Results and recommendations from an intercomparison of six Hygroscopicity-TDMA systems

The performance of six custom-built Hygrocopicity-Tandem Differential Mobility Analyser (H-TDMA) systems was investigated in the frame of an international calibration and intercomparison workshop held in Leipzig, February 2006. The goal of the workshop was to harmonise H-TDMA measurements and develop recommendations for atmospheric measurements and their data evaluation. The H-TDMA systems were compared in terms of the sizing of dry particles, relative humidity (RH) uncertainty, and consistency in determination of number fractions of different hygroscopic particle groups. The experiments were performed in an air-conditioned laboratory using ammonium sulphate particles or an external mixture of ammonium sulphate and soot particles. The sizing of dry particles of the six H-TDMA systems was within 0.2 to 4.2% of the selected particle diameter depending on investigated size and individual system. Measurements of ammonium sulphate aerosol found deviations equivalent to 4.5% RH from the set point of 90% RH compared to results from previous experiments in the literature. Evaluation of the number fraction of particles within the clearly separated growth factor modes of a laboratory generated externally mixed aerosol was done. The data from the H-TDMAs was analysed with a single fitting routine to investigate differences caused by the different data evaluation procedures used for each H-TDMA. The differences between the H-TDMAs were reduced from +12/-13% to +8/-6% when the same analysis routine was applied. We conclude that a common data evaluation procedure to determine number fractions of externally mixed aerosols will improve the comparability of H-TDMA measurements. It is recommended to ensure proper calibration of all flow, temperature and RH sensors in the systems. It is most important to thermally insulate the aerosol humidification unit and the second DMA and to monitor these temperatures to an accuracy of 0.2 degrees C. For the correct determination of external mixtures, it is necessary to take into account size-dependent losses due to diffusion in the plumbing between the DMAs and in the aerosol humidification unit.Peer reviewe

Non-volatile residuals of newly formed atmospheric particles in the boreal forest

The volatility of sub-micrometer atmospheric aerosol particles was studied in a rural background environment in Finland using a combination of a heating tube and a scanning mobility particle sizer. The analysis focused on nanoparticles formed through nucleation which were subsequently observed during their growth in the diameter range between 5 and 60 nm. During the 6 days of new particle formation shown in detail, the concentrations of newly formed particles increased up to 10 000 cm−3. The number of nucleation mode particles measured after volatilization in the heating tube at 280°C was up to 90% of the total number under ambient conditions. Taking into account the absolute accuracy of the size distribution measurements, all ambient particles found in the rural atmosphere could have a non-volatile core after volatilization at 280°C. As the regional new particle formation events developed over time as a result of further vapor condensation, the newly formed particles grew at an average growth rate of 2.4±0.3 nm h−1. Importantly, the non-volatile cores of nucleation mode particles were also observed to grow over time, however, at a lower average growth rate of 0.6±0.3 nm h−1. One implication of the volatility analysis is that the newly formed particles, which have reached ambient diameters of 15 nm, are unlikely to consist of sulfuric acid, ammonium sulfate, and water alone. A relatively constant ratio between the growth rate of the ambient particles as well as their non-volatile cores indicates that non-volatile matter is formed only gradually in the growing particles. The non-volatile fraction of the particles showed some correlation with the ambient temperature. The composition and formation mechanism of this non-volatile material in nucleation mode particles are, to date, not known

Modeling the Charging of Highly Oxidized Cyclohexene Ozonolysis Products Using Nitrate-Based Chemical Ionization

Several extremely low volatility organic compounds (ELVOCs) formed in the ozonolysis of endocyclic alkenes have recently been detected in laboratory and field studies. These experiments have been carried out with chemical ionization atmospheric pressure interface time-of-flight mass spectrometers (CI-APi-TOP) with nitrate ions as reagent ions. The nitrate ion binds to the detected species through hydrogen bonds, but it also binds very strongly to one or two neutral nitric acid molecules. This makes the measurement highly selective when there is an excess amount of neutral nitric acid in the instrument. In this work, we used quantum-chemical methods to calculate the binding energies between a nitrate ion and several highly oxidized ozonolysis products of cydohexene. These were then compared with the binding energies of nitrate ion nitric acid clusters. Systematic configurational sampling of the molecules and clusters was carried out at the B3LYP/6-31+G* and omega B97xD/aug-cc-pVTZ levels, and the final single-point energies were calculated with DLPNO-CCSD(T)/def2-QZVPP. The binding energies were used in a kinetic simulation of the measurement system to determine the relative ratios of the detected signals. Our results indicate that at least two hydrogen bond donor functional groups (in this case, hydroperoxide, OOH) are needed for an ELVOC molecule to be detected in a nitrate ion CI-APi-TOP. Also, a double bond in the carbon backbone makes the nitrate cluster formation less favorable.Peer reviewe

Painting the ideal home: using art to express visions of technologically supported independent living for older people in North East England

This paper describes the investigation of the development of future technological products to support older people in everyday living through the agency of a community art group. Recent research has identified a number of challenges facing designers seeking to use traditional participatory design approaches to gather technology requirements data from older people. Here, a project is described that sought to get a group of older people to think creatively about their needs and desires for technological support through the medium of paint. The artistic expression technique described in this article allowed the identification of issues that had also been found by previous research that used a range of different techniques. This indicates that the approach shows promise, as it allows information to be gathered in an environment that is comfortable and familiar using methods already known by the participants and which they find enjoyable. It provides a complement (or possible alternative) to standard protocols and has the potential benefit of extracting even richer information as the primary task for participants is enjoyable in its own right and is not associated with an interrogative process. Furthermore, it is argued that some of the key risks of traditional approaches are lessened or removed by the naturalistic setting of this approach

Evidence for Diverse Biogeochemical Drivers of Boreal Forest New Particle Formation

New particle formation (NPF) is an important contributor to particle number in many locations, but the chemical drivers for this process are not well understood. Daytime NPF events occur regularly in the springtime Finnish boreal forest and strongly impact aerosol abundance. In April 2014 size-resolved chemical measurements of ambient nanoparticles were made using the Time-of-Flight Thermal Desorption Chemical ionization Mass Spectrometer and we report results from two NPF events. While growth overall was dominated by terpene oxidation products, newly formed 20-70nm particles showed enhancement in apparent alkanoic acids. The events occurred on days with rapid transport of marine air, which correlated with low background aerosol loading and higher gas phase methanesulfonic acid levels. These results are broadly consistent with previous studies on Nordic NPF but indicate that further attention should be given to the sources and role of non-terpenoid organics and the possible contribution of transported marine compounds in this process. Plain Language Summary Clouds are an enormously important part of the climate system because they control the radiation entering and leaving the Earth. Clouds form as water condenses onto small particles called cloud condensation nuclei. These particles can be directly emitted from the Earth's surface, like sea spray, for example, or they can form in the atmosphere out of precursor gases. We have measured the composition of these atmosphere-formed particles to understand better how this process works in the Nordic boreal forest. We found that a diverse mix of processes and molecules are likely involved, possibly including the transport of materials from the ocean. While these results will ultimately lead to a better understanding of ocean-land-cloud interactions, they currently indicate that more work is needed to learn the processes involved.Peer reviewe

Molecular mechanism for rapid autoxidation in alpha-pinene ozonolysis

Aerosol affects Earth's climate and the health of its inhabitants. A major contributor to aerosol formation is the oxidation of volatile organic compounds. Monoterpenes are an important class of volatile organic compounds, and recent research demonstrate that they can be converted to low-volatility aerosol precursors on sub-second timescales following a single oxidant attack. The alpha -pinene + O-3 system is particularly efficient in this regard. However, the actual mechanism behind this conversion is not understood. The key challenge is the steric strain created by the cyclobutyl ring in the oxidation products. This strain hinders subsequent unimolecular hydrogen-shift reactions essential for lowering volatility. Using quantum chemical calculations and targeted experiments, we show that the excess energy from the initial ozonolysis reaction can lead to novel oxidation intermediates without steric strain, allowing the rapid formation of products with up to 8 oxygen atoms. This is likely a key route for atmospheric organic aerosol formation. Oxidation of volatile organic compounds leads to aerosol formation in the atmosphere, but the mechanism of some fast reactions is still unclear. The authors, using quantum chemical modelling and experiments, reveal that in key monoterpenes the cyclobutyl ring that would hinder the reactivity is broken in the early exothermic steps of the reaction.Peer reviewe

Computational Study of Hydrogen Shifts and Ring-Opening Mechanisms in alpha-Pinene Ozonolysis Products

Autoxidation by: sequential peroxy radical hydrogen shifts (H-shifts) and O-2 additions has recently emerged as a promising mechanism for the rapid formation of highly oxidized, low-Volatility organic Compounds in the. atmosphere: A kg prerequisite for auto)ddation is that the H-shifts of the initial peroxy radicals formed by, e.g., OH or O-3 oxidation are fast enough to compete with bimolecular sink reactions. In most atmospheric conditions, these restrict the lifetime Of peroxy.radicals to be on the order of seconds. We have systematically investigated all potentially important (nonmethyl, sterically unhindered) H-shifts of all four peroxy radicals formed in the ozonolysis of alpha-pinene using density functional (omega B97XD) and coupled cluster [CCSD(T)-F12] theory. In contrast to the related but chemically simpler tyclohexene ozonolysis system, none of the calculated li-shifts have rate constants above 1 s(-1) at 298 K, and most are below 0.01 s(-1). The law rate constants are connected to the presence of the' strained tyclobutyi sing in the alpha-pinene-derived peroxy radicals, which hinders H-shifts both from and across the ring. For autoxidation to yield the experimentally observed highly oxidized products in the alpha-pinene ozonolysis system, additional ring-opening reaction mechanisms breaking the cyclobutyl ring are therefore needed. We further investigate possible uni- and bimolecular pathways for,opening the cydobutyl ring in, the alpha-pinene ozonolysis system.Peer reviewe

Hygroscopic properties of ultrafine aerosol particles in the boreal forest: diurnal variation, solubility and the influence of sulfuric acid

International audienceThe hygroscopic growth of aerosol particles present in a boreal forest was measured at a relative humidity of 88%. Simultaneously the gas phase concentration of sulfuric acid, a very hygroscopic compound, was monitored. The focus was mainly on days with new particle formation by nucleation. The measured hygroscopic growth factors (GF) correlated positively with the gaseous phase sulfuric acid concentrations. The smaller the particles, the stronger the correlation, with r=0.20 for 50 nm and r=0.50 for 10 nm particles. The increase in GF due to condensing sulfuric acid is expected to be larger for particles with initially smaller masses. During new particle formation, the changes in solubility of the new particles were calculated during their growth to Aitken mode sizes. As the modal diameter increased, the solubility of the particles decreased. This indicated that the initial particle growth was due to more hygroscopic compounds, whereas the later growth during the evening and night was mainly caused by less hygroscopic or even hydrophobic compounds. For all the measured sizes, a diurnal variation in GF was observed both during days with and without particle formation. The GF was lowest at around midnight, with a mean value of 1.12?1.24 depending on particle size and if new particle formation occurred during the day, and increased to 1.25?1.34 around noon. This can be tentatively explained by day- and nighttime gas-phase chemistry; different vapors will be present depending on the time of day, and through condensation these compounds will alter the hygroscopic properties of the particles in different ways

Isomer-Resolved Mobility-Mass Analysis of alpha-Pinene Ozonolysis Products

Highly oxygenated organic molecules (HOMs) are important sources of atmospheric aerosols. Resolving the molecular-level formation mechanisms of these HOMs from freshly emitted hydrocarbons improves the understanding of aerosol properties and their influence on the climate. In this study, we measure the electrical mobility and mass-to-charge ratio of alpha-pinene oxidation products using a secondary electrospray-differential mobility analyzer-mass spectrometer (SESI-DMA-MS). The mass-mobility spectrum of the oxidation products is measured with seven different reagent ions generated by the electrospray. We analyzed the mobility-mass spectra of the oxidation products C9-10H14-18O2-6. Our results show that acetate and chloride yield the highest charging efficiencies. Analysis of the mobility spectra suggests that the clusters have 1-5 isomeric structures (i.e., ion-molecule cluster structures with distinct mobilities), and the number is affected by the reagent ion. Most of the isomers are likely cluster isomers originating from binding of the reagent ion to different sites of the molecule. By comparing the number of observed isomers and measured mobilities and collision cross sections between standard pinanediol and pinonic acid to the values observed for C10H18O2 and C10H16O3 produced from oxidation of alpha-pinene, we confirm that pinanediol and pinonic acid are the only isomers for these elemental compositions in our experimental conditions. Our study shows that the SESI-DMA-MS produces new information from the first steps of oxidation of alpha-pinene.Peer reviewe

How well can we predict cluster fragmentation inside a mass spectrometer?

Fragmentation of molecular clusters inside mass spectrometers is a significant source of uncertainty in a wide range of chemical applications. We have measured the fragmentation of sulfuric acid clusters driving atmospheric new-particle formation, and developed a novel model, based on first principles calculations, capable of quantitatively predicting the extent of fragmentation.Peer reviewe