High-resolution mass spectrometry (HRMS) has become a vital tool for dissolved organic matter (DOM) characterization. The upward trend in HRMS analysis of DOM presents challenges in data comparison and interpretation among laboratories operating instruments with differing performance and user operating conditions. It is therefore essential that the community establishes metric ranges and compositional trends for data comparison with reference samples so that data can be robustly compared among research groups. To this end, four identically prepared DOM samples were each measured by 16 laboratories, using 17 commercially purchased instruments, using positive-ion and negative-ion mode electrospray ionization (ESI) HRMS analyses. The instruments identified~1000 common ions in both negative-and positive-ion modes over a wide range of m/z values and chemical space, as determined by van Krevelen diagrams. Calculated metrics of abundance-weighted average indices (H/C, O/C, aromaticity, and m/z) of the commonly detected ions showed that hydrogen saturation and aromaticity were consistent for each reference sample across the instruments, while average mass and oxygenation were more affected by differences in instrument type and settings. In this paper we present 32 metric values for future benchmarking. The metric values were obtained for the four different parameters from four samples in two ionization modes and can be used in future work to evaluate the performance of HRMS instruments.

Long‐range transported free tropospheric particles can play a significant role on heterogeneous ice nucleation. Using optical and electron microscopy we examine the physicochemical characteristics of ice nucleating particles (INPs). Particles were collected on substrates from the free troposphere at the remote Pico Mountain Observatory in the Azores Islands, after long‐range transport and aging over the Atlantic Ocean. We investigate four specific events to study the ice formation potential by the collected particles with different ages and transport patterns. We use single‐particle analysis, as well as bulk analysis to characterize particle populations. Both analyses show substantial differences in particle composition between samples from the four events; in addition, single‐particle microscopy analysis indicates that most particles are coated by organic material. The identified INPs contained mixtures of dust, aged sea salt and soot, and organic material acquired either at the source or during transport. The temperature and relative humidity (RH) at which ice formed, varied only by 5% between samples, despite differences in particle composition, sources, and transport patterns. We hypothesize that this small variation in the onset RH may be due to the coating material on the particles. This study underscores and motivates the need to further investigate how long‐range transported and atmospherically aged free tropospheric particles impact ice cloud formation.

Aerosol properties are transformed by atmospheric processes during long-range transport and play a key role in the Earth's radiative balance. To understand the molecular and physical characteristics of free tropospheric aerosol, we studied samples collected at the Pico Mountain Observatory in the North Atlantic. The observatory is located in the marine free troposphere at 2225 m above sea level, on Pico Island in the Azores archipelago. The site is ideal for the study of long-range-transported free tropospheric aerosol with minimal local influence. Three aerosol samples with elevated organic carbon concentrations were selected for detailed analysis. FLEXPART retroplumes indicated that two of the samples were influenced by North American wildfire emissions transported in the free troposphere and one by North American outflow mainly transported within the marine boundary layer. Ultrahigh-resolution Fourier transform ion cyclotron resonance mass spectrometry was used to determine the detailed molecular composition of the samples. Thousands of molecular formulas were assigned to each of the individual samples. On average ∼ 60 % of the molecular formulas contained only carbon, hydrogen, and oxygen atoms (CHO), ∼ 30 % contained nitrogen (CHNO), and ∼ 10 % contained sulfur (CHOS). The molecular formula compositions of the two wildfire-influenced aerosol samples transported mainly in the free troposphere had relatively low average O/C ratios (0.48 ± 0.13 and 0.45 ± 0.11) despite the 7-10 days of transport time according to FLEXPART. In contrast, the molecular composition of the North American out-flow transported mainly in the boundary layer had a higher average O/C ratio (0.57±0.17) with 3 days of transport time. To better understand the difference between free tropospheric transport and boundary layer transport, the meteorological conditions along the FLEXPART simulated transport pathways were extracted from the Global Forecast System analysis for the model grids. We used the extracted meteorological conditions and the observed molecular chemistry to predict the relative-humidity-dependent glass transition temperatures (T g ) of the aerosol components. Comparisons of the T g to the ambient temperature indicated that a majority of the organic aerosol components transported in the free troposphere were more viscous and therefore less susceptible to oxidation than the organic aerosol components transported in the boundary layer. Although the number of observations is limited, the results suggest that biomass burning organic aerosol injected into the free troposphere is more persistent than organic aerosol in the boundary layer having broader implications for aerosol aging.

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The prediction of ice cloud formation in the atmosphere remains challenging. Free tropospheric aerosols can act as ice nucleating particles, affecting cloud properties and precipitation. The physicochemical properties of free tropospheric particles are modified upon long-range transport by different atmospheric processes. These modifications affect the ice formation potential of individual particles. We investigated the physicochemical properties of free tropospheric particles collected at the remote Pico Mountain Observatory at 2225 m a.s.l. in the North Atlantic Ocean using multimodal micro-spectroscopy and chemical imaging techniques. We probed their ice nucleation (IN) activity using an IN stage interfaced with an environmental scanning electron microscope. Retroplume analysis, chemical imaging, and micro-spectroscopy analysis indicated that the size-resolved chemical composition, mixing state, and phase state of the particles with similar aging times but different transport patterns were substantially different. Relative humidity-dependent glass-transition temperatures estimated from meteorological conditions were consistent with the observed organic component of the particles’ phase. More viscous (solid and semi-solid-like) particles are more ice active in the deposition mode at temperatures ranging from 205 to 220 K than less viscous particles. This study provides a better understanding of the phase and mixing state of long-range transported free tropospheric aerosols and their role in ice cloud formation.