemistry of atmospheric clustering, growing nanoparticles, and their precursors. In this work, we focus particularly on atmospheric gas-to-particle conversion and recent progress in its understanding.

Submicron aerosol particles were collected during July and August 2010 in Hyytiälä, Finland, to determine the composition and sources of aerosol at that boreal forest site. Submicron particles were collected on Teflon filters and analyzed by Fourier transform infrared (FTIR) spectroscopy for organic functional groups (OFGs). Positive matrix factorization (PMF) was applied to aerosol mass spectrometry (AMS) measurements and FTIR spectra to identify summertime sources of submicron aerosol mass at the sampling site. The two largest sources of organic mass (OM) in particles identified at Hyytiälä were (1) biogenic aerosol from surrounding local forest and (2) biomass burning aerosol, transported 4-5 days from large wildfires burning near Moscow, Russia, and northern Ukraine. The robustness of this apportionment is supported by the agreement of two independent analytical methods for organic measurements with three statistical techniques. FTIR factor analysis was more sensitive to the chemical differences between biogenic and biomass burning organic components, while AMS factor analysis had a higher time resolution that more clearly linked the temporal behavior of separate OM factors to that of different source tracers even though their fragment mass spectrum were similar. The greater chemical sensitivity of the FTIR is attributed to the nondestructive preparation and the functional group specificity of spectroscopy. The FTIR spectra show strong similarities among biogenic and biomass burning factors from different regions as well as with reference OM (namely olive tree burning organic aerosol and α-pinene chamber secondary organic aerosol (SOA)). The biogenic factor correlated strongly with temperature and oxidation products of biogenic volatile organic compounds (BVOCs), included more than half of the oxygenated OFGs (carbonyl groups at 29% and carboxylic acid groups at 22 %), and represented 35% of the submicron OM. Compared to previous studies at Hyytiälä, the summertime biogenic OM is 1.5 to 3 times larger than springtime biogenic OM (0.64 μgm-3 and 0.4 μgm-3, measured in 2005 and 2007, respectively), even though it contributed only 35% of OM. The biomass burning factor contributed 25% of OM on average and up to 62% of OM during three periods of transported biomass burning emissions: 26-28 July, 29-30 July, and 8-9 August, with OFG consisting mostly of carbonyl (41 %) and alcohol (25 %) groups. The high summertime terrestrial biogenic OM (1.7 μgm-3) and the high biomass burning contributions (1.2 μgm-3) were likely due to the abnormally high temperatures that resulted in both stressed boreal forest conditions with high regional BVOC emissions and numerous wildfires in upwind regions. [ABSTRACT FROM AUTHOR]

We describe a novel inlet that allows measurement of both gas and particle molecular composition when coupled to mass spectrometric, chromatographic, or optical sensors: the Filter Inlet for Gas and AEROsol (FIGAERO). The design goals for the FIGAERO are to allow unperturbed observation of ambient air while simultaneously analyzing gases and collecting particulate matter on a Teflon filter via an entirely separate sampling port. The filter is analyzed periodically by the same sensor on hourly or faster timescales using temperature-programmed thermal desorption. We assess the performance of the FIGAERO by coupling it to a high-resolution time-of-flight chemical-ionization mass spectrometer (HRToF-CIMS) in laboratory chamber studies of α-pinene oxidation and field measurements at a boreal forest location. Low instrument backgrounds give detection limits of ppt or lower for compounds in the gas-phase and in the pgm-3 range for particle phase compounds. The FIGAERO-HRToF-CIMS provides molecular information about both gases and particle composition on the 1 Hz and hourly timescales, respectively for hundreds of compounds. The FIGAERO thermal desorptions are highly reproducible (better than 10 %), allowing a calibrated assessment of the effective volatility of desorbing compounds and the role of thermal decomposition during the desorption process. We show that the often multi-modal desorption thermograms arising from secondary organic aerosol (SOA) provide additional insights into molecular composition and/or particle morphology, and exhibit changes with changes in SOA formation or aging pathways. [ABSTRACT FROM AUTHOR]

The volatility of submicron atmospheric aerosol particles was investigated at a boreal forest site in Hyytiälä Finland from January 2008 to May 2010. These long-term observations allowed for studying the seasonal behavior of aerosol evaporation with a special focus on compounds that remained in the aerosol phase at 280 C. The temperature-response of evaporation was also studied by heating the aerosol sample step-wise to six temperatures ranging from 80°C to 280°C. The mass fraction remaining after heating (MFR) was determined from the measured particle number size distributions before and after heating assuming a constant particle density (1.6 g cm ). On average 19% of the total aerosol mass remained in the particulate phase at 280°C. The particles evaporated less at low ambient temperatures during winter as compared with the warmer months. Black carbon (BC) fraction of aerosol mass correlated positively with the MFR at 280 C, but could not explain it completely: most of the time a notable fraction of this non-volatile residual was something other than BC. Using additional information on ambient meteorological conditions and results from an Aerodyne aerosol mass spectrometer (AMS), the chemical composition of MFR at 280 C and its seasonal behavior was further examined. Correlation analysis with ambient temperature and mass fractions of polycyclic aromatic hydrocarbons (PAHs) indicated that MFR at 280 C is probably affected by anthropogenic emissions. On the other hand, results from the AMS analysis suggested that there may be very low-volatile organics, possibly organonitrates, in the non-volatile (at 280°C) fraction of aerosol mass. [ABSTRACT FROM AUTHOR]

Formation of new aerosol particles by nucleation and growth is a significant source of aerosols in the atmosphere. New particle formation events usually take place during daytime, but in some locations they have been observed also at night. In the present study we have combined chamber experiments, quantum chemical calculations and aerosol dynamics models to study nocturnal new particle formation. All our approaches demonstrate, in a consistent manner, that the oxidation products of monoterpenes play an important role in nocturnal nucleation events. By varying the conditions in our chamber experiments, we were able to reproduce the very different types of nocturnal events observed earlier in the atmosphere. The exact strength, duration and shape of the events appears to be sensitive to the type and concentration of reacting monoterpenes, as well as the extent to which the monoterpenes are exposed to ozone and potentially other atmospheric oxidants. [ABSTRACT FROM AUTHOR]

Atmospheric aerosol particles influence global climate as well as impair air quality through their effects on atmospheric visibility and human health. Ultrafine (< 100 nm) particles often dominate aerosol numbers, and nucleation of atmospheric vapors is an important source of these particles. To have climatic relevance, however, the freshly nucleated particles need to grow in size. We combine observations from two continental sites (Egbert, Canada and Hyytiälä, Finland) to show that condensation of organic vapors is a crucial factor governing the lifetimes and climatic importance of the smallest atmospheric particles. We model the observed ultrafine aerosol growth with a simplified scheme approximating the condensing species as a mixture of effectively non-volatile and semi-volatile species, demonstrate that state-of-the-art organic gas-particle partitioning models fail to reproduce the observations, and propose a modeling approach that is consistent with the measurements. We find that roughly half of the mass of the condensing mass needs to be distributed proportional to the aerosol surface area (thus implying that the condensation is governed by gas-phase concentration rather than the equilibrium vapour pressure) to explain the observed aerosol growth. We demonstrate the large sensitivity of predicted number concentrations of cloud condensation nuclei (CCN) to these interactions between organic vapors and the smallest atmospheric nanoparticles -- highlighting the need for representing this process in global climate models. [ABSTRACT FROM AUTHOR]

In the field, aerosol in-situ measurements are often performed under dry conditions (relative humidity RH<30--40%). Since ambient aerosol particles experience hygroscopic growth at enhanced RH, their microphysical and optical properties -- especially the aerosol light scattering -- are also strongly dependent on RH. The knowledge of this RH effect is of crucial importance for climate forcing calculations or for the comparison of remote sensing with insitu measurements. Here, we will present results from a four-month campaign which took place in summer 2009 in Cabauw, The Netherlands. The aerosol scattering coefficient σ sp(λ) was measured dry and at various, predefined RH conditions between 20 and 95% with a humidified nephelometer. The scattering enhancement factor f (RH,λ) is the key parameter to describe the effect of RH on σ sp(λ) and is defined as σ sp(RH,λ) measured at a certain RH divided by the dry σ sp(dry,λ). The measurement of f (RH,λ) together with the dry absorption measurement (assumed not to change with RH) allows the determination of the actual extinction coefficient σ ep(RH,λ) at ambient RH. In addition, a wide range of other aerosol properties were measured in parallel. The measurements were used to characterize the effects of RH on the aerosol optical properties. A closure study showed the consistency of the aerosol in-situ measurements. Due to the large variability of air mass origin (and thus aerosol composition) a simple parameterization of f (RH,λ) could not be established. If f (RH,λ) needs to be predicted, the chemical composition and size distribution need to be known. Measurements of four MAX-DOAS (multi-axis differential optical absorption spectroscopy) instruments were used to retrieve vertical profiles of σ ep(λ). The values of the lowest layer were compared to the in-situ values after conversion of the latter ones to ambient RH. The comparison showed a good correlation of R² = 0.62--0.78, but the extinction coefficients from MAX-DOAS were a factor of 1.5--3.4 larger than the insitu values. Best agreement is achieved for a few cases characterized by low aerosol optical depths and low planetary boundary layer heights. Differences were shown to be dependent on the applied MAX-DOAS retrieval algorithm. The comparison of the in-situ extinction data to a Raman LIDAR (light detection and ranging) showed a good correlation and higher values measured by the LIDAR (R² = 0.82-0.85, slope of 1.69--1.76) if the Raman retrieved profile was used to extrapolate the directly measured extinction coefficient to the ground. The comparison improved if only nighttime measurements were used in the comparison (R² =0.96, slope of 1.12). [ABSTRACT FROM AUTHOR]

The Antarctic near-coastal sub-micrometre aerosol particle features in summer were characterised based on measured data on aerosol hygroscopicity, size distributions, volatility and chemical ion and organic carbon mass concentrations. Hysplit model was used to calculate the history of the air masses to predict the particle origin. Additional measurements of meteorological parameters were utilised. The hygroscopic properties of particles mostly resembled those of marine aerosols. The measurements took place at 130 km from the Southern Ocean, which was the most significant factor affecting the particle properties. This is explained by the lack of additional sources on the continent of Antarctica. The Southern Ocean was thus a likely source of the particles and nucleating and condensing vapours. The particles were very hygroscopic (HGF 1.75 at 90 nm) and very volatile. Most of the sub-100 nm particle volume volatilised below 100 °C. Based on chemical data, particle hygroscopic and volatile properties were explained by a large fraction of non-neutralised sulphuric acid together with organic material. The hygroscopic growth factors assessed from chemical data were similar to measured. Hygroscopicity was higher in dry continental air masses compared with the moist marine air masses. This was explained by the aging of the marine organic species and lower methanesulphonic acid volume fraction together with the changes in the inorganic aerosol chemistry as the aerosol had travelled long time over the continental Antarctica. Special focus was directed in detailed examination of the observed new particle formation events. Indications of the preference of negative over positive ions in nucleation could be detected. However, in a detailed case study, the neutral particles dominated the particle formation process. Freshly nucleated particles had the smallest hygroscopic growth factors, which increased subsequent to particle aging. [ABSTRACT FROM AUTHOR]

A unique opportunity arose during the MAP project to compare open ocean aerosol measurements with those undertaken at the Mace Head Global Atmosphere Watch Station, a station used for decades for aerosol process research and long-term monitoring. The objective of the present study is to demonstrate that the key aerosol features and processes observed at Mace Head are characteristic of the open ocean, while acknowledging and allowing for spatial and temporal gradients. Measurements were conducted for a 5-week period at Mace Head and offshore, on the Research Vessel Celtic Explorer, in generally similar marine air masses, albeit not in connected-flow scenarios. The results of the study indicate, in terms of aerosol number size distribution, higher nucleation mode particle concentrations at Mace Head than offshore, pointing to a strong coastal source of new particles that is not representative of the open ocean. The Aitken mode exhibited a large degree of similarity, with no systematic differences between Mace Head and the open ocean, while the accumulation mode showed averagely 35% higher concentrations at Mace Head. The higher accumulation mode concentration can be attributed equally to cloud processing and to a coastal enhancement in concentration. Chemical analysis showed similar or even higher offshore concentrations for dominant species, such as nss-SO4-2, WSOC, WIOC and MSA. Sea salt concentration differences determined a 40% higher supermicron mass at Mace Head, although this difference can be attributed to a higher wind speed at Mace Head during the comparison period. Moreover, the relative chemical composition as a function of size illustrated remarkable similarity. While differences to varying degrees were observed between offshore and coastal measurements, no convincing evidence was found of local coastal effects, apart from nucleation mode aerosol, thus confirming the integrity of previously reported marine aerosol characterisation studies at Mace Head. [ABSTRACT FROM AUTHOR]