Microphysical explanation of the RH-dependent water affinity of biogenic organic aerosol and its importance for climate.

A large fraction of atmospheric organic aerosol (OA) originates from natural emissions that are oxidized in the atmosphere to form secondary organic aerosol (SOA). Isoprene (IP) and monoterpenes (MT) are the most important precursors of SOA originating from forests. The climate impacts from OA are currently estimated through parameterizations of water uptake that drastically simplify the complexity of OA. We combine laboratory experiments, thermodynamic modeling, field observations, and climate modeling to (1) explain the molecular mechanisms behind RH-dependent SOA water-uptake with solubility and phase separation; (2) show that laboratory data on IP- and MT-SOA hygroscopicity are representative of ambient data with corresponding OA source profiles; and (3) demonstrate the sensitivity of the modeled aerosol climate effect to assumed OA water affinity. We conclude that the commonly used single-parameter hygroscopicity framework can introduce significant error when quantifying the climate effects of organic aerosol. The results highlight the need for better constraints on the overall global OA mass loadings and its molecular composition, including currently underexplored anthropogenic and marine OA sources.

Mass spectral analysis of organic aerosol formed downwind of the Deepwater Horizon oil spill: field studies and laboratory confirmations.

In June 2010, the NOAA WP-3D aircraft conducted two survey flights around the Deepwater Horizon (DWH) oil spill. The Gulf oil spill resulted in an isolated source of secondary organic aerosol (SOA) precursors in a relatively clean environment. Measurements of aerosol composition and volatile organic species (VOCs) indicated formation of SOA from intermediate-volatility organic compounds (IVOCs) downwind of the oil spill (Science2011, 331, doi 10.1126/science.1200320). In an effort to better understand formation of SOA in this environment, we present mass spectral characteristics of SOA in the Gulf and of SOA formed in the laboratory from evaporated light crude oil. Compared to urban primary organic aerosol, high-mass-resolution analysis of the background-subtracted SOA spectra in the Gulf (for short, "Gulf SOA") showed higher contribution of C(x)H(y)O(+) relative to C(x)H(y)(+) fragments at the same nominal mass. In each transect downwind of the DWH spill site, a gradient in the degree of oxidation of the Gulf SOA was observed: more oxidized SOA (oxygen/carbon = O/C ∼0.4) was observed in the area impacted by fresher oil; less oxidized SOA (O/C ∼0.3), with contribution from fragments with a hydrocarbon backbone, was found in a broader region of more-aged surface oil. Furthermore, in the plumes originating from the more-aged oil, contribution of oxygenated fragments to SOA decreased with downwind distance. Despite differences between experimental conditions in the laboratory and the ambient environment, mass spectra of SOA formed from gas-phase oxidation of crude oil by OH radicals in a smog chamber and a flow tube reactor strongly resembled the mass spectra of Gulf SOA (r(2) > 0.94). Processes that led to the observed Gulf SOA characteristics are also likely to occur in polluted regions where VOCs and IVOCs are coemitted.

Chemical and microphysical characterization of ambient aerosols with the aerodyne aerosol mass spectrometer.

The application of mass spectrometric techniques to the real-time measurement and characterization of aerosols represents a significant advance in the field of atmospheric science. This review focuses on the aerosol mass spectrometer (AMS), an instrument designed and developed at Aerodyne Research, Inc. (ARI) that is the most widely used thermal vaporization AMS. The AMS uses aerodynamic lens inlet technology together with thermal vaporization and electron-impact mass spectrometry to measure the real-time non-refractory (NR) chemical speciation and mass loading as a function of particle size of fine aerosol particles with aerodynamic diameters between approximately 50 and 1,000 nm. The original AMS utilizes a quadrupole mass spectrometer (Q) with electron impact (EI) ionization and produces ensemble average data of particle properties. Later versions employ time-of-flight (ToF) mass spectrometers and can produce full mass spectral data for single particles. This manuscript presents a detailed discussion of the strengths and limitations of the AMS measurement approach and reviews how the measurements are used to characterize particle properties. Results from selected laboratory experiments and field measurement campaigns are also presented to highlight the different applications of this instrument. Recent instrumental developments, such as the incorporation of softer ionization techniques (vacuum ultraviolet (VUV) photo-ionization, Li+ ion, and electron attachment) and high-resolution ToF mass spectrometers, that yield more detailed information about the organic aerosol component are also described.

Ozonolysis of mixed oleic-acid/stearic-acid particles: reaction kinetics and chemical morphology.

The ozonolysis of mixed oleic-acid/stearic-acid (OL/SA) aerosol particles from 0/100 to 100/0 wt % composition is studied. The magnitude of the divergence of the particle beam inside an aerosol mass spectrometer shows that, in the concentration range 100/0 to 60/40, the mixed OL/SA particles are liquid prior to reaction. Upon ozonolysis, particles having compositions of 75/25 and 60/40 change shape, indicating that they have solidified during reaction. Transmission electron micrographs show that SA(s) forms needles. For particles having compositions of 75/25, 60/40, and greater SA content, the reaction kinetics exhibit an initial fast decay of OL for low O(3) exposure with no further loss of OL at higher O(3) exposures. For compositions from 50/50 to 10/90, the residual OL concentration remains at 28 +/- 2% of its initial value. The initial reactive uptake coefficient for O(3), as determined by OL loss, decreases linearly from 1.25 (+/-0.2) x 10(-3) to 0.60 (+/-0.15) x 10(-3) for composition changes of 100/0 to 60/40. At 50/50 composition, the uptake coefficient drops abruptly to 0.15 (+/-0.1) x 10(-3), and there are no further changes with increased SA content. These observations can be explained with a combination of three postulates: (1) Unreacted mixed particles remain as supersaturated liquids up to 60/40 composition, and the OL in this form rapidly reacts with O(3). (2) SA, as it solidifies, locks into its crystal structure a significant amount of OL, and this OL is completely inaccessible to O(3). (3) Accompanying crystallization, some stearic acid molecules connect as a filamentous network to form a semipermeable gel containing liquid OL but with a reduced uptake coefficient because of the decrease in molecular diffusivity in the gel. An individual particle of 50/50 to 90/10 is hypothesized as a combination of SA crystals having OL impurities (postulate 2) that are partially enveloped by an SA/OL gel (postulate 3) to explain (a) the abrupt drop in the uptake coefficient from 60/40 to 50/50 and (b) the residual OL content even after high ozone exposure. The results of this study, pointing out the important effects of particle phase, composition, and morphology on chemical reactivity, contribute to an improved understanding of the aging processes of atmospheric aerosol particles.

Uptake of organic gas phase species by 1-methylnaphthalene.

Organic compounds are a significant component of tropospheric aerosols. In the present study, 1-methylnaphthalene was selected as a surrogate for aromatic hydrocarbons (PAHs) found in tropospheric aerosols. Mass accommodation coefficients (alpha) on 1-methylnaphthalene were determined as a function of temperature (267 K to 298 K) for gas-phase m-xylene, ethylbenzene, butylbenzene, alpha-pinene, gamma-terpinene, p-cymene, and 2-methyl-2-hexanol. The gas uptake studies were performed with droplets maintained under liquid-vapor equilibrium conditions using a droplet train flow reactor. The mass accommodation coefficients for all of the molecules studied in these experiments exhibit negative temperature dependence. The upper and lower values of alpha at 267 and 298 K respectively are as follows: for m-xylene 0.44 +/- 0.05 and 0.26 +/- 0.03; for ethylbenzene 0.37 +/- 0.03 and 0.22 +/- 0.04; for butylbenzene 0.47 +/- 0.06 and 0.31 +/- 0.04; for alpha-pinene 0.47 +/- 0.07 and 0.10 +/- 0.05; for gamma-terpinene 0.37 +/- 0.04 and 0.12 +/- 0.06; for p-cymene 0.74 +/- 0.05 and 0.36 +/- 0.07; for 2-methyl-2-hexanol 0.44 +/- 0.06 and 0.29 +/- 0.06. The uptake measurements also yielded values for the product HD(l)(1/2) for most of the molecules studied (H = Henry's law constant, D(l) = liquid-phase diffusion coefficient). Using calculated values of D(l), the Henry's law constants (H) for these molecules were obtained as a function of temperature. The H values at 298 K in units 10(3) M atm(-1) are as follows: for m-xylene (0.48 +/- 0.05); for ethylbenzene (0.50 +/- 0.08); for butylbenzene (3.99 +/- 0.93); for alpha-pinene (0.53 +/- 0.07); for p-cymene (0.23 +/- 0.07); for 2-methyl-2-hexanol (1.85 +/- 0.29).

Sacral agenesis: usefulness of CT study.

The authors report on a case of sacral agenesis evaluated by Computed Tomography (CT) of the spine. Sacral agenesis is an exceedingly rare, nongenetic, developmental anomaly which consists in an absence of the entire sacrococcygeal complex. Although maternal diabetes appears to be the most important etiologic factor, the significant teratogenetic effects related to maternal diabetes are not yet completely understood. Only few cases have been reported in neurological and neurosurgical literature because most authors believe that the neurological deficits associated with sacral agenesis are static and, therefore, myelography and surgical approach are useless. However, sacral agenesis can be surgically treated when dural sac stenosis is evident in presence of progressive neurological deficits. The usefulness of CT in depicting nervous anomalies which may favorably respond to surgical treatment is emphasized, in particular when compared with contrast myelography. CT scan seems able to replace contrast myelography in delineating the intraspinal nervous anomalies, thus avoiding the myelographic risks.

Cervical myelopathy due to ossification of the posterior longitudinal ligament.

Ossification of the posterior longitudinal ligament in the cervical spine may be a cause of cervical myelopathy. This ossification has often been encountered in Japan, but only sporadically among the Caucasian races. It is therefore probable that racial factors are relevant to the pathology. During the past four years, due to the routine use of computerised axial tomography (CAT) in the pre-operative study of cervical myelopathy, we were able to show that in 13 cases stenosis of the vertebral canal was due to ossification of the posterior longitudinal ligament. This was visible in the standard radiographs in only two out of these 13 cases. The clinical data, diagnostic criteria and results of treatment are reported. This is the largest series yet reported outside Japan.

Cervical myelopathy. Technique and results of spinal cord decompression by lateral laminectomy.

The Authors describe the technique of lateral laminectomy devised by Gui in 1965 for the treatment of cervical myelopathy secondary to cervical spondylosis. Spinal cord decompression is obtained by a lateral laminectomy with the maximum saving of bone, ligaments and muscles of the cervical spine. CAT scan demonstrated very well the effective decompression of the spinal cord achieved with this technique. The results of 87 cases treated in this way between 1968 and 1980 are reported. The average follow-up was 2.5 years. There was an improvement in the neurological symptoms in 82% of the cases.

Isotope separation in a "seeded beam%".

A new method of separating isotopes in a gaseous mixture is described. The method takes advantage of the differences in velocities of isotopic species in a molecular beam formed by expansion of the mixture with a light gas from a nozzle source. For the separation of the hexafluorides of uranium-235 and uranium-238 the technique has an estimated separative work factor about 500 times higher than the gaseous diffusion process and 100 times higher than the curved-jet method.

Scanning laser microscope for biological investigations.

The theory and design of a special purpose scanning laser microscope are described. This microscope, particularly suited for biological investigations, is intended for the observation of objects embedded within transparent or translucent bodies, such as nerve cells in an intact brain. Some photographs made with a prototype are shown.