Athanasios Nenes

ISORROPIA: A New Thermodynamic Equilibrium Model for Multiphase Multicomponent Inorganic Aerosols

A computationally efficient and rigorous thermodynamic model that predicts the physical state and composition of inorganic atmospheric aerosol is presented. One of the main features of the model is the implementation of mutual deliquescence of multicomponent salt particles, which lowers the deliquescence point of the aerosol phase.The model is used to examine the behavior of four types of tropospheric aerosol (marine, urban, remote continental and non-urban continental), and the results are compared with the predictions of two other models currently in use. The results of all three models were generally in good agreement. Differences were found primarily in the mutual deliquescence humidity regions, where the new model predicted the existence of water, and the other two did not. Differences in the behavior (speciation and water absorbing properties) between the aerosol types are pointed out. The new model also needed considerably less CPU time, and always shows stability and robust convergence.

A Continuous-Flow Streamwise Thermal-Gradient CCN Chamber for Atmospheric Measurements

We have addressed the need for improved measurements of cloud condensation nuclei (CCN) by developing a continuous-flow instrument that provides in situ measurements of CCN. The design presented in this article can operate between 0.1 and 3% supersaturation, at sampling rates sufficient for airborne operation. The design constitutes a cylindrical continuous-flow thermal-gradient diffusion chamber employing a novel technique of generating a supersaturation: by establishing a constant streamwise temperature gradient so that the difference in water vapor and thermal diffusivity yield a quasi-uniform centerline supersaturation. Our design maximizes the growth rate of activated droplets, thereby enhancing the performance of the instrument. The temperature gradient and the flow through the column control the supersaturation and may be modified to retrieve CCN spectra. The principle of the CCN instrument was validated in controlled laboratory experiments at different operating conditions using a monodisperse aerosols with known composition and size. These experiments yield sharp activation curves, even for those kinetically limited particles that have not exceeded their critical diameter. The performance of the CCN instrument was also assessed using polydisperse laboratory-generated aerosol of known composition and size distributions similar to ambient particulate matter. In all tests, the measured CCN concentrations compared well with predicted values and highlight the instruments ability to measure CCN at various size distributions. The full potential of the new design has yet to be explored; however, model simulations suggest that direct measurements in the climatically important range of supersaturations of less than 0.1% (certainly down to 0.07%) are possible. The new instrument clearly offers a unique level of design simplicity, robustness, and flexilibity (temperature control, large range of supersaturations without flow reversal, and multiple configurations for same supersaturation) necessary for atmospheric studies.

Continued development and testing of a new thermodynamic aerosol module for urban and regional air quality models

A computationally efficient and rigorous thermodynamic model (ISORROPIA) that predicts the physical state and composition of inorganic atmospheric aerosol is presented. The advantages of this particular model render it suitable for incorporation into urban and regional air quality models. The model is embodied into the UAM-AERO air quality model, and the performance is compared with two other thermodynamic modules currently in use, SEQUILIB 1.5 and SEQUILIB 2.1. The new model yields predictions that agree with experimental measurements and the results of the other models, but at the same time proves to be much faster and computationally efficient. Using ISORROPIA accelerates the thermodynamic calculations by more than a factor of six, while the overall speed-up of UAM-AERO is at least twofold. This speedup is possible by the optimal solution of the thermodynamic equations, and the usage of precalculated tables, whenever possible.

Phytoplankton and Cloudiness in the Southern Ocean

The effect of ocean biological productivity on marine clouds is explored over a large phytoplankton bloom in the Southern Ocean with the use of remotely sensed data. Cloud droplet number concentration over the bloom was twice what it was away from the bloom, and cloud effective radius was reduced by 30%. The resulting change in the short-wave radiative flux at the top of the atmosphere was –15 watts per square meter, comparable to the aerosol indirect effect over highly polluted regions. This observed impact of phytoplankton on clouds is attributed to changes in the size distribution and chemical composition of cloud condensation nuclei. We propose that secondary organic aerosol, formed from the oxidation of phytoplankton-produced isoprene, can affect chemical composition of marine cloud condensation nuclei and influence cloud droplet number. Model simulations support this hypothesis, indicating that 100% of the observed changes in cloud properties can be attributed to the isoprene secondary organic aerosol.

Effects of anthropogenic emissions on aerosol formation from isoprene and monoterpenes in the southeastern United States

Significance Atmospheric secondary organic aerosol has substantial impacts on climate, air quality, and human health. However, the formation mechanisms of secondary organic aerosol remain uncertain, especially on how anthropogenic pollutants (from human activities) control aerosol formation from biogenic volatile organic compounds (emitted by vegetation) and the magnitude of anthropogenic influences. Although possible mechanisms have been proposed based on laboratories studies, a coherent understanding of anthropogenic−biogenic interactions in ambient environments has not emerged. Here, we provide direct observational evidence that secondary organic aerosol formed from biogenic isoprene and monoterpenes is greatly mediated by anthropogenic SO2 and NOx emissions based on integrated ambient measurements and laboratory studies. Secondary organic aerosol (SOA) constitutes a substantial fraction of fine particulate matter and has important impacts on climate and human health. The extent to which human activities alter SOA formation from biogenic emissions in the atmosphere is largely undetermined. Here, we present direct observational evidence on the magnitude of anthropogenic influence on biogenic SOA formation based on comprehensive ambient measurements in the southeastern United States (US). Multiple high-time-resolution mass spectrometry organic aerosol measurements were made during different seasons at various locations, including urban and rural sites in the greater Atlanta area and Centreville in rural Alabama. Our results provide a quantitative understanding of the roles of anthropogenic SO2 and NOx in ambient SOA formation. We show that isoprene-derived SOA is directly mediated by the abundance of sulfate, instead of the particle water content and/or particle acidity as suggested by prior laboratory studies. Anthropogenic NOx is shown to enhance nighttime SOA formation via nitrate radical oxidation of monoterpenes, resulting in the formation of condensable organic nitrates. Together, anthropogenic sulfate and NOx can mediate 43–70% of total measured organic aerosol (29–49% of submicron particulate matter, PM1) in the southeastern US during summer. These measurements imply that future reduction in SO2 and NOx emissions can considerably reduce the SOA burden in the southeastern US. Updating current modeling frameworks with these observational constraints will also lead to more accurate treatment of aerosol formation for regions with substantial anthropogenic−biogenic interactions and consequently improve air quality and climate simulations.

Mapping the Operation of the DMT Continuous Flow CCN Counter

This work thoroughly analyzes a new commercial instrument for measuring Cloud Condensation Nuclei (CCN), the Droplet Measurement Technologies Cylindrical Continuous-Flow Streamwise Thermal Gradient CCN Chamber (CFSTGC). This instrument can measure CCN concentrations at supersaturations from 0.06% to 3% (potentially up to 6%), at a 1 Hz sampling rate that is sufficient for airborne operation. Our analysis employs a fully coupled numerical flow model to simulate the water vapor supersaturation, temperature, velocity profiles and CCN growth in the CFSTGC for its entire range of operation (aerosol sample flow rates 0.25–2.0 L min − 1 , temperature differences 2–15 K and ambient pressures 100–1000 mb). The model was evaluated by comparing simulated instrument responses for calibration aerosol against actual measurements from an existing CCN instrument. The model was used to evaluate the CCN detection efficiency for a wide range of ambient pressures, flow rates, temperature gradients, and droplet growth kinetics. Simulations overestimate the instrument supersaturation when the thermal resistance across the walls of the flow chamber is not considered. We have developed a methodology to determine the thermal resistance and temperature drop across the wetted walls of the flow chamber, by combining simulations and calibration experiments. Finally, we provide parameterizations for determining the thermal resistance, the instrument supersaturation and the optimal detection threshold for the optical particle counter.

Can chemical effects on cloud droplet number rival the first indirect effect

An increase in cloud droplet number concentration resulting from an increase in ambient aerosol (and subsequent albedo increase) is typically identified as the first indirect (or “Twomey”) climatic effect of aerosols [Twomey, 1974]. A key question is whether chemical effects (dissolution of soluble gases and slightly soluble substances, surface tension depression by organic substances and accommodation coefficient changes) could potentially rival changes in droplet number from changes in aerosol number concentration. We assess the sensitivity of cloud droplet number concentration to such chemical factors, using a cloud parcel model. We find that numerous conditions exist, for which chemical influences on cloud droplet activation can indeed rival the Twomey effect.

Microbiome of the upper troposphere: Species composition and prevalence, effects of tropical storms, and atmospheric implications

The composition and prevalence of microorganisms in the middle-to-upper troposphere (8–15 km altitude) and their role in aerosol-cloud-precipitation interactions represent important, unresolved questions for biological and atmospheric science. In particular, airborne microorganisms above the oceans remain essentially uncharacterized, as most work to date is restricted to samples taken near the Earth’s surface. Here we report on the microbiome of low- and high-altitude air masses sampled onboard the National Aeronautics and Space Administration DC-8 platform during the 2010 Genesis and Rapid Intensification Processes campaign in the Caribbean Sea. The samples were collected in cloudy and cloud-free air masses before, during, and after two major tropical hurricanes, Earl and Karl. Quantitative PCR and microscopy revealed that viable bacterial cells represented on average around 20% of the total particles in the 0.25- to 1-μm diameter range and were at least an order of magnitude more abundant than fungal cells, suggesting that bacteria represent an important and underestimated fraction of micrometer-sized atmospheric aerosols. The samples from the two hurricanes were characterized by significantly different bacterial communities, revealing that hurricanes aerosolize a large amount of new cells. Nonetheless, 17 bacterial taxa, including taxa that are known to use C1–C4 carbon compounds present in the atmosphere, were found in all samples, indicating that these organisms possess traits that allow survival in the troposphere. The findings presented here suggest that the microbiome is a dynamic and underappreciated aspect of the upper troposphere with potentially important impacts on the hydrological cycle, clouds, and climate.

Kinetic limitations on cloud droplet formation and impact on cloud albedo

Under certain conditions mass transfer limitations on the growth of cloud condensation nuclei (CCN) may have a significant impact on the number of droplets that can form in a cloud. The assumption that particles remain in equilibrium until activated may therefore not always be appropriate for aerosol populations existing in the atmosphere. This work identifies three mechanisms that lead to kinetic limitations, the effect of which on activated cloud droplet number and cloud albedo is assessed using a one-dimensional cloud parcel model with detailed microphysics for a variety of aerosol size distributions and updraft velocities. In assessing the effect of kinetic limitations, we have assumed as cloud droplets not only those that are strictly activated (as dictated by classical Köhler theory), but also unactivated drops large enough to have an impact on cloud optical properties. Aerosol number concentration is found to be the key parameter that controls the significance of kinetic effects. Simulations indicate that the equilibrium assumption leads to an overprediction of droplet number by less than 10% for marine aerosol; this overprediction can exceed 40% for urban type aerosol. Overall, the effect of kinetic limitations on cloud albedo can be considered important when equilibrium activation theory consistently overpredicts droplet number by more than 10%. The maximum change in cloud albedo as a result of kinetic limitations is less than 0.005 for cases such as marine aerosol; however albedo differences can exceed 0.1 under more polluted conditions. Kinetic limitations are thus not expected to be climatically significant on a global scale, but can regionally have a large impact on cloud albedo.

Aerosol-cloud drop concentration closure in warm cumulus

Our understanding of the activation of aerosol particles into cloud drops during the formation of warm cumulus clouds presently has a limited observational foundation. Detailed observations of aerosol size and composition, cloud microphysics and dynamics, and atmospheric thermodynamic state were collected in a systematic study of 21 cumulus clouds by the Center for Interdisciplinary Remotely-Piloted Aircraft Studies (CIRPAS) Twin Otter aircraft during NASAs Cirrus Regional Study of Tropical Anvils and Cirrus Layers–Florida Area Cirrus Experiment (CRYSTAL-FACE). An “aerosol-cloud” closure study was carried out in which a detailed cloud activation parcel model, which predicts cloud drop concentration using observed aerosol concentration, size distribution, cloud updraft velocity, and thermodynamic state, is evaluated against observations. On average, measured droplet concentration in adiabatic cloud regions is within 15% of the predictions. This agreement is corroborated by independent measurements of aerosol activation carried out by two cloud condensation nucleus (CCN) counters on the aircraft. Variations in aerosol concentration, which ranged from 300 to 3300 cm^(−3), drives large microphysical differences (250–2300 cm^(−3)) observed among continental and maritime clouds in the South Florida region. This is the first known study in which a cloud parcel model is evaluated in a closure study using a constraining set of data collected from a single platform. Likewise, this is the first known study in which relationships among aerosol size distribution, CCN spectrum, and cloud droplet concentration are all found to be consistent with theory within experimental uncertainties much less than 50%. Vertical profiles of cloud microphysical properties (effective radius, droplet concentration, dispersion) clearly demonstrate the boundary layer aerosols effect on cloud microphysics throughout the lowest 1 km of cloud depth. Onboard measurements of aerosol hygroscopic growth and the organic to sulfate mass ratio are related to CCN properties. These chemical data are used to quantify the range of uncertainty associated with the simplified treatment of aerosol composition assumed in the closure study.