The Arctic is experiencing the greatest warming on Earth, as most evident by rapid sea ice loss. Delayed sea ice freeze-up in the Alaskan Arctic is decreasing wintertime sea ice extent and changing marine biological activity. However, the impacts of newly open water on wintertime sea spray aerosol (SSA) production and atmospheric composition are unknown. Herein, we identify SSA, produced locally from open sea ice fractures (leads), as the dominant aerosol source in the coastal Alaskan Arctic during winter, highlighting the year-round nature of Arctic SSA emissions. Nearly all of the individual SSA featured thick organic coatings, consisting of marine saccharides, amino acids, fatty acids, and divalent cations, consistent with exopolymeric secretions produced as cryoprotectants by sea ice algae and bacteria. In contrast, local summertime SSA lacked these organic carbon coatings, or featured thin coatings, with only open water nearby. The individual SSA composition was not consistent with frost flowers or surface snow above sea ice, suggesting that neither hypothesized frost flower aerosolization nor blowing snow sublimation resulted in the observed SSA. These results further demonstrate the need for inclusion of lead-based SSA production in modeling of Arctic atmospheric composition. The identified connections between changing sea ice, microbiology, and SSA point to the significance of sea ice lead biogeochemistry in altering Arctic atmospheric composition, clouds, and climate feedbacks during winter.

Abstract. Aerosols in the atmosphere are chemically complex with thousands of chemical species distributed in different proportions across individual particles in an aerosol population. An internal mixing assumption, with species present in the same proportions across all aerosols, is used in many models and calculations of secondary organic aerosol (SOA) formation, cloud activation, and aerosol optical properties. However, many of these effects depend on the distribution of species within individual particles, and important information can be lost when internal mixtures are assumed. Herein, we show that – as found during the Southern Oxidant and Aerosol Study (SOAS) in Centreville, Alabama, at a rural, forested location – aerosols frequently are not purely internally mixed, even in the accumulation mode (0.2–1.0 µm). A range of aerosol sources and the mixing state were determined using computer-controlled scanning electron microscopy with energy-dispersive X-ray spectroscopy (CCSEM-EDX) and scanning transmission X-ray microscopy–near-edge X-ray absorption fine structure spectroscopy (STXM-NEXAFS). Particles that were dominated by SOA and inorganic salts (e.g., ammonium sulfate) were the majority of particles by number fraction from 0.2 to 5 µm with an average of 78 % SOA in the accumulation mode. However, during certain periods contributions by sea spray aerosol (SSA) and mineral dust were significant to accumulation (22 % SSA and 26 % dust) and coarse-mode number concentrations (38 % SSA and 63 % dust). The fraction of particles containing key elements (Na, Mg, K, Ca, and Fe) were determined as a function of size for specific classes of particles. Within internally mixed SOA/sulfate particles < 5 % contained Na, Mg, K, Ca, or Fe, though these nonvolatile cations were present in particles from the other sources (e.g., SSA and dust). Mass estimates of the aerosol elemental components were used to determine the extent of internal versus external mixing by calculating the mixing state index (χ). The aerosol population was more externally mixed than internally mixed during all time periods analyzed. Accumulation mode aerosol ranged from more internally mixed during SOA periods to mostly externally mixed during dust periods. Supermicron aerosols were most externally mixed during SOA time periods, when more SOA particles added a distinct supermicron class, and more internally mixed when dominated by a single particle type (e.g., SSA or dust). These results emphasize that neither external nor internal mixtures fully represent the mixing state of atmospheric aerosols, even in a rural, forested environment, which has important implications for air quality and climate modeling.

Abstract. Few measurements of aerosol chemical composition have been made during the winter–spring transition (following polar sunrise) to constrain Arctic aerosol–cloud–climate feedbacks. Herein, we report the first measurements of individual particle chemical composition near Utqiaġvik (Barrow), Alaska, in winter (seven sample days in January and February 2014). Individual particles were analyzed by computer-controlled scanning electron microscopy with energy dispersive X-ray spectroscopy (CCSEM-EDX, 24 847 particles), Raman microspectroscopy (300 particles), and scanning transmission X-ray microscopy with near-edge X-ray absorption fine structure spectroscopy (STXM-NEXAFS, 290 particles). Sea spray aerosol (SSA) was observed in all samples, with fresh and aged SSA comprising 99 %, by number, of 2.5–7.5 µm diameter particles, 65–95 % from 0.5–2.5 µm, and 50–60 % from 0.1–0.5 µm, indicating SSA is the dominant contributor to accumulation and coarse-mode aerosol during the winter. The aged SSA particles were characterized by reduced chlorine content with 94 %, by number, internally mixed with secondary sulfate (39 %, by number, internally mixed with both nitrate and sulfate), indicative of multiphase aging reactions during transport. There was a large number fraction (40 % of 1.0–4.0 µm diameter particles) of aged SSA during periods when particles were transported from near Prudhoe Bay, consistent with pollutant emissions from the oil fields participating in atmospheric processing of aerosol particles. Organic carbon and sulfate particles were observed in all samples and comprised 40–50 %, by number, of 0.1–0.4 µm diameter particles, indicative of Arctic haze influence. Soot was internally mixed with organic and sulfate components. All sulfate was mixed with organic carbon or SSA particles. Therefore, aerosol sources in the Alaskan Arctic and resulting aerosol chemical mixing states need to be considered when predicting aerosol climate effects, particularly cloud formation, in the winter Arctic.

Two complementary techniques, Scanning Transmission X-ray Microscopy/Near Edge Fine Structure spectroscopy (STXM/NEXAFS) and Scanning Electron Microscopy/Energy Dispersive X-ray spectroscopy (SEM/EDX), have been quantitatively combined to characterize individual atmospheric particles. This pair of techniques was applied to particle samples at three sampling sites (ATTO, ZF2, and T3) in the Amazon basin as part of the Observations and Modeling of the Green Ocean Amazon (GoAmazon2014/5) field campaign during the dry season of 2014. The combined data was subjected to k-means clustering using mass fractions of the following elements: C, N, O, Na, Mg, P, S, Cl, K, Ca, Mn, Fe, Ni, and Zn. Cluster analysis identified 12 particle types across different sampling sites and particle sizes. Samples from the remote Amazon Tall Tower Observatory (ATTO, also T0a) exhibited less cluster variety and fewer anthropogenic clusters than samples collected at the sites nearer to the Manaus metropolitan region, ZF2 (also T0t) or T3. Samples from the ZF2 site contained aged/anthropogenic clusters not readily explained by transport from ATTO or Manaus, possibly suggesting the effects of long range atmospheric transport or other local aerosol sources present during sampling. In addition, this data set allowed for recently established diversity parameters to be calculated. All sample periods had high mixing state indices (χ) that were >0.8. Two individual particle diversity (D i ) populations were observed, with particles <0.5 µm having a D i of~2.4 and >0.5 µm particles having a D i of~3.6, which likely correspond to fresh and aged aerosols, respectively. The diversity parameters determined by the quantitative method presented here will serve to aid in the accurate representation of aerosol mixing state, source apportionment, and aging in both less polluted and more developed environments in the Amazon Basin.

Sea spray aerosol (SSA) can have complex carbon speciation that is affected by biological conditions in the seawater from which it originates. Biologically derived molecules can also interact with other longer-lived organic and inorganic carbon species in the sea surface microlayer and in the process of bubble bursting. An isolated wave channel facility was used to generate sea spray aerosol during a 1 month mesocosm study. Two consecutive phytoplankton blooms occurred, and sea spray aerosol was sampled throughout. Scanning transmission X-ray microscopy coupled with near-edge X-ray absorption fine structure spectroscopy (STXM-NEXAFS) was used to determine spatially resolved carbon speciation within individual particles from 0.18 to 3.2 μm. During phytoplankton blooms, coarse-mode particles exhibited an increased abundance of carboxylic acid-rich needlelike structures. The extent of organic enrichment in fine-mode particles correlates with the occurrence of aliphatic-rich organic species, as detected by an intense C 1s → σ(C−H)* excitation. These aliphatic-rich species had a strong association with graphitic carbon, as detected by a C 1s → σ* exciton excitation. This enrichment was unique to particles collected in the aerodynamic size range 0.18−0.32 μm and corresponded with the decrease in hygroscopicity. Aliphatic organics can significantly suppress the particle hygroscopicity when they replace salt, thus influencing the effect of sea spray aerosol on light scattering and cloud formation. These results suggest that graphitic carbon is concentrated in the sea surface microlayer during phytoplankton blooms and released through wave action. These results may have implications for radiative transfer and carbon cycling in the ocean−atmosphere system.