• Energy Research

Atomic chlorine (Cl•) affects air quality and atmospheric oxidizing capacity. Nitryl chloride (ClNO2) - a common Cl• source-forms when chloride-containing aerosols react with dinitrogen pentoxide (N2O5). A recent study showed that saline lakebed (playa) dust is an inland source of particulate chloride (Cl-) that generates high ClNO2. However, the underlying physiochemical factors responsible for observed yields are poorly understood. To elucidate these controlling factors, we utilized single particle and bulk techniques to determine the chemical composition and mineralogy of playa sediment and dust samples from the southwest United States. Single particle analysis shows trace highly hygroscopic magnesium and calcium Cl-containing minerals are present and likely facilitate ClNO2 formation at low humidity. Single particle and mineralogical analysis detected playa sediment organic matter that hinders N2O5 uptake as well as 10 Å-clay minerals (e.g., Illite) that compete with water and chloride for N2O5. Finally, we show that the composition of the aerosol surface, rather than the bulk, is critical in ClNO2 formation. These findings underscore the importance of mixing state, competing reactions, and surface chemistry on N2O5 uptake and ClNO2 yield for playa dusts and, likely, other aerosol systems. Therefore, consideration of particle surface composition is necessary to improve ClNO2 and air quality modeling.

Abstract During the Ice in Clouds Experiment–Layer Clouds (ICE-L), aged biomass-burning particles were identified within two orographic wave cloud regions over Wyoming using single-particle mass spectrometry and electron microscopy. Using a suite of instrumentation, particle chemistry was characterized in tandem with cloud microphysics. The aged biomass-burning particles comprised ∼30%–40% by number of the 0.1–1.0-μm clear-air particles and were composed of potassium, organic carbon, elemental carbon, and sulfate. Aerosol mass spectrometry measurements suggested these cloud-processed particles were predominantly sulfate by mass. The first cloud region sampled was characterized by primarily homogeneously nucleated ice particles formed at temperatures near −40°C. The second cloud period was characterized by high cloud droplet concentrations (∼150–300 cm−3) and lower heterogeneously nucleated ice concentrations (7–18 L−1) at cloud temperatures of −24° to −25°C. As expected for the observed particle chemistry and dynamics of the observed wave clouds, few significant differences were observed between the clear-air particles and cloud residues. However, suggestive of a possible heterogeneous nucleation mechanism within the first cloud region, ice residues showed enrichments in the number fractions of soot and mass fractions of black carbon, measured by a single-particle mass spectrometer and a single-particle soot photometer, respectively. In addition, enrichment of biomass-burning particles internally mixed with oxalic acid in both the homogeneously nucleated ice and cloud droplets compared to clear air suggests either preferential activation as cloud condensation nuclei or aqueous phase cloud processing.

AbstractMarine aerosol plays a vital role in cloud‐aerosol interactions during summer in the Arctic. The recent rise in temperature and decrease in sea ice extent have the potential to impact marine biogenic sources. Compounds like methanesulfonic acid (MSA) and non‐sea‐salt sulfate (nss‐SO42−), oxidation products of dimethyl sulfide (DMS) emitted by marine primary producers, are likely to increase in concentration. Long‐term studies are vital to understand these changes in marine sulfur aerosol and potential interactions with Arctic climate. Samples were collected over three summers at two coastal sites on the North Slope of Alaska (Utqiaġvik and Oliktok Point). MSA concentrations followed previously reported seasonal trends, with evidence of high marine primary productivity influencing both sites. When added to an additional data set collected at Utqiaġvik, an increase in MSA concentration of + 2.5% per year and an increase in nss‐SO42− of + 2.1% per year are observed for the summer season over the 20‐year record (1998–2017). This study identifies ambient air temperature as a strong factor for MSA, likely related to a combination of interrelated factors including warmer sea surface temperature, reduced sea ice, and temperature‐dependent chemical reactions. Analysis of individual particles at Oliktok Point, within the North Slope of Alaska oil fields, showed evidence of condensation of MSA onto anthropogenic particles, highlighting the connection between marine and oil field emissions and secondary organic aerosol. This study shows the continued importance of understanding MSA in the Arctic while highlighting the need for further research into its seasonal relationship with organic carbon.

As the Arctic continues to change and warm rapidly, it is increasingly important to understand the organic carbon (OC) contribution to Arctic aerosol. Biogenic sources of primary and secondary OC in the Arctic will be impacted by climate change, including warming temperatures and earlier snow and ice melt. This study focuses on identifying potential sources and regional influences on the seasonal concentration of organic aerosol through analysis of chemical and isotopic composition. Aerosol samples were collected at two sites on the North Slope of Alaska (Utqiaġvik, UQK, and Oliktok Point, OLK, which is in an Arctic oilfield) over three summers from 2015 to 2017. The elemental carbon (EC) trends at each site were used to understand local combustion influences. Local sources drove EC concentrations at Oliktok Point, where high EC was attributed to oil and gas extraction activity, including diesel combustion emissions. Utqiaġvik had very low EC in the summer. OC was more similar in concentration and well correlated between the two sites with high contributions of contemporary carbon by radiocarbon apportionment (UQK = 74%, OLK = 63%), which could include both marine and terrestrial sources of contemporary carbon (e.g. primary and secondary biogenic, biomass burning and/or associated SOA, and bioaerosols). OC concentrations are strongly correlated to maximum ambient temperatures on the NSA during the summer, which may have implications for predicting future OC aerosol concentrations in a warming Arctic. Biomass burning was determined to be an episodic influence at both sites, based on interpretation of combined aerosol composition, air mass trajectories, and remote sensing of smoke plumes. The results from this study overall strongly suggests contribution from regional sources of contemporary organic aerosol on the NSA, but additional analysis is needed to better constrain contributions from both biogenic sources (terrestrial and/or marine) and bioaerosol to better understand temperature-related aerosol processes in the Arctic.

Abstract Ice concentrations in orographic wave clouds at temperatures between −24° and −29°C were shown to be related to aerosol characteristics in nearby clear air during five research flights over the Rocky Mountains. When clouds with influence from colder temperatures were excluded from the dataset, mean ice nuclei and cloud ice number concentrations were very low, on the order of 1–5 L−1. In this environment, ice number concentrations were found to be significantly correlated with the number concentration of larger particles, those larger than both 0.1- and 0.5-μm diameter. A variety of complementary techniques was used to measure aerosol size distributions and chemical composition. Strong correlations were also observed between ice concentrations and the number concentrations of soot and biomass-burning aerosols. Ice nuclei concentrations directly measured in biomass-burning plumes were the highest detected during the project. Taken together, this evidence indicates a potential role for biomass-burning aerosols in ice formation, particularly in regions with relatively low concentrations of other ice nucleating aerosols.