Atmospheric chemistry of bioaerosols: heterogeneous and multiphase reactions with atmospheric oxidants and other trace gases.

Advances in analytical techniques and instrumentation have now established methods for detecting, quantifying, and identifying the chemical and microbial constituents of particulate matter in the atmosphere. For example, recent cryo-TEM studies of sea spray have identified whole bacteria and viruses ejected from ocean seawater into air. A focal point of this perspective is directed towards the reactivity of aerosol particles of biological origin with oxidants (OH, NO3, and O3) present in the atmosphere. Complementary information on the reactivity of aerosol particles is obtained from field investigations and laboratory studies. Laboratory studies of different types of biologically-derived particles offer important information related to their impacts on the local and global environment. These studies can also unravel a range of different chemistries and reactivity afforded by the complexity and diversity of the chemical make-up of these particles. Laboratory experiments as the ones reviewed herein can elucidate the chemistry of biological aerosols

Humidity-dependent surface tension measurements of individual inorganic and organic submicrometre liquid particles.

Surface tension, an important property of liquids, is easily measured for bulk samples. However, for droplets smaller than one micron in size, there are currently no reported measurements. In this study, atomic force microscopy (AFM) and force spectroscopy have been utilized to measure surface tension of individual submicron sized droplets at ambient pressure and controlled relative humidity (RH). Since the surface tension of atmospheric aerosols is a key factor in understanding aerosol climate effects, three atmospherically relevant systems (NaCl, malonic and glutaric acids) were studied. Single particle AFM measurements were successfully implemented in measuring the surface tension of deliquesced particles on the order of 200 to 500 nm in diameter. Deliquesced particles continuously uptake water at high RH, which changes the concentration and surface tension of the droplets. Therefore, surface tension as a function of RH was measured. AFM based surface tension measurements are close to predicted values based on bulk measurements and activities of these three chemical systems. Non-ideal behaviour in concentrated organic acid droplets is thought to be important and the reason for differences observed between bulk solution predictions and AFM data. Consequently, these measurements are crucial in order to improve atmospheric climate models as direct measurements hitherto have been previously inaccessible due to instrument limitations

Sea Spray Aerosol: Where Marine Biology Meets Atmospheric Chemistry.

Atmospheric aerosols have long been known to alter climate by scattering incoming solar radiation and acting as seeds for cloud formation. These processes have vast implications for controlling the chemistry of our environment and the Earth's climate. Sea spray aerosol (SSA) is emitted over nearly three-quarters of our planet, yet precisely how SSA impacts Earth's radiation budget remains highly uncertain. Over the past several decades, studies have shown that SSA particles are far more complex than just sea salt. Ocean biological and physical processes produce individual SSA particles containing a diverse array of biological species including proteins, enzymes, bacteria, and viruses and a diverse array of organic compounds including fatty acids and sugars. Thus, a new frontier of research is emerging at the nexus of chemistry, biology, and atmospheric science. In this Outlook article, we discuss how current and future aerosol chemistry research demands a tight coupling between experimental (observational and laboratory studies) and computational (simulation-based) methods. This integration of approaches will enable the systematic interrogation of the complexity within individual SSA particles at a level that will enable prediction of the physicochemical properties of real-world SSA, ultimately illuminating the detailed mechanisms of how the constituents within individual SSA impact climate

Interactions of Water with Mineral Dust Aerosol: Water Adsorption, Hygroscopicity, Cloud Condensation, and Ice Nucleation

Mineral dust aerosol is one of the major types of aerosol present in the troposphere. The molecular level interactions of water vapor with mineral dust are of global significance. Hygroscopicity, light scattering and absorption, heterogneous reactivity and the ability to form clouds are all related to water–dust interactions. In this review article, experimental techniques to probe water interactions with dust and theoretical frameworks to understand these interactions are discussed. A comprehensive overview of laboratory studies of water adsorption, hygroscopicity, cloud condensation, and ice nucleation of fresh and atmspherically aged mineral dust particles is provided. Finally, we relate laboratory studies and theoretical simulations that provide fundemental insights into these processes on the molecular level with field measurements that illustrate the atmospheric significance of these processes. Overall, the details of water interactions with mineral dust are covered from multiple perspectives in this review article.United States. National Aeronautics and Space Administration (Grant NNX13AO15G)Massachusetts Institute of Technology. Victor P. Starr Career Development Chai

Hydrogen bonded complexes between nitrogen dioxide, nitric acid, nitrous acid and water with SiH3OH and Si(OH)4

The inter-conversion of nitrogen oxides and oxy acids on silica surfaces is of major atmospheric importance. As a preliminary step towards rationalising experimental observations, and understanding the mechanisms behind such reactions we have looked at the binding energies of NO2, N2O4, HNO3, HONO and H2O with simple proxies of a silica surface, namely SiH3OH and Si(OH)4 units. The geometries of these molecular clusters were optimised at both HF/6-311+G(d) and B3LYP/6-311+G(d) level of theory. The SCF energies of the species were determined at the HF/6-311++G(3df,2pd) and B3LYP/6-311++G(3df,2pd) level. The values indicate that nitric acid is by far the most strongly bound species, in agreement with experimental observations. It was also found that the dimer N2O4 is significantly more strongly bound to the Si(OH)4 and SiH3OH units than NO2 itself. The vibrational frequencies calculated for the hydrogen-bonded complexes are compared to the experimentally observed frequencies of the adsorbed species where possible

Export efficiency of black carbon aerosol in continental outflow: Global implications

We use aircraft observations of Asian outflow from the NASA Transport and Chemical Evolution over the Pacific (TRACE-P) mission over the NW Pacific in March–April 2001 to estimate the export efficiency of black carbon (BC) aerosol during lifting to the free troposphere, as limited by scavenging from the wet processes (warm conveyor belts and convection) associated with this lifting. Our estimate is based on the enhancement ratio of BC relative to CO in Asian outflow observed at different altitudes and is normalized to the enhancement ratio observed in boundary layer outflow (0–1 km). We similarly estimate export efficiencies of sulfur oxides (SO x = SO2(g) + fine SO4 2−) and total inorganic nitrate (HNO3 T = HNO3(g) + fine NO3 −) for comparison to BC. Normalized export efficiencies for BC are 0.63–0.74 at 2–4 km altitude and 0.27–0.38 at 4–6 km. Values at 2–4 km altitude are higher than for SO x (0.48–0.66) and HNO3 T (0.29–0.62), implying that BC is scavenged in wet updrafts but not as efficiently as sulfate or nitrate. Simulation of the TRACE-P period with a global three-dimensional model (GEOS-CHEM) indicates that a model timescale of 1 ± 1 days for conversion of fresh hydrophobic to hydrophilic BC provides a successful fit to the export efficiencies observed in TRACE-P. The resulting mean atmospheric lifetime of BC is 5.8 ± 1.8 days, the global burden is 0.11 ± 0.03 Tg C, and the decrease in Arctic snow albedo due to BC deposition is 3.1 ± 2.5%.Earth and Planetary Science

Salting Up of Proteins at the Air/Water Interface.

Vibrational sum frequency generation (VSFG) spectroscopy and surface pressure measurements are used to investigate the adsorption of a globular protein, bovine serum albumin (BSA), at the air/water interface with and without the presence of salts. We find at low (2 to 5 ppm) protein concentrations, which is relevant to environmental conditions, both VSFG and surface pressure measurements of BSA behave drastically different from at higher concentrations. Instead of emerging to the surface immediately, as observed at 1000 ppm, protein adsorption kinetics is on the order of tens of minutes at lower concentrations. Most importantly, salts strongly enhance the presence of BSA at the interface. This "salting up" effect differs from the well-known "salting out" effect as it occurs at protein concentrations well-below where "salting out" occurs. The dependence on salt concentration suggests this effect relates to a large extent electrostatic interactions and volume exclusion. Additionally, results from other proteins and the pH dependence of the kinetics indicate that salting up depends on the flexibility of proteins. This initial report demonstrates "salting up" as a new type of salt-driven interfacial phenomenon, which is worthy of continued investigation given the importance of salts in biological and environmental aqueous systems

Psychiatric Effects of Solitary Confinement

The author, Dr. Grassian, is a Board Certified Psychiatrist who was on the faculty of the Harvard Medical School for over twenty-five years. He has had extensive experience in evaluating the psychiatric effects of solitary confinement, and in the course of his professional involvement, has been involved as an expert regarding the psychiatric impact of federal and state segregation and disciplinary units in many settings. The following statement is largely a redacted, non-institution and non-inmate specific, version of a declaration which was submitted in September 1993 in Madrid v. Gomez

Dream a Little Dream of Us ... United for Success!

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