8High resolution, high accuracy mass spectrometry is widely used to characterise environmental 9 or biological samples with highly complex composition enabling the identification of chemical 10 composition of often unknown compounds. Despite instrumental advancements, the accurate 11 molecular assignment of compounds acquired in high resolution mass spectra remains time 12consuming and requires automated algorithms, especially for samples covering a wide mass 13 range and large numbers of compounds. A new processing scheme is introduced implementing 14filtering methods based on element assignment, instrumental error, and blank subtraction. 15Optional post-processing incorporates common ion selection across replicate measurements 16and shoulder ion removal. The scheme allows both positive and negative direct infusion 17 electrospray ionisation (ESI) and atmospheric pressure photoionisation (APPI) acquisition with 18 the same programs. An example application to atmospheric organic aerosol samples using an 19Orbitrap mass spectrometer is reported for both ionisation techniques resulting in final spectra 20 with 0.8% and 8.4% of the peaks retained from the raw spectra for APPI positive and ESI 21 negative acquisition, respectively. 22 23 Highlights 24• Ultra-high resolution mass spectrometry processing scheme from acquisition to 25 analysis. 26• Method implementable with APPI and ESI ionisation in both polarities. 27• Example application for environmental samples showing >90% peak filtering. 28 Keywords 29

Current portable particle detection instruments typically rely on optical methods which are limited to 100 nm diameter particles. Microfabricated bulk acoustic resonators, when used as mass balances, could take particle detection below this limit. This study examines the collection of particles onto piezoelectric bulk acoustic mode resonators from gaseous flow using classical impaction. Collection of both polystyrene latex-pinene secondary organic aerosol particles was examined in terms of frequency shift and collection efficiency. A new experimental setup was introduced which allows for adjusting major impactor, resonator, and aerosol properties. Preliminary results show the setup works for both particles while the saturation limit was not reached within an hour despite highly elevated particle concentrations.

Aerosol-cloud interaction contributes to the largest uncertainties in the estimation and interpretation of the Earth’s changing energy budget. The present study explores experimentally the impacts of water condensation-evaporation events, mimicking processes occurring in atmospheric clouds, on the molecular composition of secondary organic aerosol (SOA) from the photooxidation of methacrolein. A range of on- and off-line mass spectrometry techniques were used to obtain a detailed chemical characterization of SOA formed in control experiments in dry conditions, in triphasic experiments simulating gas-particle-cloud droplet interactions (starting from dry conditions and from 60% relative humidity (RH)), and in bulk aqueous-phase experiments. We observed that cloud events trigger fast SOA formation accompanied by evaporative losses. These evaporative losses decreased SOA concentration in the simulation chamber by 25–32% upon RH increase, while aqueous SOA was found to be metastable and slowly evaporated after cloud dissipation. In the simulation chamber, SOA composition measured with a high-resolution time-of-flight aerosol mass spectrometer, did not change during cloud events compared with high RH conditions (RH > 80%). In all experiments, off-line mass spectrometry techniques emphasize the critical role of 2-methylglyceric acid as a major product of isoprene chemistry, as an important contributor to the total SOA mass (15–20%) and as a key building block of oligomers found in the particulate phase. Interestingly, the comparison between the series of oligomers obtained from experiments performed under different conditions show a markedly different reactivity. In particular, long reaction times at high RH seem to create the conditions for aqueous-phase processing to occur in a more efficient manner than during two relatively short cloud events.

The spatial sensitivity of bulk acoustic mode resonators can influence calibrations when they are implemented as accurate mass sensors of surface-bound particles. A new spatial sensitivity model based on images of the resonator surface is introduced from early principles. The adsorption of particles was studied empirically by repeatedly drying particle laden droplets on the surface of two 3.14 MHz bulk acoustic mode resonators. Theoretical and experimental results were compared to identify three scenarios over the course of consecutive droplet evaporation with varying spatial sensitivity influences. Examining different surface treatments for the resonators revealed the hydrophilic surface to have a higher rate of particle stacking and conglomeration.

The interaction between atmospheric aerosol particles and water vapor influences aerosol size, phase, and composition, parameters which critically influence their impacts in the atmosphere. Methods to accurately measure aerosol water uptake for a wide range of particle types are therefore merited. We present here a new method for characterizing aerosol hygroscopicity, an impaction stage containing a microelectromechanical systems (MEMS) microresonator. We find that deliquescence and efflorescence relative humidities (RHs) of sodium chloride and ammonium sulfate are easily diagnosed via changes in resonant frequency and peak sharpness. These agree well with literature values and thermodynamic models. Furthermore, we demonstrate that, unlike other resonator-based techniques, full hygroscopic growth curves can be derived, including for an inorganic-organic mixture (sodium chloride and malonic acid) which remains liquid at all RHs. The response of the microresonator frequency to temperature and particle mechanical properties and the resulting limitations when measuring hygroscopicity are discussed. MEMS resonators show great potential as miniaturized ambient aerosol mass monitors, and future work will consider the applicability of our approach to complex ambient samples. The technique also offers an alternative to established methods for accurate thermodynamic measurements in the laboratory.