Validating a nondestructive optical method for apportioning colored particulate matter into black carbon and additional components.

Exposure of black carbon (BC) is associated with a variety of adverse health outcomes. A number of optical methods for estimating BC on Teflon filters have been adopted but most assume all light absorption is due to BC while other sources of colored particulate matter exist. Recently, a four-wavelength-optical reflectance measurement for distinguishing second hand cigarette smoke (SHS) from soot-BC was developed (Brook et al., 2010; Lawless et al., 2004). However, the method has not been validated for soot-BC nor SHS and little work has been done to look at the methodological issues of the optical reflectance measurements for samples that could have SHS, BC, and other colored particles. We refined this method using a lab-modified integrating sphere with absorption measured continuously from 350 nm to 1000 nm. Furthermore, we characterized the absorption spectrum of additional components of particulate matter (PM) on PM(2.5) filters including ammonium sulfate, hematite, goethite, and magnetite. Finally, we validate this method for BC by comparison to other standard methods. Use of synthesized data indicates that it is important to optimize the choice of wavelengths to minimize computational errors as additional components (more than 2) are added to the apportionment model of colored components. We found that substantial errors are introduced when using 4 wavelengths suggested by Lawless et al. to quantify four substances, while an optimized choice of wavelengths can reduce model-derived error from over 10% to less than 2%. For environmental samples, the method was sensitive for estimating airborne levels of BC and SHS, but not mass loadings of iron oxides and sulfate. Duplicate samples collected in NYC show high reproducibility (points consistent with a 1:1 line, R(2) = 0.95). BC data measured by this method were consistent with those measured by other optical methods, including Aethalometer and Smoke-stain Reflectometer (SSR); although the SSR looses sensitivity at filter loadings above 90 ng/mm(2). Furthermore, positive correlations (R(2) = 0.7) were observed between EC measured by NIOSH Method 5040 on quartz filters and BC measured in co-located Teflon filter samples collected from both heating and non-heating seasons. Overall, the validation data demonstrates the usefulness of this method to evaluate BC from archived Teflon filters while potentially providing additional component information.

Probing liquid surfaces under vacuum using SEM and ToF-SIMS.

We report a newly developed self-contained interface for high-vapor pressure liquid surfaces to vacuum-based analytical instruments. It requires no wires or tubing connections to the outside of the instrument and uses a microfluidic channel with a 3 µm diameter window into the flowing fluid beneath it. This window supports the liquid against the vacuum by the liquid's surface tension and limits the high-density vapor region traversed by the probe beams to only a few microns. We demonstrate this microfluidic interface for in situ liquid surfaces in a time-of-flight secondary ion mass spectrometer (ToF-SIMS) and a scanning electron microscope (SEM) with chemical analysis.

The oil-water interface: mapping the solvation potential.

An ion moving across an oil-water interface experiences strong solvation changes. We have directly measured the solvation potential from 0.4 to 4 nm for Cs(+) ions approaching the oil-water interface from the oil side ("oil" = 3-methylpentane). The interfaces were built at 30 K using molecular beam epitaxy. Ions were precisely placed within the film during its growth using a soft-landing ion beam. The ion's collective electric field was progressively increased (by adding more ions) until it balanced the individual ion's solvation potential slope. As the samples were slowly warmed, near 90 K the ions began moving, as measured by a Kelvin probe. Their motion precisely determines the local slope of the solvation potential, which was integrated to get the potential. The potential is Born-like for z > 0.4 nm away from the oil-water interface. Our method could provide important tests of theoretical estimates of ion motion at biological interfaces and in atmospheric aerosols.

Pyroelectricity of water ice.

Water ice usually is thought to have zero pyroelectricity by symmetry. However, biasing it with ions breaks the symmetry because of the induced partial dipole alignment. This unmasks a large pyroelectricity. Ions were soft-landed upon 1 mum films of water ice at temperatures greater than 160 K. When cooled below 140-150 K, the dipole alignment locks in. Work function measurements of these films then show high and reversible pyroelectric activity from 30 to 150 K. For an initial approximately 10 V induced by the deposited ions at 160 K, the observed bias below 150 K varies approximately as 10 Vx(T/150 K)2. This implies that water has pyroelectric coefficients as large as that of many commercial pyroelectrics, such as lead zirconate titanate (PZT). The pyroelectricity of water ice, not previously reported, is in reasonable agreement with that predicted using harmonic analysis of a model system of SPC ice. The pyroelectricity is observed in crystalline and compact amorphous ice, deuterated or not. This implies that for water ice between 0 and 150 K (such as astrophysical ices), temperature changes can induce strong electric fields (approximately 10 MV/m) that can influence their chemistry, ion trajectories, or binding.

Design and performance of an instrument for soft landing of biomolecular ions on surfaces.

A new ion deposition apparatus was designed and constructed in our laboratory. Our research objectives were to investigate interactions of biomolecules with hydrophilic and hydrophobic surfaces and to carry out exploratory experiments aimed at highly selective deposition of spatially defined and uniquely selected biological molecules on surfaces. The apparatus includes a high-transmission electrospray ion source, a quadrupole mass filter, a bending quadrupole that deflects the ion beam and prevents neutral molecules originating in the ion source from impacting the surface, an ultrahigh vacuum (UHV) chamber for ion deposition by soft landing, and a vacuum lock system for introducing surfaces into the UHV chamber without breaking vacuum. Ex situ analysis of surfaces following soft landing of mass-selected peptide ions was performed using 15 keV Ga+ time-of-flight secondary ion mass spectrometry and grazing incidence infrared reflection-absorption spectroscopy. It is shown that these two techniques are highly complementary methods for characterization of surfaces prepared with a range of doses of mass-selected biomolecular ions. We also demonstrated that soft landing of peptide ions on surfaces can be utilized for controlled preparation of peptide films of known coverage for fundamental studies of matrix effects in SIMS.

Hydronium ion motion in nanometer 3-methyl-pentane films.

An ion soft-landing approach was applied to study the motion of hydronium (D(3)O(+)) and cesium (Cs(+)) ions from 84 to 104 K in glassy 3-methyl-pentane (3MP) films vapor deposited on Pt(111). Both ions were found to have very similar mobilities in 3MP. The span of ion mobilities probed is from approximately 10(-18) to approximately 10(-13) m(2) V(-1) s(-1). Ion transport in these films was studied as a function of film thickness and electric field strength. The drift velocity was found to be linear with applied field below about 2 x 10(8) Vm and deviated from linearity above this. To a large extent, D(3)O(+) and Cs(+) motion in 3MP was well predicted by a simple continuum-based ion mobility model in films from 25 to 20,000 ML thick (including pronounced perturbations 7 ML from both the vacuum and Pt interfaces). The mobility varied with temperature more slowly than predicted by Stokes' law, which may be due to extended inhomogeneous structures in the 3MP near its glass transition at 77 K.

Dissociation of water buried under ice on Pt(111).

Water on Pt(111) is generally thought to be nondissociative. However, by adsorbing a thick ice film [>150 monolayers (ML)], substantial (approximately 0.16 to 1 ML) dissociation of the "buried water" occurs for T>151 K. New temperature-programmed desorption peaks signal the dissociation (after careful isothermal predesorption of the overlying ice films). The buried water likely dissociates via the elevated temperatures and/or solvation changes experienced under the ice. Dissociation charges the growing ice film (up to +9 V) due to trapping of approximately 0.007 ML H3O+ at the vacuum-ice interface.

A new approach to determining gas-particle reaction probabilities and application to the heterogeneous reaction of deliquesced sodium chloride particles with gas-phase hydroxyl radicals.

The reaction kinetics for gaseous hydroxyl radicals (OH) with deliquesced sodium chloride particles (NaCl(aq)) were investigated using a novel experimental approach. The technique utilizes the exposure of substrate-deposited aerosol particles to reactive gases followed by chemical analysis of the particles using computer-controlled scanning electron microscopy with energy-dispersive analysis of X-rays (CCSEM/EDX) capability. Experiments were performed at room temperature and atmospheric pressure with deliquesced NaCl particles in the micron size range at 70-80% RH and with OH concentrations in the range of 1 to 7 x 10(9) cm(-3). The apparent, pseudo first-order rate constant for the reaction was determined from measurements of changes in the chloride concentration of individual particles upon reaction with OH as a function of the particle loading on the substrate. Quantitative treatment of the data using a model that incorporates both diffusion and reaction kinetics yields a lower limit to the net reaction probability of gamma(net) > or = 0.1, with an overall uncertainty of a factor of 2.

Reactions at interfaces as a source of sulfate formation in sea-salt particles.

Understanding the formation of sulfate particles in the troposphere is critical because of their health effects and their direct and indirect effects on radiative forcing, and hence on climate. Laboratory studies of the chemical and physical changes in sodium chloride, the major component of sea-salt particles, show that sodium hydroxide is generated upon reaction of deliquesced sodium chloride particles with gas-phase hydroxide. The increase in alkalinity will lead to an increase in the uptake and oxidation of sulfur dioxide to sulfate in sea-salt particles. This chemistry is missing from current models but is consistent with a number of previously unexplained field study observations.

Nanometer-resolved interfacial fluidity.

Confined liquids can have properties that are poorly predicted from bulk parameters. We resolve with 0.5 nm resolution the nanoscale perturbations that interfaces cause on fluidity, in thin 3-methylpentane (3MP) films. The films of glassy 3MP are much less viscous at the vacuum-liquid interface and much more viscous at the 3MP-metal interface, compared to the bulk of the film. We find that the viscosity at the interfaces continuously returns to the bulk value over about a 3 nm distance. The amorphous 3MP films are constructed using molecular beam epitaxy on a Pt(111) substrate at low temperatures (<30 K). Ions are gently inserted at specific distances from the substrate with a 1 eV hydronium (D(3)O(+)) or Cs(+) ion beam. The voltage across the film, which is directly proportional to the position of the ions within the film, is monitored electrostatically as the film is heated at a rate of 0.2 K/s. Above the bulk glass transition temperature (T(g)) of 3MP (77 K), the ions are expected to begin to move down through the film. However, ion movement is observed at temperatures as low as 50 K near the vacuum interface, well below the bulk T(g). The fitted kinetics predict that at 85 K, the glass is about 6 orders of magnitude less viscous near the free interface compared to that of the bulk.

Quantitative time-resolved monitoring of nitrate formation in sea salt particles using a CCSEM/EDX single particle analysis.

Progress of the nitrate formation in individual sea salt particles was detected as a function of time using aerosol samples collected during the TexAQS 2080 experiment We demonstrate that the time-resolved collection approach coupled with the automated EDX single particle analysis made it possible to follow in detail the time evolution of sea salt particles within a diverse aerosol mixture. Using a custom built Time-Resolved Aerosol Collector (TRAC), particulate samples were taken sequentially on grid-supported 50 nm carbon films with a time resolution of 10 min between two consecutive samples. The samples were analyzed in the laboratory using Computer Controlled Scanning Electron Microscopy with Energy-Dispersed analysis of X-rays (CCSEM/EDX). Between midnight of 08/16/00 and the early morning of 08/17/00, a steady, particularly sea salt rich aerosol was observed at the measurement site, which later showed the effects of atmospheric processing. During the night of 08/17/00 the sea salt particles were almost unprocessed, having elemental composition close to that of seawater. By 12 noon, the evolving atmosphere was able to completely convert them, predominantly to sodium nitrate particles. During the next night this process had nearly stopped and fairly virgin sea salt particles appeared again.