Christina S. McCluskey

Sea spray aerosol as a unique source of ice nucleating particles

Ice nucleating particles (INPs) are vital for ice initiation in, and precipitation from, mixed-phase clouds. A source of INPs from oceans within sea spray aerosol (SSA) emissions has been suggested in previous studies but remained unconfirmed. Here, we show that INPs are emitted using real wave breaking in a laboratory flume to produce SSA. The number concentrations of INPs from laboratory-generated SSA, when normalized to typical total aerosol number concentrations in the marine boundary layer, agree well with measurements from diverse regions over the oceans. Data in the present study are also in accord with previously published INP measurements made over remote ocean regions. INP number concentrations active within liquid water droplets increase exponentially in number with a decrease in temperature below 0 °C, averaging an order of magnitude increase per 5 °C interval. The plausibility of a strong increase in SSA INP emissions in association with phytoplankton blooms is also shown in laboratory simulations. Nevertheless, INP number concentrations, or active site densities approximated using “dry” geometric SSA surface areas, are a few orders of magnitude lower than corresponding concentrations or site densities in the surface boundary layer over continental regions. These findings have important implications for cloud radiative forcing and precipitation within low-level and midlevel marine clouds unaffected by continental INP sources, such as may occur over the Southern Ocean.

Microbial Control of Sea Spray Aerosol Composition: A Tale of Two Blooms.

With the oceans covering 71% of the Earth, sea spray aerosol (SSA) particles profoundly impact climate through their ability to scatter solar radiation and serve as seeds for cloud formation. The climate properties can change when sea salt particles become mixed with insoluble organic material formed in ocean regions with phytoplankton blooms. Currently, the extent to which SSA chemical composition and climate properties are altered by biological processes in the ocean is uncertain. To better understand the factors controlling SSA composition, we carried out a mesocosm study in an isolated ocean-atmosphere facility containing 3,400 gallons of natural seawater. Over the course of the study, two successive phytoplankton blooms resulted in SSA with vastly different composition and properties. During the first bloom, aliphatic-rich organics were enhanced in submicron SSA and tracked the abundance of phytoplankton as indicated by chlorophyll-a concentrations. In contrast, the second bloom showed no enhancement of organic species in submicron particles. A concurrent increase in ice nucleating SSA particles was also observed only during the first bloom. Analysis of the temporal variability in the concentration of aliphatic-rich organic species, using a kinetic model, suggests that the observed enhancement in SSA organic content is set by a delicate balance between the rate of phytoplankton primary production of labile lipids and enzymatic induced degradation. This study establishes a mechanistic framework indicating that biological processes in the ocean and SSA chemical composition are coupled not simply by ocean chlorophyll-a concentrations, but are modulated by microbial degradation processes. This work provides unique insight into the biological, chemical, and physical processes that control SSA chemical composition, that when properly accounted for may explain the observed differences in SSA composition between field studies.

Characteristics of atmospheric ice nucleating particles associated with biomass burning in the US: Prescribed burns and wildfires

An improved understanding of atmospheric ice nucleating particles (INP), including sources and atmospheric abundance, is needed to advance our understanding of aerosol-cloud-climate interactions. This study examines diverse biomass burning events to better constrain our understanding of how fires impact populations of INP. Sampling of prescribed burns and wildfires in Colorado and Georgia, U.S.A., revealed that biomass burning leads to the release of particles that are active as condensation/immersion freezing INP at temperatures from −32 to −12°C. During prescribed burning of wiregrass, up to 64% of INP collected during smoke-impacted periods were identified as soot particles via electron microscopy analyses. Other carbonaceous types and mineral-like particles dominated INP collected during wildfires of ponderosa pine forest in Colorado. Total measured nINP and the excess nINP associated with smoke-impacted periods were higher during two wildfires compared to the prescribed burns. Interferences from non-smoke sources of INP, including long-range transported mineral dust and local contributions of soils and plant materials lofted from the wildfires themselves, presented challenges in using the observations to develop a smoke-specific nINP parameterization. Nevertheless, these field observations suggest that biomass burning may serve as an important source of INP on a regional scale, particularly during time periods that lack other robust sources of INP such as long-range transported mineral dust.

A Dynamic Link between Ice Nucleating Particles Released in Nascent Sea Spray Aerosol and Oceanic Biological Activity during Two Mesocosm Experiments

AbstractEmission rates and properties of ice nucleating particles (INPs) are required for proper representation of aerosol–cloud interactions in atmospheric models. Few investigations have quantified marine INP emissions, a potentially important INP source for remote oceanic regions. Previous studies have suggested INPs in sea spray aerosol (SSA) are linked to oceanic biological activity. This proposed link was explored in this study by measuring INP emissions from nascent SSA during phytoplankton blooms during two mesocosm experiments. In a Marine Aerosol Reference Tank (MART) experiment, a phytoplankton bloom was produced with chlorophyll-a (Chl a) concentrations reaching 39 μg L−1, while Chl a concentrations more representative of natural ocean conditions were obtained during the Investigation into Marine Particle Chemistry and Transfer Science (IMPACTS; peak Chl a of 5 μg L−1) campaign, conducted in the University of California, San Diego, wave flume. Dynamic trends in INP emissions occurred for INPs ...

Rapidly evolving ultrafine and fine mode biomass smoke physical properties: Comparing laboratory and field results

Combining field and laboratory results, we present biomass smoke physical properties. We report sub-0.56 µm diameter (Dp) particle sizing (fast mobility particle sizer, FMPS) plus light absorption and scattering at 870 nm (photoacoustic extinctiometer). For Dp   100 nm), while flaming combustion produced very high number concentrations of smaller (Dp ~ 50 nm) absorbing particles. Due to smoldering and particle growth processes, Dp approached 100 nm within 3 h after emission. Increased particle cross-sectional area and Mie scattering efficiency shifted the relative importance of light absorption (flaming maximum) and light scattering (smoldering maximum), increasing ω over time. Measurements showed a consistent picture of smoke properties from emission to aging.

A New Method to Determine the Number Concentrations of Refractory Black Carbon Ice Nucleating Particles

Ice nucleating particles (INP) initiate heterogeneous ice nucleation in mixed-phase clouds, influencing cloud phase and onset temperatures for ice formation. Determination of particle types contributing to atmospheric INP populations requires isolation of the relatively rare INP from a total particle sample, typically followed by time-consuming single-particle characterization. We propose a method to estimate the contributions of light-absorbing, primarily refractory black carbon (rBC), particles to INP populations by selectively removing them prior to determination of INP concentrations. Absorbing particles are heated to their vaporization temperature using laser induced incandescence in a single particle soot photometer (SP2) and the change in INP number concentrations, compared to unheated samples, is assessed downstream in the CSU Continuous Flow Diffusion Chamber (CFDC). We tested this approach in the laboratory using strongly-absorbing and nonabsorbing aerosol types to confirm effective removal of rBC INP and to explore the impact of the processing on non-light-absorbing INP. An INP-active rBC particle type was efficiently removed, while nonabsorbing kaolinite and a soil-based INP were not affected by laser exposure. Results for the products of wiregrass combustion indicated that absorbing particles, primarily rBC, accounted for about 40% of all INP, consistent with electron microscopy of INP emitted during prescribed burns of this fuel type. However, kaolinite internally mixed with rBC exhibited reduced activity after passing through the SP2, suggesting that the validity of the method for realistic internal mixtures needs additional research. The sensitivity of the CFDC presently limits applicability of the method to relatively high INP number concentration samples. Copyright 2014 American Association for Aerosol Research

A Mesocosm Double Feature: Insights into the Chemical Makeup of Marine Ice Nucleating Particles

AbstractThe abundance of atmospheric ice nucleating particles (INPs) is a source of uncertainty for numerical representation of ice-phase transitions in mixed-phase clouds. While sea spray aerosol ...

Marine and Terrestrial Organic Ice‐Nucleating Particles in Pristine Marine to Continentally Influenced Northeast Atlantic Air Masses

Sea spray aerosol (SSA) generated by bubble bursting at the ocean surface is an important component of aerosol-cloud interactions over remote oceans, providing the atmosphere with ice-nucleating particles (INPs) or particles required for heterogeneous ice nucleation. Studies have shown that organic INPs are emitted during phytoplankton blooms, but changes in INP number concentrations (nINPs) due to ocean biological activity have not been directly demonstrated in natural SSA. In this study, a clean sector sampler was used to differentiate ice nucleation and composition of pristine SSA from terrestrial aerosol at the Mace Head Research Station in August 2015. Average nINPs active at 15 °C (nINPs, 15 °C) were 0.0011 L , and large variability (up to a factor of 200) was observed for INPs active warmer than 22 °C. Highest nINPs in the clean sector occurred during a period of elevated marine organic aerosol from offshore biological activity (M1, nINPs, 15 °C = 0.0077 L ). A peak in nINPs was also observed in terrestrial organic aerosol (T1, nINPs, 15 °C = 0.0076 L ). The impacts of heating and hydrogen peroxide digestion on nINPs indicate that INPs at Mace Head Research Station were largely organic and that INPs observed during M1 and T1 were biological (i.e., protein containing). Complexities of predicting increases in nINPs due to offshore biological activity are explored. A parameterization for pristine SSA INPs over the North Atlantic Ocean was developed, illustrating that SSA is associated with a factor of 1,000 fewer ice-nucleating sites per surface area of aerosol compared to mineral dust.

Ice nucleation by particles containing long-chain fatty acids of relevance to freezing by sea spray aerosols

Heterogeneous ice nucleation in the atmosphere regulates cloud properties, such as phase (ice versus liquid) and lifetime. Aerosol particles of marine origin are relevant ice nucleating particle sources when marine aerosol layers are lifted over mountainous terrain and in higher latitude ocean boundary layers, distant from terrestrial aerosol sources. Among many particle compositions associated with ice nucleation by sea spray aerosols are highly saturated fatty acids. Previous studies have not demonstrated their ability to freeze dilute water droplets. This study investigates ice nucleation by monolayers at the surface of supercooled droplets and as crystalline particles at temperatures exceeding the threshold for homogeneous freezing. Results show the poor efficiency of long chain fatty acid (C16, C18) monolayers in templating freezing of pure water droplets and seawater subphase to temperatures of at least -30 °C, consistent with theory. This contrasts with freezing of fatty alcohols (C22 used here) at nearly 20 °C warmer. Evaporation of μL-sized droplets to promote structural compression of a C19 acid monolayer did not favor warmer ice formation of drops. Heterogeneous ice nucleation occurred for nL-sized droplets condensed on 5 to 100 μm crystalline particles of fatty acid (C12 to C20) at a range of temperatures below -28 °C. These experiments suggest that fatty acids nucleate ice at warmer than -36 °C only when the crystalline phase is present. Rough estimates of ice active site densities are consistent with those of marine aerosols, but require knowledge of the proportion of surface area comprised of fatty acids for application.

Biological ice nuclei and the impact of rain on ice nuclei populations

With 18% of total US landmass devoted to croplands, farmland is a potentially major source of biogenic particles to the atmosphere. We investigated two farms as potential sources of biological ice nuclei (IN). We found that each of these farms contained abundant INA bacteria on the vegetation; however, airborne ina gene concentrations were typically below detectable limits, demonstrating a disconnect between local vegetative sources and the air above them. The question remains, then, as to how biological IN are released into the atmosphere. In a second study, we investigated how precipitation impacted the concentration and composition of IN. Results from these measurements show that ground level IN concentrations were enhanced during rain events, and that some portion of these IN were biological. In this paper, we present results from both of these studies, and discuss modified measurement techniques aimed at characterizing the often very low number concentrations of biological IN.