Olga Laskina

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.

Analysis of Organic Anionic Surfactants in Fine and Coarse Fractions of Freshly Emitted Sea Spray Aerosol.

The inclusion of organic compounds in freshly emitted sea spray aerosol (SSA) has been shown to be size-dependent, with an increasing organic fraction in smaller particles. Here we have used electrospray ionization-high resolution mass spectrometry in negative ion mode to identify organic compounds in nascent sea spray collected throughout a 25 day mesocosm experiment. Over 280 organic compounds from ten major homologous series were tentatively identified, including saturated (C8-C24) and unsaturated (C12-C22) fatty acids, fatty acid derivatives (including saturated oxo-fatty acids (C5-C18) and saturated hydroxy-fatty acids (C5-C18), organosulfates (C2-C7, C12-C17) and sulfonates (C16-C22). During the mesocosm, the distributions of molecules within some homologous series responded to variations among the levels of phytoplankton and bacteria in the seawater. The average molecular weight and carbon preference index of saturated fatty acids significantly decreased within fine SSA during the progression of the mesocosm, which was not observed in coarse SSA, sea-surface microlayer or in fresh seawater. This study helps to define the molecular composition of nascent SSA and biological processes in the ocean relate to SSA composition.

Size matters in the water uptake and hygroscopic growth of atmospherically relevant multicomponent aerosol particles.

Understanding the interactions of water with atmospheric aerosols is crucial for determining the size, physical state, reactivity, and climate impacts of this important component of the Earths atmosphere. Here we show that water uptake and hygroscopic growth of multicomponent, atmospherically relevant particles can be size dependent when comparing 100 nm versus ca. 6 μm sized particles. It was determined that particles composed of ammonium sulfate with succinic acid and of a mixture of chlorides typical of the marine environment show size-dependent hygroscopic behavior. Microscopic analysis of the distribution of components within the aerosol particles show that the size dependence is due to differences in the mixing state, that is, whether particles are homogeneously mixed or phase separated, for different sized particles. This morphology-dependent hygroscopicity has consequences for heterogeneous atmospheric chemistry as well as aerosol interactions with electromagnetic radiation and clouds.

Quantifying the Hygroscopic Growth of Individual Submicrometer Particles with Atomic Force Microscopy

The water uptake behavior of atmospheric aerosol dictates their climate effects. In many studies, aerosol particles are deposited onto solid substrates to measure water uptake; however, the effects of the substrate are not well understood. Furthermore, in some cases, methods used to analyze and quantify water uptake of substrate deposited particles use a two-dimensional (2D) analysis to monitor growth by following changes in the particle diameter with relative humidity (RH). However, this 2D analysis assumes that the droplet grows equally in all directions. If particle growth is not isotropic in height and diameter, this assumption can cause inaccuracies when quantifying hygroscopic growth factors (GFs), where GF for a for a spherical particle is defined as the ratio of the particle diameter at a particular relative humidity divided by the dry particle diameter (typically about 5% RH). However, as shown here, anisotropic growth can occur in some cases. In these cases, a three-dimensional (3D) analysis of the growth is needed. This study introduces a way to quantify the hygroscopic growth of substrate deposited particles composed of model systems relevant to atmospheric aerosols using atomic force microscopy (AFM), which gives information on both the particle height and area and thus a three-dimensional view of each particle. In this study, we compare GFs of submicrometer sized particles composed of single component sodium chloride (NaCl) and malonic acid (MA), as well as binary mixtures of NaCl and MA, and NaCl and nonanoic acid (NA) determined by AFM using area (2D) equivalent diameters, similar to conventional microscopy methods, to GFs determined using volume (3D) equivalent diameter. We also compare these values to GFs determined by a hygroscopic tandem differential mobility analyzer (HTDMA; substrate free, 3D method). It was found that utilizing volume equivalent diameter for quantifying GFs with AFM agreed well with those determined by substrate-free HTDMA method, regardless of particle composition but area equivalent derived GFs varied for different chemical systems. Furthermore, the NaCl and MA mixture was substrate-deposited both wet and dry, revealing that the hydration state of the particle at the time of impaction influences how the particle grows on the substrate upon water uptake. Most importantly, for the binary mixtures it is shown here that different populations of particles can be distinguished with AFM, an individual particle method, whereas HTDMA sees the ensemble average. Overall, this study establishes the methodology of using AFM to accurately quantify the water uptake of individual submicrometer particles at ambient conditions over a wide range of RH values. Furthermore, the importance of single particle AFM analysis is demonstrated.

Optical and Physicochemical Properties of Brown Carbon Aerosol: Light Scattering, FTIR Extinction Spectroscopy, and Hygroscopic Growth

A great deal of attention has been paid to brown carbon aerosol in the troposphere because it can both scatter and absorb solar radiation, thus affecting the Earths climate. However, knowledge of the optical and chemical properties of brown carbon aerosol is still limited. In this study, we have investigated different aspects of the optical properties of brown carbon aerosol that have not been previously explored. These properties include extinction spectroscopy in the mid-infrared region and light scattering at two different visible wavelengths, 532 and 402 nm. A proxy for atmospheric brown carbon aerosol was formed from the aqueous reaction of ammonium sulfate with methylglyoxal. The different optical properties were measured as a function of reaction time for a period of up to 19 days. UV/vis absorption experiments of bulk solutions showed that the optical absorption of aqueous brown carbon solution significantly increases as a function of reaction time in the spectral range from 200 to 700 nm. The analysis of the light scattering data, however, showed no significant differences between ammonium sulfate and brown carbon aerosol particles in the measured scattering phase functions, linear polarization profiles, or the derived real parts of the refractive indices at either 532 or 402 nm, even for the longest reaction times with greatest visible extinction. The light scattering experiments are relatively insensitive to the imaginary part of the refractive index, and it was only possible to place an upper limit of k ≤ 0.01 on the imaginary index values. These results suggest that after the reaction with methylglyoxal the single scattering albedo of ammonium sulfate aerosol is significantly reduced but that the light scattering properties including the scattering asymmetry parameter, which is a measure of the relative amount of forward-to-backward scattering, remain essentially unchanged from that of unprocessed ammonium sulfate. The optical extinction properties in the mid-IR range (800 to 7000 cm(-1)) also showed no significant changes in either the real or the imaginary parts of the refractive indices for brown carbon aerosol particles when compared to ammonium sulfate. Therefore, changes in the optical properties of ammonium sulfate in the mid-IR spectral range due to reaction with methylglyoxal appear to be insignificant. In addition to these measurements, we have characterized additional physicochemical properties of the brown carbon aerosol particles including hygroscopic growth using a tandem-differential mobility analyzer. Compared to ammonium sulfate, brown carbon aerosol particles are found to have lower deliquescence relative humidity (DRH), efflorescence relative humidity (ERH), and hygroscopic growth at the same relative humidities. Overall, our study provides new details of the optical and physicochemical properties of a class of secondary organic aerosol which may have important implications for atmospheric chemistry and climate.

Substrate-Deposited Sea Spray Aerosol Particles: Influence of Analytical Method, Substrate, and Storage Conditions on Particle Size, Phase, and Morphology.

Atmospheric aerosols are often collected on substrates and analyzed weeks or months after the initial collection. We investigated how the selection of substrate and microscopy method influence the measured size, phase, and morphology of sea spray aerosol (SSA) particles and how sample storage conditions affect individual particles using three common microscopy techniques: optical microscopy, atomic force microscopy, and scanning electron microscopy. Micro-Raman spectroscopy was used to determine changes in the water content of stored particles. The results show that microscopy techniques operating under ambient conditions provide the most relevant and robust measurement of particle size. Samples stored in a desiccator and at ambient conditions leads to similar sizes and morphologies, while storage that involves freezing and thawing leads to irreversible changes due to phase changes and water condensation. Typically, SSA particles are deposited wet and, if possible, samples used for single-particle analysis should be stored at or near conditions at which they were collected in order to avoid dehydration. However, if samples need to be dry, as is often the case, then this study found that storing SSA particles at ambient laboratory conditions (17-23% RH and 19-21 °C) was effective at preserving them and reducing changes that would alter samples and subsequent data interpretation.

Processing and Ageing in the Atmosphere

Transport through the atmosphere exposes mineral dust to a number of processes that alter its physicochemical properties, which in turn affects its direct and indirect impacts on climate. In this chapter, we review the physical and chemical processes that alter dust properties and their impacts on dust’s radiative properties, cloud condensation nucleus activity, morphology, nutrient and trace element solubility and the impacts of heterogeneous chemistry on dust surfaces on atmospheric composition.

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 ...

Infrared Optical Constants of Organic Aerosols: Organic Acids and Model Humic-Like Substances (HULIS)

Aerosols are important atmospheric constituents as they impact the Earths energy balance and climate. An analysis of the impact of aerosols depends on the detailed knowledge of aerosol optical properties. However, there is a lack of refractive index data for atmospherically relevant organic compounds in the infrared (IR) region which complicates the quantitative estimation of the aerosol influence on the radiative balance. In this study, we investigate the optical properties of atmospherically relevant carboxylic acids and HUmic-LIke Substances (HULIS) proxies. Aerosol size distributions are measured simultaneously with Fourier transform infrared (FTIR) extinction spectra to calculate the complex refractive index. Scanning electron microscopy (SEM) images are also collected to investigate particle shape. Analysis of SEM images shows evidence for agglomeration in some cases. The experimentally measured IR resonances do not appear to be highly sensitive to agglomeration effects. However, there is an increase in the scattering efficiency at shorter wavelengths as the result of larger overall particle size of the agglomerates. Refractive indices are retrieved from the IR extinction spectra of organic acids and HULIS proxies. Mie simulation results confirm the quality of the retrieved optical constants. Interestingly, the optical constants determined for the acids are in agreement with the published data for fire smoke plumes. Copyright 2014 American Association for Aerosol Research