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Free tropospheric aerosol particles have important but poorly constrained climate effects due to transformations of their physicochemical properties during long-range transport. In this study, we investigate the chemical composition and provide an overview of the phase states of individual particles that have undergone long-range transport over the North Atlantic Ocean in June and July 2014, 2015, and 2017 to the Observatory of Mount Pico (OMP) in the Azores. The OMP is an ideal site for studying long-range-transported free tropospheric particles because local emissions have a negligible influence and contributions from the boundary layer are rare. We used the FLEXible PARTicle Lagrangian particle dispersion model (FLEXPART) to determine the origins and transport trajectories of sampled air masses and found that most of them originated from North America and recirculated over the North Atlantic Ocean. The FLEXPART analysis showed that the sampled air masses were highly aged (average plume age >10 d). Size-resolved chemical compositions of individual particles were probed using computer-controlled scanning electron microscopy with an energy-dispersive X-ray spectrometer (CCSEM-EDX) and scanning transmission X-ray microscopy with near-edge X-ray absorption fine structure spectroscopy (STXM-NEXAFS). CCSEM-EDX results showed that the most abundant particle types were carbonaceous (∼ 29.9 % to 82.0 %), sea salt (∼ 0.3 % to 31.6 %), and sea salt with sulfate (∼ 2.4 % to 31.5 %). We used a tilted stage interfaced within an environmental scanning electron microscope (ESEM) to determine the phase states of individual submicron particles. We found that most particles (∼ 47 % to 99 %) were in the liquid state at the time of collection due to inorganic inclusions. Moreover, we also observed substantial fractions of solid and semisolid particles (∼ 0 % to 30 % and ∼ 1 % to 42 %, respectively) during different transport patterns and events, reflecting the particles' phase-state variability for different atmospheric transport events and sources. Combining phase state measurements with FLEXPART CO tracer analysis, we found that wildfire-influenced plumes can result in particles with a wide range of viscosities after long-range transport in the free troposphere. We also used temperature and RH values extracted from the Global Forecast System (GFS) along the FLEXPART-simulated path to predict the phase state of the particles during transport and found that neglecting internal mixing with inorganics would lead to an overestimation of the viscosity of free tropospheric particles. Our findings warrant future investigation aiming at the quantitative assessment of the influence of internal mixing on the phase states of the individual particles. This study also provides insights into the chemical composition and phase state of free tropospheric particles, which can help models to reduce uncertainties about the effects of ambient aerosol particles on climate.

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 physic...

Free tropospheric aerosol particles have important but poorly constrained climate effects due to transformations of their physicochemical properties during long-range transport. In this study, we investigated the chemical composition and provided an overview of the phase state of individual particles that have been long-range transported over the North Atlantic Ocean in June and July 2014, 2015, and 2017 to the Observatory of Mount Pico (OMP), in the Azores. OMP is an ideal site for studying long-range transported free tropospheric particles with negligible influence from local emissions and rare contributions from the boundary layer. We used the FLEXible PARTicle Lagrangian particle dispersion model (FLEXPART) to determine the origin and transport trajectories of sampled air masses and found that most originated from North America and recirculated over the North Atlantic Ocean. The FLEXPART analysis show that the sampled air masses were highly aged (average plume age > 10 days). Size-resolved chemical compositions of individual particles were probed using computer-controlled scanning electron microscopy with an energy dispersive X-ray spectrometer (CCSEM-EDX) and scanning transmission X-ray microscopy with near-edge X-ray absorption fine structure spectroscopy (STXM-NEXAFS). CCSEM-EDX results show that the most abundant particle types were carbonaceous (~29.9 to 82.0 %), sea salt (~0.3 to 31.6 %), and sea salt with sulfate (~2.4 to 31.5 %). We used a tilted stage interfaced within an Environmental Scanning Electron Microscope (ESEM) to determine the phase state of individual submicron particles. We found that most particles (~47 to 99 %) were in the liquid state at the time of collection due to inorganic inclusions. Moreover, we also observed a substantial fraction of solid and semisolid particles (~0 to 30 % and ~1 to 42 %, respectively) during different transport patterns/events, reflecting the particles' phase state variability for different atmospheric transport events and sources. Combining phase state measurements with FLEXPART CO tracer analysis, we found that wildfire-influenced plumes can result in particles with a wide range of viscosities after long-range transport in the free troposphere. We also used temperature and RH values extracted from the Global Forecast System (GFS) along the FLEXPART simulated path to predict the phase state of the particles during transport and found that neglecting internal mixing with inorganics would overestimate the viscosity of free tropospheric particles. Our findings warrant future investigation on the quantitative assessment of the influence of internal mixing on the phase state of the individual particles. This study also provides insights into the chemical composition and phase state of free tropospheric particles, which can benefit models to reduce uncertainties in ambient aerosol particles' effects on climate.

We report on the Azores Stratocumulus Measurements of Radiation, Turbulence and Aerosols (ACORES) campaign, which took place around Graciosa and Pico Islands/Azores in July 2017. The main objective was to investigate the vertical distribution of aerosol particles, stratocumulus microphysical and radiative properties, and turbulence parameters in the eastern North Atlantic. The vertical exchange of mass, momentum, and energy between the free troposphere (FT) and the cloudy marine boundary layer (MBL) was explored over a range of scales from submeters to kilometers. To cover these spatial scales with appropriate measurements, helicopter-borne observations with unprecedented high resolution were realized using the Airborne Cloud Turbulence Observation System (ACTOS) and Spectral Modular Airborne Radiation Measurement System–Helicopter-Borne Observations (SMART-HELIOS) instrumental payloads. The helicopter-borne observations were combined with ground-based aerosol measurements collected at two continuously running field stations on Pico Mountain (2,225 m above sea level, in the FT), and at the Atmospheric Radiation Measurement (ARM) station on Graciosa (at sea level). First findings from the ACORES observations we are discussing in the paper are as follows: (i) we have observed a high variability of the turbulent cloud-top structure on horizontal scales below 100 m with local temperature gradients of up to 4 K over less than 1 m vertical distance, (ii) we have collected strictly collocated radiation measurements supporting the relevance of small-scale processes by revealing significant inhomogeneities in cloud-top brightness temperature to scales well below 100 m, and (iii) we have concluded that aerosol properties are completely different in the MBL and FT with often-complex stratification and frequently observed burst-like new particle formation.

Ultrahigh resolution mass spectrometry is widely used for nontargeted analysis of complex environmental and biological mixtures, such as dissolved organic matter, due to its unparalleled ability to provide accurate mass measurements. Accurate and efficient characterization of these mixtures is critical to being better able to evaluate their effect on human health and climate. This characterization requires accurate mass signals free from isobaric interferences, instrument noise, and mass measurement biases, allowing for molecular formula identification. To address this need, an open source post-processing pipeline for ultrahigh resolution mass spectra of environmental complex mixtures software was developed. MFAssignR contains functions that perform noise estimation, 13C and 34S polyisotopic mass filtering, mass measurement recalibration, and molecular formula assignment as part of a consistent data processing environment. Novel applications of mass defect analysis were used in the functions for noise estimation and isotope pair identification. Using formula extensions, exact mass measurements are converted to unambiguous molecular formulas via data dependent pathways, reducing a priori decisions. Optional molecular formula ambiguity and multiple non-oxygen heteroatoms are provided for custom user applications, including isotopically labeled reactive species, halogen-containing species, or tandem ultrahigh resolution mass spectrometry. This represents uncommon flexibility for an open-source software package. To evaluate the performance of MFAssignR, it was used to characterize a sample of biomass burning influenced organic aerosol and the results were compared to those from other available methods of molecular formula assignment and noise estimation. The differences between the methods are described here. Overall, the inclusion of a full pipeline of data preparation functions and the data-dependent ambiguity reductions in MFAssignR render excellent results and make MFAssignR well-suited for the consistent and efficient analysis of environmental complex mixtures. MFAssignR is publicly available via GitHub.

Fresh and atmospherically aged biomass-burning (BB) aerosol mass is mostly comprised of strongly light-absorbing black carbon (BC) and of organic carbon (OC) with its light-absorbing fraction – brown carbon (BrC). There is a lack of data on the physical and chemical properties of atmospheric BB aerosols, leading to high uncertainties in estimates of the BB impact on air quality and climate, especially for BrC. The polarity of chemical compounds influences their fate in the atmosphere including wet/dry deposition and chemical and physical processing. So far, most of the attention has been given to the water-soluble (polar) fraction of BrC, while the non-polar BrC fraction has been largely ignored. In the present study, the light absorption properties of polar and non-polar fractions of fresh and aged BB emissions were examined to estimate the contribution of different-polarity organic compounds to the light absorption properties of BB aerosols. In our experiments, four globally and regionally important fuels were burned under flaming and smoldering conditions in the Desert Research Institute (DRI) combustion chamber. To mimic atmospheric oxidation processes (5–7 days), BB emissions were aged using an oxidation flow reactor (OFR). Fresh and OFR-aged BB aerosols were collected on filters and extracted with water and hexane to study absorption properties of polar and non-polar organic species. Results of spectrophotometric measurements (absorption weighted by the solar spectrum and normalized to mass of fuel consumed) over the 190 to 900 nm wavelength range showed that the non-polar (hexane-soluble) fraction is 2–3 times more absorbing than the polar (water-soluble) fraction. However, for emissions from fuels that undergo flaming combustion, an increased absorbance was observed for the water extracts of oxidized/aged emissions while the absorption of the hexane extracts was lower for the aged emissions for the same type of fuels. Absorption Ångström exponent (AAE) values, computed based on absorbance values from spectrophotometer measurements, were changed with aging and the nature of this change was fuel dependent. The light absorption by humic-like substances (HULIS) was found to be higher in fuels characteristic of the southwestern USA. The absorption of the HULIS fraction was lower for OFR-aged BB emissions. Comparison of the light absorption properties of different-polarity extracts (water, hexane, HULIS) provides insight into the chemical nature of BB BrC and its transformation during oxidation processes.

Two separate liquid chromatography (LC)-mass spectrometry (MS) methods were developed for determination and quantification of water-soluble and fat-soluble vitamins in human tear and blood serum samples. The water-soluble vitamin method was originally developed to detect vitamins B1, B2, B3 (nicotinamide), B5, B6 (pyridoxine), B7, B9 and B12 while the fat-soluble vitamin method detected vitamins A, D3, 25(OH)D3, E and K1. These methods were then validated with tear and blood serum samples. In this data in brief article, we provide details on the two LC-MS methods development, methods sensitivity, as well as precision and accuracy for determination of vitamins in human tears and blood serum. These methods were then used to determine the vitamin concentrations in infant and parent samples under a clinical study which were reported in "Determination of Water-Soluble and Fat-Soluble Vitamins in Tears and Blood Serum of Infants and Parents by Liquid Chromatography/Mass Spectrometry DOI:10.1016/j.exer.2016.12.007 [1]". This article provides more details on comparison of vitamin concentrations in the samples with the ranges reported in the literature along with the medically accepted normal ranges. The details on concentrations below the limits of detection (LOD) and limits of quantification (LOQ) are also discussed. Vitamin concentrations were also compared and cross-correlated with clinical data and nutritional information. Significant differences and strongly correlated data were reported in [1]. This article provides comprehensive details on the data with slight differences or slight correlations.

We studied the molecular formula composition of six β-caryophyllene SOA samples using ultrahigh resolution Fourier transform ion cyclotron resonance mass spectrometry under various reaction conditions. The SOA samples were generated in dry or low relative humidity (RH) chamber conditions with or without cyclohexane. All of the studied SOA mass spectra have three distinct clusters of hundreds of negative ions referred to as Group I (100

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.

Tears serve as a viable diagnostic fluid with advantages including less invasive sample to collect and less complex to prepare for analysis. Several water-soluble and fat-soluble vitamins were detected and quantified in human tears and compared with blood serum levels. Samples from 15 family pairs, each pair consisting of a four-month-old infant and one parent were analyzed; vitamin concentrations were compared between tears and blood serum for individual subjects, between infants and parents, and against self-reported dietary intakes. Water-soluble vitamins B1, B2, B3 (nicotinamide), B5, B9 and fat-soluble vitamin E (α-tocopherol) were routinely detected in tears and blood serum while fat-soluble vitamin A (retinol) was detected only in blood serum. Water-soluble vitamin concentrations measured in tears and blood serum of single subjects were comparable, while higher concentrations were measured in infants compared to their parents. Fat-soluble vitamin E concentrations were lower in tears than blood serum with no significant difference between infants and parents. Serum vitamin A concentrations were higher in parents than infants. Population trends were compiled and quantified using a cross correlation factor. Strong positive correlations were found between tear and blood serum concentrations of vitamin E from infants and parents and vitamin B3 concentrations from parents, while slight positive correlations were detected for infants B3 and parents B1 and B2 concentrations. Correlations between infants and parents were found for the concentrations of B1, B2, B3, and E in tears, and the concentrations of B2, A, and E in blood serum. Stronger vitamin concentration correlations were found between infants and parents for the breast-fed infants, while no significant difference was observed between breast-fed and bottle-fed infants. This work is the first to demonstrate simultaneous vitamin A, B, and E detection and to quantify correlations between vitamin concentrations in tears and blood serum. Our results suggest that tears are a viable biofluid to monitor nutritional health because they sufficiently mirror blood serum data and may enhance the speed of deficiency diagnoses.

Due to the atmospheric abundance and chemical complexity of water soluble organic carbon (WSOC), its contribution to the hydration behavior of atmospheric aerosol is both significant and difficult to assess. For the present study, the hygroscopicity and CCN activity of isolated atmospheric WSOC particulate matter was measured without the compounding effects of common, soluble inorganic aerosol constituents. WSOC was extracted with high purity water from daily high-volume PM2.5 filter samples and separated from water soluble inorganic constituents using solid-phase extraction. The WSOC filter extracts were concentrated and combined to provide sufficient mass for continuous generation of the WSOC-only aerosol over the combined measurement time of the tandem differential mobility analyzer and coupled scanning mobility particle sizer–CCN counter used for the analysis. Aerosol samples were taken at Great Smoky Mountains National Park during the summer of 2006 and fall–winter of 2007–2008; Mount Rainier National Park during the summer of 2009; Storm Peak Laboratory (SPL) near Steamboat Springs, Colorado, during the summer of 2010; and Acadia National Park during the summer of 2011. Across all sampling locations and seasons, the hygroscopic growth of WSOC samples at 90 % RH, expressed in terms of the hygroscopicity parameter, κ, ranged from 0.05 to 0.15. Comparisons between the hygroscopicity of WSOC and that of samples containing all soluble materials extracted from the filters implied a significant modification of the hydration behavior of inorganic components, including decreased hysteresis separating efflorescence and deliquescence and enhanced water uptake between 30 and 70 % RH.

Soot particles form during combustion of carbonaceous materials and impact climate and air quality. When freshly emitted, they are typically fractal-like aggregates. After atmospheric aging, they can act as cloud condensation nuclei, and water condensation or evaporation restructure them to more compact aggregates, affecting their optical, aerodynamic, and surface properties. Here we survey the morphology of ambient soot particles from various locations and different environmental and aging conditions. We used electron microscopy and show extensive soot compaction after cloud processing. We further performed laboratory experiments to simulate atmospheric cloud processing under controlled conditions. We find that soot particles sampled after evaporating the cloud droplets, are significantly more compact than freshly emitted and interstitial soot, confirming that cloud processing, not just exposure to high humidity, compacts soot. Our findings have implications for how the radiative, surface, and aerodynamic properties, and the fate of soot particles are represented in numerical models.

A detailed understanding of interactions of aerosols, cloud droplets/ice crystals, and trace gases within the atmosphere is of prime importance for an accurate understanding of Earth’s weather and climate. One aspect that remains especially vexing is that clouds are ubiquitously turbulent, and therefore thermodynamic and compositional variables, such as water vapor supersaturation, fluctuate in space and time. With these problems in mind, a multiphase, turbulent reaction chamber—called the Π chamber because of the internal volume of 3.14 m3 with the cylindrical insert installed—has been developed. It is capable of pressures ranging from 1,000 to –60 hPa and can sustain temperatures of –55° to 55°C, thereby spanning much of the range of tropospheric clouds. To control the relative humidity in the chamber, it can be operated with a stable, unstable, or neutral temperature difference between the top and bottom surfaces, with or without expansion. A negative temperature difference induces turbulent Rayleigh–Bénard convection and associated supersaturation generation through isobaric mixing. Supporting instrumentation includes a suite of aerosol generation and characterization techniques; temperature, pressure, and humidity sensors; and a phase Doppler interferometer. Initial characterization experiments demonstrate the ability to sustain steady-state turbulent cloud conditions for times greater than 1 day, with droplet diameters typically in the range of 5–40 µm. Typical turbulence has root-mean-square velocity fluctuations on the order of 10 cm s–1 and kinetic energy dissipation rates of 1 × 10–3 W kg–1.

Free tropospheric aerosol was sampled at the Pico Mountain Observatory located at 2225 m above mean sea level on Pico Island of the Azores archipelago in the North Atlantic. The observatory is located ~ 3900 km east and downwind of North America, which enables studies of free tropospheric air transported over long distances. Aerosol samples collected on filters from June to October 2012 were analyzed to characterize organic carbon, elemental carbon, and inorganic ions. The average ambient concentration of aerosol was 0.9 ± 0.7 μg m−3. On average, organic aerosol components represent the largest mass fraction of the total measured aerosol (60 ± 51%), followed by sulfate (23 ± 28%), nitrate (13 ± 10%), chloride (2 ± 3%), and elemental carbon (2 ± 2%). Water-soluble organic matter (WSOM) extracted from two aerosol samples (9/24 and 9/25) collected consecutively during a pollution event were analyzed using ultrahigh-resolution electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry. Approximately 4000 molecular formulas were assigned to each of the mass spectra in the range of m/z 100–1000. The majority of the assigned molecular formulas had unsaturated structures with CHO and CHNO elemental compositions. FLEXPART retroplume analyses showed the sampled air masses were very aged (average plume age > 12 days). These aged aerosol WSOM compounds had an average O/C ratio of ~ 0.45, which is relatively low compared to O/C ratios of other aged aerosol. The increase in aerosol loading during the measurement period of 9/24 was linked to biomass burning emissions from North America by FLEXPART retroplume analysis and Moderate Resolution Imaging Spectroradiometer (MODIS) fire counts. This was confirmed with biomass burning markers detected in the WSOM and with the morphology and mixing state of particles as determined by scanning electron microscopy. The presence of markers characteristic of aqueous-phase reactions of phenolic species suggests that the aerosol collected at the Pico Mountain Observatory had undergone cloud processing before reaching the site. Finally, the air masses of 9/25 were more aged and influenced by marine emissions, as indicated by the presence of organosulfates and other species characteristic of marine aerosol. The change in the air masses for the two samples was corroborated by the changes in ethane, propane, and ozone, morphology of particles, as well as by the FLEXPART retroplume simulations. This paper presents the first detailed molecular characterization of free tropospheric aged aerosol intercepted at a lower free troposphere remote location and provides evidence of low oxygenation after long-range transport. We hypothesize this is a result of the selective removal of highly aged and polar species during long-range transport, because the aerosol underwent a combination of atmospheric processes during transport facilitating aqueous-phase removal (e.g., clouds processing) and fragmentation (e.g., photolysis) of components.

Considering the increasing identification of trace organic contaminants in natural aquatic environments, the removal of trace organic contaminants from water or wastewater discharge is an urgent task. Ultraviolet (UV) and UV-based advanced oxidation processes (AOPs), such as UV/hydrogen peroxide (UV/H2O2), UV/free chlorine and UV/persulfate, are attractive and promising approaches for the removal of these contaminants due to the high reactivity of active radical species produced in these UV-AOPs with a wide variety of organic contaminants. However, the removal efficiency of trace contaminants is greatly affected by the presence of background dissolved organic matter (DOM). In this study, we use ultrahigh resolution mass spectrometry to evaluate the transformation of a standard Suwanee River fulvic acid DOM isolate in UV photolysis and UV-AOPs. The use of probe compounds allows for the determination of the steady-state concentrations of active radical species in each UV-AOP. The changes in the H/C and O/C elemental ratios, double bond equivalents, and the low-molecular-weight transformation product concentrations of organic acids reveal that different DOM transformation patterns are induced by each UV-AOP. By comparison with the known reactivities of each radical species with specific organic compounds, we mechanistically and systematically elucidate the molecular-level DOM transformation pathways induced by hydroxyl, chlorine, and sulfate radicals in UV-AOPs. We find that there is a distinct transformation in the aliphatic components of DOM due to HO• in UV/H2O2 and UV/free chlorine. Cl• induced transformation of olefinic species is also observed in the UV/free chlorine system. Transformation of aromatic and olefinic moieties by SO4•- are the predominant pathways in the UV/persulfate system.

Ten-year observations of trace gases at Pico Mountain Observatory (PMO), a free troposphere site in the central North Atlantic, were classified by transport patterns using the Lagrangian particle dispersion model, FLEXPART. The classification enabled identifying trace gas mixing ratios associated with background air and long- range transport of continental emissions, which were defined as chemical signatures. Comparison between the chemical signatures revealed the impacts of natural and anthropogenic sources, as well as chemical and physical processes during long transport,on air composition in the remote North Atlantic. Transport of North American anthropogenic emissions(NA-Anthro) and summertime wildfire plumes (Fire) significantly enhanced CO and O3 at PMO. Summertime CO enhancements caused by NA-Anthro were found to have been decreasing by a rate of 0.67 ± 0.60 ppbv/year in the ten-year period, due possibly to reduction of emissions in North America. Downward mixing from the upper troposphere and stratosphere due to the persistent Azores-Bermuda anticyclone causes enhanced O3 and nitrogen oxides. The d[O3]/d [CO] value was used to investigate O3 sources and chemistry in different transport patterns. The transport pattern affected by Fire had the lowest d [O3]/d [CO], which was likely due to intense CO production and depressed O3 production in wildfire plumes. Slightly enhanced O3 and d [O3]/d [CO] were found in the background air, suggesting that weak downward mixing from the upper troposphere is common at PMO. Enhancements of both butane isomers were found during upslope flow periods, indicating contributions from local sources. The consistent ratio of butane isomers associated with the background air and NA-anthro implies no clear difference in the oxidation rates of the butane isomers during long transport. Based on observed relationships between non-methane hydrocarbons, the averaged photochemical age of the air masses at PMO was estimated to be 11 ± 4 days.

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Studies conducted across northern Europe and North America have shown increases in dissolved organic carbon (DOC) in aquatic systems in recent decades. While there is little consensus as to the exact mechanisms for the increases in DOC, hypotheses converge on such climate change factors as warming, increased precipitation variability, and changes in atmospheric deposition. In this study, we tested the effects of warming on peat porewater composition by actively warming a peatland with infrared lamps mounted 1.24 m above the peat surface for 3 years. Mean growing season peat temperatures in the warmed plots (n = 5) were 1.9 ± 0.4 °C warmer than the control plots at 5 cm depth (t statistic = 5.03, p = 0.007). Mean porewater DOC concentrations measured throughout the growing season were 15 % higher in the warmed plots (73.4 ± 3.2 mg L−1) than in the control plots (63.7 ± 2.1 mg L−1) at 25 cm (t = 4.69, p

Clouds alter the composition of atmospheric aerosol by acting as a medium for interactions between gas- and particulate-phase substances. To determine the cloud water atmospheric organic matter (AOM) composition and study the cloud processing of aerosols, two samples of supercooled clouds were collected at the Storm Peak Laboratory near Steamboat Springs, Colorado (3220 m a.s.l.). Approximately 3000 molecular formulas were assigned to ultrahigh-resolution mass spectra of the samples after using a reversed-phase extraction procedure to isolate the AOM components from the cloud water. Nitrogen-containing compounds (CHNO compounds), sulfur-containing compounds (CHOS and CHNOS compounds) and other oxygen-containing compounds (CHO compounds) with molecular weights up to 700 Da were observed. Average oxygen-to-carbon ratios of ∼0.6 indicate a slightly more oxidized composition than most water-soluble organic carbon identified in aerosol studies, which may result from aqueous oxidation in the clouds. The AOM composition indicates significant influences from biogenic secondary organic aerosol (SOA) and residential wood combustion. We observed 60% of the cloud water CHO molecular formulas to be identical to SOA samples of α-pinene, β-pinene, d-limonene, and β-caryophyllene ozonolysis. CHNO compounds had the highest number frequency and relative abundances and are associated with residential wood combustion and NOx oxidation. Multiple nitrogen atoms in the assigned molecular formulas for the nighttime cloud sample composite were observed, indicating the significance of nitrate radical reactions on the AOM composition. Several CHOS and CHNOS compounds with reduced sulfur (in addition to the commonly observed oxidized sulfur-containing compounds) were also observed; however further investigation is needed to determine the origin of the reduced sulfur-containing compounds. Overall, the molecular composition determined using ultrahigh-resolution Fourier-transform ion cyclotron resonance (FT-ICR) mass spectrometry provides an unambiguous identification of the cloud water organic anion composition in the Rocky Mountain area that could help to improve the understanding of aqueous-phase processes.

[1] A combined field and laboratory study was conducted to improve our understanding of the chemical and hygroscopic properties of organic compounds in aerosols sampled in the background continental atmosphere. PM2.5 (particles with aerodynamic diameters smaller than 2.5 µm) aerosols were collected from 24 June to 28 July 2010 at Storm Peak Laboratory (SPL) in the Park Range of northwestern Colorado. New particle formation (NPF) was frequent at SPL during this campaign, and the samples were not influenced by regional dust storms. Filter samples were analyzed for organic carbon (OC) and elemental carbon (EC), water soluble OC (WSOC), major inorganic ions, and detailed organic speciation. WSOC was isolated from inorganic ions using solid phase absorbents. Hygroscopic growth factors (GFs) and cloud condensation nucleus (CCN) activity of the WSOC were measured in the laboratory. Organic compounds compose the majority (average of 64% with a standard deviation (SD) of 9%) of the mass of measured species and WSOC accounted for an average of 89% (with a SD of 21%) of OC mass. Daily samples were composited according to back trajectories. On average, organic acids, sugars, and sugar alcohols accounted for 12.5 ± 6.2% (average ± SD) of WSOC. Based on the composition of these compounds and that of high molecular weight compounds identified using ultra high resolution mass spectrometry, the organic mass to OC ratio of the WSOC is estimated to be 2.04. The average hygroscopic GFs at RH = 80% (GF80) were 1.10 ± 0.03 for particles derived from isolated WSOC and 1.27 ± 0.03 for particles derived from the total water-soluble material (WSM). CCN activity followed a similar pattern. The critical diameters at a super-saturation of 0.35% were 0.072 ± 0.009 and 0.094 ± 0.006 µm for particles derived from WSM and isolated WSOC, respectively. These GF results compare favorably with estimates from thermodynamic models, which explicitly relate the water activity (RH) to concentration for the total soluble material identified in this study.

The detailed molecular composition of secondary organic aerosols (SOA) from limonene ozonolysis was studied using ultrahigh-resolution Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry. High molecular weight (MW) compounds (m/z > 300) were found to constitute a significant number fraction of the identified SOA components. Double bond equivalents (DBE = the number of rings plus the number of double bonds) increased with MW. The O:C ratios and relative abundances of compounds decreased with increasing MW. The mass spectra of limonene contain 4 distinct clusters of negative ions: Group I (140 < m/z < 300), Group II (300 < m/z < 500), Group III (500 < m/z < 700) and Group IV (700 < m/z < 850). A number of CH2 and O homologous series of low MW SOA (Group 1) with carbon number 7–15 and oxygen number 3–9 were observed. Their occurrence can be explained with isomerization and elimination reactions of Criegee radicals, reactions between alkyl peroxy radicals, and scission of alkoxy radicals resulting from the Criegee radicals. Additionally, fragmentation analysis and observations of formaldehyde homologous series provide evidence for aerosol growth by the reactive uptake of generated gas-phase carbonyls in limonene ozonolysis. The decreasing O:C ratios between group of compounds indicated the importance of condensation (aldol and esterification) reaction pathways for high MW compound formation. However, the prominent DBE changes of 2 between the groups of compounds and selected fragmentation (MS/MS) analysis of Group II and Group III ions indicated a predominance of non-condensation (hydroperoxide, Criegee and hemi-acetal) reaction pathways. A reaction matrix created with the combination of low MW SOA, hydroperoxides, and Criegee radicals indicated higher frequencies for the hemi-acetal and condensation reaction pathways. Overall, the combined approach confirms the importance of non-condensation reaction pathways over condensation reaction pathways. Among the non-condensation reaction pathways, hemi-acetal reactions appear to be most dominant followed by hydroperoxide and Criegee reactions.

Isolated water-soluble atmospheric organic matter (AOM) analytes extracted from radiation fogwater samples were analyzed using collision induced dissociation with ultrahigh-resolution Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS). Tandem mass analysis was performed on several mass ranges between 100 and 400 Da to characterize the functional groups of AOM species. Compounds containing nitrogen and/or sulfur were targeted because of the high number of oxygen atoms contained in their molecular formulas. Due to the large number of isobaric ions in the precursor isolation ranges, large numbers of product ions resulted from collision induced dissociation. Common neutral losses were assigned by matching the molecular formulas of the expected product ions with the detected product ions within the appropriate mass spectra. Since polar functional groups are expected to affect the hygroscopic properties of aerosols, the losses of H(2)O, CO(2), CH(3)OH, HNO(3), CH(3)NO(3), SO(3), SO(4) and combinations of these were specifically targeted. Among the 421 compounds studied, the most frequently observed neutral losses were CO(2) (54%), H(2)O (43%) and CH(3)OH (40%). HNO(3) losses were observed for 63% of the studied nitrogen containing compounds and 33% of the studied compounds containing both nitrogen and sulfur. SO(3) losses were observed for 85% of the studied sulfur containing compounds and 42% of studied compounds containing both nitrogen and sulfur. A number of molecular formulas matching those of monoterpene ozonolysis SOA were observed; they include organonitrates, organosulfates, and nitroxy-organosulfates. Overall, the results of fragmentation analysis of 400+ individual molecular precursors elucidate the complexity and multifunctional nature of the isolated water-soluble AOM.

Secondary organic aerosol (SOA) of α-pinene ozonolysis with and without hydroxyl radical scavenging hexane was characterized by ultrahigh-resolution Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS). Molecular formulas for more than 900 negative ions were identified over the mass range of 100–850 u. Hydroxyl radicals formed during the ozonolysis of α-pinene might be expected to alter the composition of SOA, however a majority of the molecular formulas were identified in all three experiments and with a few exceptions they had similar relative abundances. Thus, the detailed composition of SOA was only slightly influenced by the presence or absence of hydroxyl radical scavenging hexane. The negative-ion mass spectra of the SOA contained four groups of peaks with increasing mass spectral complexity corresponding to increasing molecular weight. The mean values of O:C decreased from 0.55 to 0.42 with increasing molecular weight, but the mean value of H:C, approximately 1.5, did not change with increasing molecular weight. The molecular formulas with the highest relative abundances in Groups I and II contained 5–7 and 7–10 oxygen atoms and 3–4 and 5–7 double bond equivalents, respectively. The molecular formulas with the highest relative abundances in Groups III and IV contained 10–13 and 13–16 oxygen atoms and 7–9 and 9–11 double bond equivalents, respectively. Observations of the oxygen content and the double bond equivalents of the SOA products suggest a complex mixture of accretion reaction mechanisms, without an easily confirmable dominating pathway.

Water extracts of atmospheric particulate matter (PM 2.5 ) collected at the Storm Peak Laboratory (SPL) (3210 MSL, 40.45° N, 106.74° W) were analyzed for a wide variety of polar organic compounds. The unique geographical character of SPL allows for extended observations/sampling of the free tropospheric interface. Under variable meteorological conditions between January 9th and January14th 2007, the most abundant compounds were levoglucosan (9–72 ng m −3 ), palmitic acid (10–40 ng m −3 ) and succinic acid (18–27 ng m −3 ). Of 84 analytes included in the GC–MS method, over 50 individual water extractable polar organic compounds (POC) were present at concentrations greater than 0.1 ng m −3 . During a snow event (Jan. 11th–13th), the concentrations of several presumed atmospheric transformation compounds (dicarboxylic acids) were reduced. Lower actinic flux, reduced transport distance, and ice crystal scavenging may explain this variability. Diurnal averages over the sampling period revealed a higher total concentration of water extractable POC at night, 211 ng m −3 (105–265 ng m −3 ), versus day, 160 ng m −3 (137–205 ng m −3 ), which suggests a more aged nighttime aerosol character. This may be due to the increased daytime convective mixing of local primary emissions from the Yampa Valley. XAD resin extracts revealed a gas-phase partitioning of several compounds, and analysis of cloud water collected at this site in 2002 revealed a similar compound abundance trend. Levoglucosan, a wood smoke tracer was generally found to be the most abundant compound in both aerosol and cloud water samples. Variations in meteorological parameters and local/regional transport analysis play an important interpretive role in understanding these results.

The U.S. Department of Energy Gasoline/Diesel PM Split Study examined the sources of uncertainties in using an organic compound-based chemical mass balance receptor model to quantify the contributions of spark-ignition (SI) and compression-ignition (CI) engine exhaust to ambient fine particulate matter (PM2.5). This paper presents the chemical composition profiles of SI and CI engine exhaust from the vehicle-testing portion of the study. Chemical analysis of source samples consisted of gravimetric mass, elements, ions, organic carbon (OC), and elemental carbon (EC) by the Interagency Monitoring of Protected Visual Environments (IMPROVE) and Speciation Trends Network (STN) thermal/optical methods, polycyclic aromatic hydrocarbons (PAHs), hopanes, steranes, alkanes, and polar organic compounds. More than half of the mass of carbonaceous particles emitted by heavy-duty diesel trucks was EC (IMPROVE) and emissions from SI vehicles contained predominantly OC. Although total carbon (TC) by the IMPROVE and STN protocols agreed well for all of the samples, the STN/IMPROVE ratios for EC from SI exhaust decreased with decreasing sample loading. SI vehicles, whether low or high emitters, emitted greater amounts of high-molecular-weight particulate PAHs (benzo[ghi]perylene, indeno[1,2,3-cd]pyrene, and coronene) than did CI vehicles. Diesel emissions contained higher abundances of two- to four-ring semivolatile PAHs. Diacids were emitted by CI vehicles but are also prevalent in secondary organic aerosols, so they cannot be considered unique tracers. Hopanes and steranes were present in lubricating oil with similar composition for both gasoline and diesel vehicles and were negligible in gasoline or diesel fuels. CI vehicles emitted greater total amounts of hopanes and steranes on a mass per mile basis, but abundances were comparable to SI exhaust normalized to TC emissions within measurement uncertainty. The combustion-produced high-molecular-weight PAHs were found in used gasoline motor oil but not in fresh oil and are negligible in used diesel engine oil. The contributions of lubrication oils to abundances of these PAHs in the exhaust were large in some cases and were variable with the age and consumption rate of the oil. These factors contributed to the observed variations in their abundances to total carbon or PM2.5 among the SI composition profiles.

Sources of PM2.5 at the Fresno Supersite during high PM2.5 episodes occurring from 15 December 2000–3 February 2001 were estimated with the Chemical Mass Balance (CMB) receptor model. The ability of source profiles with organic markers to distinguish motor vehicle, residential wood combustion (RWC), and cooking emissions was evaluated with simulated data. Organics improved the distinction between gasoline and diesel vehicle emissions and allowed a more precise estimate of the cooking source contribution. Sensitivity tests using average ambient concentrations showed that the gasoline vehicle contribution was not resolved without organics. Organics were not required to estimate hardwood contributions. The most important RWC marker was the water-soluble potassium ion. The estimated cooking contribution did not depend on cholesterol because its concentrations were below the detection limit in most samples. Winter time source contributions were estimated by applying the CMB model to individual and average sample concentrations. RWC was the largest source, contributing 29–31% of measured PM2.5. Hardwood and softwood combustion accounted for 16–17% and 12–15%, respectively. Secondary ammonium nitrate and motor vehicle emissions accounted for 31–33% and 9–15%, respectively. The gasoline vehicle contribution (3–10%) was comparable to the diesel vehicle contribution (5–6%). The cooking contribution was 5–19% of PM2.5. Fresno source apportionment results were consistent with those estimated in previous studies.

A record spanning ten years of non-methane hydrocarbon (NMHC) data from the Pico Mountain Observatory (PMO), Pico Island, Azores, Portugal, was analyzed for seasonal NMHC behavior, atmospheric processing, and trends, focusing on ethane and propane. The location of this site in the central North Atlantic, at an elevation of 2225 m asl, allows these data to be used to investigate the background conditions and pollution transport events occurring in the lower free North Atlantic troposphere. The quantity ln([propane]/[ethane]) was used as an indicator of both photochemical processing and a marker for the occurrence of pollution transport events detected at the station. The Pico data were compared with three other continuous NMHC data sets from sites bordering the North Atlantic, i.e. the Global Atmospheric Watch (GAW) stations at Summit, Greenland, Hohenpeisssenberg, Germany, and Cape Verde, using ln([propane]/[ethane]) results as an indicator for the degree of photochemical processing (‘aging’) seen in the data. Comparisons of these three data sets showed some significant differences in the seasonal background and range of observed values. The statistical distribution of binned monthly data was determined, and individual sample events were then scaled to the monthly median observed value. Back trajectories, determined by the HYSPLIT model were used to investigate the geographic origin of the observed trace gases as a function of the degree of photochemical processing. Results show that PMO samples have been subjected to a diversity of air transport and aging, from highly processed air to freshly emitted air throughout the year, and in particular during summer months. The predominant air transport is from North America, with only occasional influence from continental areas located east and southeast (Europe and Africa). The available record was found to be too variable and still too short to allow deciphering NMHC trends from the data. Ethane and propane measurements at the PMO were compared with the MOZART-4 atmospheric chemistry and transport model at the appropriate time and location. The model was found to yield good agreement in the description of the lower range of atmospheric mole fractions observed, of the seasonal cycle, and the regional oxidation chemistry. However, ethane and propane enhancements in transport events were underestimated, indicating that after the ≥ 3 days of synoptic transport to PMO the spatial extent of plumes frequently is smaller than the 2.8° × 2.8° (∼300 km) model grid resolution. FUNDING INFORMATION : The PMO research has been supported by US National Science Foundation Awards #AGS-1011968, #AGS-1109568, #AGS-1110059, the NOAA Climate and Global Change Program grant NA03OAR4310072, and the U.S. Department of Energy Atmospheric Systems Research program, grant #DE-SC0006941. Funding was also received from the UK National Environment Research Council, grant number NE/F017391/1 and from PIP’s Philip Leverhulme Prize. The Regional Government of Azores has supported the Pico Mountain Observatory and operation through the Regional Secretary for Science, Technology and Infrastructures, and the Secretary for the Environment and the Sea. The NMHC monitoring at Summit was supported through the NASA ROSES program, grant number NNX07AR26G. NCAR is operated by the University Corporation of Atmospheric Research under sponsorship of the National Science Foundation. info:eu-repo/semantics/publishedVersion

The article of record as published may be found at http://dx.doi.org/10.1002/2014GL062404 The data for this paper are available upon request from the authors. The radiative properties of soot particles depend on their morphology and mixing state, but their evolution during transport is still elusive. Here we report observations from an electron microscopy analysis of individual particles transported in the free troposphere over long distances to the remote Pico Mountain Observatory in the Azores in the North Atlantic. Approximately 70% of the soot particles were highly compact and of those 26% were thinly coated. Discrete dipole approximation simulations indicate that this compaction results in an increase in soot single scattering albedo by a factor of ≤2.17. The top of the atmosphere direct radiative forcing is typically smaller for highly compact than mass-equivalent lacy soot. The forcing estimated using Mie theory is within 12% of the forcing estimated using the discrete dipole approximation for a high surface albedo, implying that Mie calculations may provide a reasonable approximation for compact soot above remote marine clouds. U.S. Department of Energy’s Atmospheric System Research National Science Foundation NASA’s Earth and Space Science Graduate Fellowship Earth Planetary and Space Sciences Institute U.S. Department of Energy’s Atmospheric System Research grant DE-SC0006941 National Science Foundation grant AGS-1110059 NASA’s Earth and Space Science Graduate Fellowship grant NNX13AN68H

[1] Humic-like substances (HULIS) constitute a significant fraction of aerosol particles in different environments. Studies of the role of HULIS in hygroscopic growth and cloud condensation nuclei (CCN) activity of aerosol particles are scarce, and results differ significantly. In this work the hygroscopic growth and CCN activity of water extracts (WE) and HULIS extracted from particulate matter (PM) collected at a polluted urban site (Copenhagen, Denmark), a rural site (Melpitz, Germany) and the remote site Storm Peak Laboratory (Colorado, USA) were investigated. Measurements of inorganic ions, elemental carbon, organic carbon and water soluble organic carbon (WSOC) within the PM confirmed that the sources of aerosol particles most likely differed for the three samples. The hygroscopic properties of the filtered WE were characterized by hygroscopicity parameters for subsaturated conditions (κGF) of 0.25, 0.41 and 0.22, and for supersaturated conditions κCCN were 0.23, 0.29 and 0.22 respectively for the urban, rural and remote WE samples. The measured hygroscopic growth and CCN activity were almost identical for the three HULIS samples and could be well represented by κGF = 0.07 and κCCN = 0.08–0.10 respectively. Small amounts of inorganic ions were present in the HULIS samples so the actual values for pure HULIS are expected to be slightly lower (κGF* = 0.04–0.06 and κCCN* = 0.07–0.08). The HULIS samples are thus less hygroscopic compared to most previous studies. To aid direct comparison of hygroscopic properties of HULIS from different studies, we recommend that the fraction of inorganic species in the HULIS samples always is measured and reported.

A detailed understanding of the sources, transformations and fates of organic species in the environment is crucial because of the central roles that they play in human health, biogeochemical cycles and the Earth's climate. However, such an understanding is hindered by the immense chemical complexity of environmental mixtures of organics; for example, atmospheric organic aerosol consists of at least thousands of individual compounds, all of which likely evolve chemically over their atmospheric lifetimes. Here, we demonstrate the utility of describing organic aerosol (and other complex organic mixtures) in terms of average carbon oxidation state, a quantity that always increases with oxidation, and is readily measured using state-of-the-art analytical techniques. Field and laboratory measurements of the average carbon oxidation state, using several such techniques, constrain the chemical properties of the organics and demonstrate that the formation and evolution of organic aerosol involves simultaneous changes to both carbon oxidation state and carbon number.

The detailed molecular composition of water-soluble atmospheric organic matter (AOM) contained in fog water was studied by use of electrospray ionization ultrahigh-resolution Fourier transform ion cyclotron resonance mass spectrometry. We identified 1368 individual molecular masses in the range of 100-400 Da from negative-ion spectra obtained after reversed-phase extraction with a hydrophilic solid phase sorbent. The detected organic anions are multifunctional with a variety of oxygenated functional groups. We observe organic nitrogen, organic sulfur, and organic nitrogen-sulfur compounds as well as many species with only C, H, and O elemental composition. Analysis of the double bond equivalents (DBE = the number of rings plus the number of double bonds to carbon) suggests that these compound structures range from highly aliphatic to aromatic with DBE values of 1-11. The compounds range in their extent of oxidation with oxygen to carbon ratios from 0.2 to 2 with an average value of 0.43. Several homologous series of compounds and multifunctional oligomers were identified in this AOM. The high extent of homologous series of compounds likely originates from primary components that have become oxidized. The multifunctional oligomers appear to represent atmospheric processing of primary and secondary compounds. The isolated water-soluble components identified here are amphiphilic, meaning that they contain both hydrophilic oxygenated functional groups and hydrophobic aliphatic and aromatic structural moieties. Despite the high number of compounds with very high oxygen content, 60% of assigned chemical formulas have measured organic mass-to-organic carbon ratiosor=2.25 (ranging from 1.25 to 3.5). Because the results reported here are not quantitative, an average ratio cannot be determined.

Particulate matter (PM) with an aerodynamic diameter < or = 2.5 microm (PM2.5) was collected daily (mid-July 1998 to the end of December 1999) over a 24-hr sampling period in a mixed light industrial-residential area in Atlanta, GA, to provide a subset of data for the Aerosol Research and Inhalation Epidemiology Study (ARIES). This study included the measurement of organic carbon (OC), elemental carbon (EC), and individual organic compounds. OC and EC average mean concentrations were 4.50 +/- 0.33 and 2.08 +/- 0.19 microg/m3, respectively. The ratio of organic matter mass (OM) to OC in PM2.5 aerosols in Atlanta was measured using three different approaches: (1) solvent extract residue gravimetric masses to individual OC concentrations of sequential apolar to polar solvent extracts (dichloromethane, acetone, and water); (2) mass balance of the PM2.5 measured gravimetric mass minus the mass concentrations of the inorganic/elemental constituents to the total OC concentration; and (3) polar organic compound speciation with the concentration weighted ratio to the total OC concentration. We found very good agreement between approach 1 and 2. The average OM/OC ratio calculated from the extract residue mass was 2.14 +/- 0.17. The average OM/OC ratio determined by mass balance was 2.16 +/- 0.43 for the whole period. The concentration weighted ratio calculated from the concentrations of polar organic compounds ranged between 1.55 and 1.72, which was likely a lower limit for the ratio because of the limited number of the polar organic compounds that can be quantified using gas chromatographic methods. We found seasonal differences with an OM/OC range of 1.77 in December 1999 to 2.39 in July 1999. These results suggest that the previously accepted value of 1.4 for the OM/OC ratio was too low even for urban locations during the winter months. Molecular-level speciation of the PM2.5-associated organic compounds showed that the concentrations of the molecular markers for wood smoke represented approximately 12-15% of the total polar organic compound concentrations during the winter months.

Biomass combustion emissions make a significant contribution to the overall particulate pollution in the troposphere. Wildland or prescribed burns and residential wood combustion emissions can vary due to differences in fuel, season, time of day, and the nature of the combustion. Inadequate understanding of the relevance of these biomass combustion emissions is due to the lack of characterization of open combustion emissions and the limited understanding of the differences between these and residential wood combustion. To provide new insight to biomass combustion emissions, sampling was conducted in several types of conditions. Semi-volatile organic compounds (SVOC) were collected during four separate prescribed burns in three different ecosystems, Mariposa Sequoia Grove within Yosemite National Park, CA, desert brushes of central rural Nevada, and Toiyabye National Forest near Lake Tahoe, NV. SVOC samples were also collected under controlled conditions for several wildland fuels, including conifer needles, wildland grasses, and sagebrush. Fireplace emissions from simulated residential wood combustion were also collected and are included here for comparison. A high degree of variability was found in the emissions of organic carbon, elemental carbon, levoglucosan, methoxy phenols, and organic acids. The variability in the emissions of levoglucosan does not correlate with the PM2.5 gravimetric mass and thus may affect source apportionment estimates.

The ability to monitor and quantify anionic components of aerosols is important for developing a better fundamental understanding of temporal and spatial variations in aerosol composition. Of the many methods that can be used to detect anions, capillary electrophoresis is among the most attractive ones because of its high separation efficiency, high resolving power for ionic compounds, and ability to be miniaturized for in-field monitoring. Here we present a method to baseline resolve common aerosol components nitrate, sulfate, chloride, and over two dozen organic acids in a single separation. A capillary electrophoresis separation utilizing a pH 5.78 piperazine buffer with 1,5-naphthalenedisulfonic acid as a probe for indirect UV absorbance detection was developed for this analysis. Previously, two different buffers were required to adequately separate all of these compounds. Electrophoretic mobilities, limits of detection, and migration time reproducibilities were measured for 38 organic and 8 inorganic anions. For solutions of low conductivity, detection limits for electrokinetic injections were found to be up to two orders of magnitude lower (0.2–0.4 μM) than those for pressure injection (1–45 μM). This separation was optimized and used for routine analysis of aqueous extracts of ambient atmospheric aerosols, but may be extended to other samples containing similar mixtures of anions.

Environmental context The organic fraction of atmospheric aerosols is a complex mixture of thousands of species, which play an important role in many atmospheric processes, such as absorbing and scattering solar radiation. We analysed the water-soluble organic fraction of ambient aerosol samples, and quantified over 45 carboxylic acids, sugars, sugar anhydrides and sugar alcohols. The presence of fairly high concentrations of sugars and sugar-alcohols suggests a significant biological input (e.g. pollen, fungi and bacteria) to the water-soluble organic fraction of non-urban aerosols. Abstract Water-soluble organic constituents of PM2.5 aerosol (particulate matter with an aerodynamic diameter ≤2.5µm) have not been well characterised so far. The goal of this work was to perform quantitative analysis of individual water-soluble organic species in aerosol samples collected in July of 2010 at the Storm Peak Laboratory (3210m above sea level) located in the Colorado Park Range (Steamboat Springs, CO, USA). Aqueous extracts were combined into six composites and analysed for organic carbon (OC), water-soluble organic carbon (WSOC), water-insoluble OC, inorganic ions, organic acids, lignin derivatives, sugar-alcohols, sugars and sugar-anhydrates. Analysis of higher molecular weight water-soluble organics was done using ultrahigh resolution mass spectrometry. Approximately 2400 positive and 4000 negative ions were detected and assigned to monoisotopic molecular formulae in the mass range of 100–800Da. The higher number of negative ions reflects a predominant presence of highly oxidised organic compounds. Individual identified organic species represented up to 30% of the water-soluble organic mass (WSOM). The WSOM fractions of the low molecular weight organic acids, sugars and sugar alcohols were 3–12%, 1.0–16% and 0.4–1.9%. Significant amounts of arabitol, mannitol and oxalic acid are most likely associated with airborne fungal spores and conidia that were observed on the filters using high resolution electron microscopy. Overall, higher concentrations of sugars (glucose, sucrose, fructose etc.) in comparison with biomass burning tracer levoglucosan indicate that a significant mass fraction of WSOC is related to airborne biological species.

Environmental contextAerosol water-soluble organic carbon is a complex mixture of thousands of organic compounds which may have a significant influence on the climate-relevant properties of atmospheric aerosols. Using ultrahigh resolution mass spectrometry, more than 4000 individual molecular formulas were identified in non-urban aerosol water-soluble organic carbon. A significant fraction of the assigned molecular formulas were matched to assigned molecular formulas of laboratory generated secondary organic aerosols. AbstractWater-soluble organic carbon (WSOC) is a complex mixture of thousands of organic compounds which may have significant influence on the climate-relevant properties of atmospheric aerosols. An improved understanding of the molecular composition of WSOC is needed to evaluate the effect of aerosol composition upon aerosol physical properties. In this work, ultrahigh-resolution Fourier transform–ion cyclotron resonance mass spectrometry (FT-ICR MS) was used to characterise aerosol WSOC collected during the summer of 2010 at the Storm Peak Laboratory (3210 m ASL) near Steamboat Springs, CO. Approximately 4000 molecular formulas were assigned in the mass range of 100–800 Da after negative-ion electrospray ionisation and more than 50 % of them contained nitrogen or sulfur. The double bond equivalents (DBEs) of the molecular formulas were inversely proportional to the O : C ratio, despite a relatively constant H : C ratio of ~1.5. Despite the range of DBE values, the elemental ratios and the high number of oxygen atoms per formula indicate that a majority of the compounds are aliphatic to olefinic in nature. These trends indicate significant non-oxidative accretion reaction pathways for the formation of high molecular weight WSOC components. In addition, a significant number of molecular formulas assigned in this work matched those previously identified as secondary organic aerosol components of monoterpene and sesquiterpene ozonolysis.

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 Research Funding: Beatriu de Pinos. Grant Number: 2016‐00215 Division of Chemical, Bioengineering, Environmental, and Transport Systems. Grant Number: 1802388 Engineering and Physical Sciences Research Council. Grant Number: EP/L015307/1 French National FT‐ICR network. Grant Number: FR 3624 CNRS H2020 European Research Council. Grant Number: ERC‐STG 716196 H2020 Marie Skłodowska‐Curie Actions. Grant Number: CHROME‐839709 National Science Foundation. Grant Number: AGS‐1531454 Newton Fund. Grant Number: 275910721 NIH. Grant Number: S10OD018475 Vetenskapsrådet. Grant Number: 2018‐04618