Using advanced mass spectrometry techniques to fully characterize atmospheric organic carbon: current capabilities and remaining gaps.

Organic compounds in the atmosphere vary widely in their molecular composition and chemical properties, so no single instrument can reasonably measure the entire range of ambient compounds. Over the past decade, a new generation of in situ, field-deployable mass spectrometers has dramatically improved our ability to detect, identify, and quantify these organic compounds, but no systematic approach has been developed to assess the extent to which currently available tools capture the entire space of chemical identity and properties that is expected in the atmosphere. Reduced-parameter frameworks that have been developed to describe atmospheric mixtures are exploited here to characterize the range of chemical properties accessed by a suite of instruments. Multiple chemical spaces (e.g. oxidation state of carbon vs. volatility, and oxygen number vs. carbon number) were populated with ions measured by several mass spectrometers, with gas- and particle-phase α-pinene oxidation products serving as the test mixture of organic compounds. Few gaps are observed in the coverage of the parameter spaces by the instruments employed in this work, though the full extent to which comprehensive measurement was achieved is difficult to assess due to uncertainty in the composition of the mixture. Overlaps between individual ions and regions in parameter space were identified, both between gas- and particle-phase measurements, and within each phase. These overlaps were conservatively found to account for little (<10%) of the measured mass. However, challenges in identifying overlaps and in accurately converting molecular formulas into chemical properties (such as volatility or reactivity) highlight a continued need to incorporate structural information into atmospheric measurements.

Overview of surface measurements and spatial characterization of submicrometer particulate matter during the DISCOVER-AQ 2013 campaign in Houston, TX.

The sources of submicrometer particulate matter (PM1) remain poorly characterized in the industrialized city of Houston, TX. A mobile sampling approach was used to characterize PM1 composition and concentration across Houston based on high-time-resolution measurements of nonrefractory PM1 and trace gases during the DISCOVER-AQ Texas 2013 campaign. Two pollution zones with marked differences in PM1 levels, character, and dynamics were established based on cluster analysis of organic aerosol mass loadings sampled at 16 sites. The highest PM1 mass concentrations (average 11.6 ± 5.7 µg/m3) were observed to the northwest of Houston (zone 1), dominated by secondary organic aerosol (SOA) mass likely driven by nighttime biogenic organonitrate formation. Zone 2, an industrial/urban area south/east of Houston, exhibited lower concentrations of PM1 (average 4.4 ± 3.3 µg/m3), significant organic aerosol (OA) aging, and evidence of primary sulfate emissions. Diurnal patterns and backward-trajectory analyses enable the classification of airmass clusters characterized by distinct PM sources: biogenic SOA, photochemical aged SOA, and primary sulfate emissions from the Houston Ship Channel. Principal component analysis (PCA) indicates that secondary biogenic organonitrates primarily related with monoterpenes are predominant in zone 1 (accounting for 34% of the variability in the data set). The relevance of photochemical processes and industrial and traffic emission sources in zone 2 also is highlighted by PCA, which identifies three factors related with these processes/sources (~50% of the aerosol/trace gas concentration variability). PCA reveals a relatively minor contribution of isoprene to SOA formation in zone 1 and the absence of isoprene-derived aerosol in zone 2. The relevance of industrial amine emissions and the likely contribution of chloride-displaced sea salt aerosol to the observed variability in pollution levels in zone 2 also are captured by PCA. IMPLICATIONS: This article describes an urban-scale mobile study to characterize spatial variations in submicrometer particulate matter (PM1) in greater Houston. The data set indicates substantial spatial variations in PM1 sources/chemistry and elucidates the importance of photochemistry and nighttime oxidant chemistry in producing secondary PM1. These results emphasize the potential benefits of effective control strategies throughout the region, not only to reduce primary emissions of PM1 from automobiles and industry but also to reduce the emissions of important secondary PM1 precursors, including sulfur oxides, nitrogen oxides, ammonia, and volatile organic compounds. Such efforts also could aid in efforts to reduce mixing ratios of ozone.

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.

Rainbow refractometry applied to radially inhomogeneous spheres: the critical case of evaporating droplets.

A detailed study of rainbow thermometry and its application to droplets in reactive systems is presented. To this end the light-scattering history of a vaporizing droplet under unsteady conditions is discussed. Unlike in previous papers, the reduction of the droplet's diameter is also taken into account in addition to the variation of the refractive-index profile. A finely stratified sphere model with thousands of layers (i.e., 20,000) is used to compute the scattering patterns of a radially inhomogeneous evaporating droplet at different heating times and therefore with different diameters and refractive-index profiles. In the studied case the temperatures inferred from rainbow thermometry do not represent the actual temperatures inside the droplet. They do not represent an average internal temperature or even the surface or the core temperature. For droplets with a temperature that increases from the core to the surface, the inferred values are always lower than the minimum temperature inside the droplet. Therefore the rainbow technique should be applied with caution in all cases in which droplet inhomogeneities are suspected. In addition, a careful analysis of the scattering in the rainbow region is presented. Because of the physical structure of the rainbow, a marked uncertainty in the inferred temperatures also has to be considered in the case of homogenous droplets. For inhomogeneous spheres this intrinsic uncertainty has to be added to the effects caused by the internal profiles of the refractive index.

Scattering of electromagnetic-plane waves by radially inhomogeneous spheres: a finely stratified sphere model.

A new recursive algorithm to calculate the internal and scattered fields of finely stratified inhomogeneous spheres has been developed. No restriction on the number of layers-the thicknesses of which can be arbitrarily small-is imposed by this method. The number of layers is restricted only by the computer's capability: calculations with spheres with more than 10,000 layers were successfully performed with a HP work station. The new algorithm circumvents the limitations introduced by the numerical round-off errors encountered when using the previously developed recursive relations to calculate the ratios of Riccati-Bessel functions. Tests and calculations show that the method is stable and accurate for a large range of size parameters and optical properties. By employing the proposed algorithm, the problems encountered in analyzing the scattering by spheres with continuous-profile refractive indices can be solved with good accuracy.

Temperature and size of single transparent droplets by light scattering in the forward and rainbow regions.

A light-scattering anaysis based on Lorenz-Mie theory shows that the size and refractive index of transparent droplets can be determined by measuring the polarized components of the scattered light at two angles in the forward direction. The horizontally polarized cross section C(HH)(33°) depends exclusively on the droplet diameter, whereas the ratio C(HH)(33°)/C(HH)(60°) is a sensitive function of the refractive index and hence of the temperature. On this basis, a new optical system for measuring the temperature, size, and velocity of transparent droplets has been developed. This system can make possible the determination of droplet temperature within a few degrees centigrade. In addition, a critical review of the rainbow method to determine droplet temperature is also presented. These techniques have been applied to vaporizing tetradecane droplets (D(0) = 72 µm), which are heated up in a tube furnace with a temperature range of 20°-200 °C.

Single droplet size, velocity, and optical characteristics by the polarization properties of scattered light.

A method is described for obtaining size, velocity, and optical properties of transparent spherical droplets employing the polarization characteristics of scattered light. A preliminary analysis of the Lorenz-Mie solution, in comparison with geometrical optics, points out the importance of surface waves in the side scattering region between theta = 85 degrees and theta = 120 degrees . Here the horizontal component of scattered light due to surface waves prevails over that due to external reflection for droplets smaller than 100 microm and the polarization ratiogamma = C(HH)/C(VV) can be employed for determining the particle size. A dual-beam system is made of two equal intensity circularly counterotating polarized laser beams which generate a polarized fringe pattern in the interference volume. The polarization ratio of scattered light, at a fixed scattering angle theta, and velocity is obtained by analysis of the bursts produced by individual droplets. The method was tested by determining the size and velocity distribution functions of droplet arrays produced by a Berglund-Liu atomizer operated either in monodisperse or in bidisperse regimes. The angular pattern of the polarization ratio was determined on calibrated streams of transparent droplets with different refractive indices, and the influence of this parameter on the role of surface waves in different angular scattering regions is discussed.

[Beta-thromboglobulin and fibrinopeptide A in acute myocardial infarction]. / Beta-tromboglobulina e fibrinopeptide A nell'infarto acuto del miocardio.

Fifty patients suffering from acute myocardial infarction were evaluated for beta-thromboglobulin and fibrinopeptide A (FpA) during the first 12 hours after admission. It has been noted that beta-thromboglobulin levels were higher than normal in most of patients examined, whereas FpA levels were higher only in four cases. On the contrary, after 12 hours beta-thromboglobulin levels were normal in all subjects whereas FpA levels showed the same high values. These results indicate that platelets may play an important role only in the acute phase of infarction and that the thrombus formation, accounted for by presence of fibrinogen derivative, only later might occur.