Size-Resolved Identification, Characterization, and Quantification of Primary Biological Organic Aerosol at a European Rural Site.

Primary biological organic aerosols (PBOA) represent a major component of the coarse organic matter (OMCOARSE, aerodynamic diameter > 2.5 µm). Although this fraction affects human health and the climate, its quantification and chemical characterization currently remain elusive. We present the first quantification of the entire PBOACOARSE mass and its main sources by analyzing size-segregated filter samples collected during the summer and winter at the rural site of Payerne (Switzerland), representing a continental Europe background environment. The size-segregated water-soluble OM was analyzed by a newly developed offline aerosol mass spectrometric technique (AMS). Collected spectra were analyzed by three-dimensional positive matrix factorization (3D-PMF), showing that PBOA represented the main OMCOARSE source during summer and its contribution to PM10 was comparable to that of secondary organic aerosol. We found substantial cellulose contributions to OMCOARSE, which in combination with gas chromatography mass spectrometry molecular markers quantification, underlined the predominance of plant debris. Quantitative polymerase chain reaction (qPCR) analysis instead revealed that the sum of bacterial and fungal spores mass represented only a minor OMCOARSE fraction (<0.1%). X-ray photoelectron spectroscopic (XPS) analysis of C and N binding energies throughout the size fractions revealed an organic N increase in the PM10 compared to PM1 consistent with AMS observations.

Ozone-induced band bending on metal-oxide surfaces studied under environmental conditions.

Ozone adsorption and decomposition on metal oxides is of wide interest in technology and in atmospheric chemistry. Here, ozone-adsorption-induced band bending is observed on Ti- and Fe-oxide model surfaces under dry and humid conditions. Photoelectron spectroscopic studies indicate the effect of charge transfer to O3, which limits the surface coverage of the precursor to decomposition reactions. This is also consistent with the negative pressure dependence observed in previous studies. These results contribute to our fundamental understanding of ozone adsorption and decomposition mechanisms on metal oxides of environmental and technological relevance.

Adsorption of acetic acid on ice studied by ambient-pressure XPS and partial-electron-yield NEXAFS spectroscopy at 230-240 K.

Ice plays a key role in the environment, and the ice-air interface influences heterogeneous chemical reactions between snowpack or cirrus clouds and the surrounding air. Soluble gases have been suspected to affect the topmost, disordered layer on ice (often referred to as a quasiliquid layer, QLL). Changes are especially expected in the hydrogen-bonding structure of water in the presence of solutes at the ice surface. Here, we used ambient-pressure X-ray photoelectron spectroscopy (XPS) to detect acetic acid at the ice surface at 230-240 K under atmospheric conditions for the first time. Electron-kinetic-energy-dependent C 1s spectra indicate that acetic acid remains confined to the topmost ice surface layers. Spectral analysis provides information about the protonation state of acetate at the ice surface. Surface-sensitive Auger-electron-yield C-edge near-edge X-ray absorption fine structure (NEXAFS) spectra were recorded to probe the molecular state of the adsorbed species. The O-edge NEXAFS spectra show only minor differences between clean ice and ice with adsorbed acetic acid and thus indicate that acetic acid does not lead to an extended disordered layer on the ice surface between 230 and 240 K.

Surface chemical properties of eutectic and frozen NaCl solutions probed by XPS and NEXAFS.

We study the surface of sodium chloride-water mixtures above, at, and below the eutectic temperature using X-ray photoelectron spectroscopy (XPS) and electron-yield near-edge X-ray absorption fine structure (NEXAFS) spectroscopy. The NaCl frozen solutions are mimicking sea-salt deposits in ice or snow. Sea-salt particles emitted from the oceans are a major contributor to the global aerosol burden and can act as a catalyst for heterogeneous chemistry or as cloud condensation nuclei. The nature of halogen ions at ice surfaces and their influence on surface melting of ice are of significant current interest. We found that the surface of the frozen solution, depending on the temperature, consists of ice and different NaCl phases, that is, NaCl, NaCl·2H(2)O, and surface-adsorbed water.

The nature of nitrate at the ice surface studied by XPS and NEXAFS.

Trace contaminants such as strong acids have been suggested to affect the thickness of the quasi-liquid layer at the ice/air interface, which is at the heart of heterogeneous chemical reactions between snowpacks or cirrus clouds and the surrounding air. We used X-ray photoelectron spectroscopy (XPS) and electron yield near edge X-ray absorption fine structure (NEXAFS) spectroscopy at the Advanced Light Source (ALS) to probe the ice surface in the presence of HNO(3) formed from the heterogeneous hydrolysis of NO(2) at 230 K. We studied the nature of the adsorbed species at the ice/vapor interfaces as well as the effect of HNO(3) on the hydrogen bonding environment at the ice surface. The NEXAFS spectrum of ice with adsorbed HNO(3) can be represented as linear combination of the clean ice and nitrate solution spectrum, thus indicating that in the presence of HNO(3) the ice surface consists of a mixture of clean ice and nitrate ions that are coordinated as in a concentrated solution at the same temperature but higher HNO(3) pressures.

Structural characterization of U(VI) surface complexes on kaolinite in the presence of humic acid using EXAFS spectroscopy.

To determine the influence of humic acid (HA), pH, and presence of atmospheric CO2 on the sorption of U(VI) onto kaolinite, the structure of the surface complexes was studied by U L III-edge extended X-ray absorption fine structure (EXAFS) spectroscopy. The best fits to the experimental EXAFS data were obtained by including two uranium coordination shells with two axial (O ax) and five equatorial (O eq) oxygen atoms at 1.77+/-0.02 and 2.34+/-0.02 A, respectively, and two coordination shells with one Al/Si atom each at 3.1 and 3.3 A. As in the case of the binary system U(VI)-kaolinite, uranium forms inner-sphere surface complexes by edge sharing with aluminum octahedra and/or silicon tetrahedra. HA and atmospheric CO2 as well as pH had no influence on the EXAFS structural parameters in the pH range of 5-8. Despite the presence of HA, U(VI) prefers to sorb directly onto kaolinite and not to HA that is bound to the clay surface. X-ray photoelectron spectroscopy (XPS) measurements of kaolinite particles that had been exposed to HA suspensions showed that significant parts of the kaolinite surface are not covered by HA.

U(VI)-kaolinite surface complexation in absence and presence of humic acid studied by TRLFS.

Time-resolved laser-induced fluorescence spectroscopy (TRLFS) was applied to study the U(VI) surface complexes on kaolinite in the presence and absence of humic acid (HA). Two uranyl surface species with fluorescence lifetimes of 5.9 +/- 1.4 and 42.5 +/- 3.4 micros and 4.4 +/- 1.2 and 30.9 +/- 7.2 micros were identified in the binary (U(VI)-kaolinite) and ternary system (U(VI)-HA-kaolinite), respectively. The fluorescence spectra of adsorbed uranyl surface species are described with six and five fluorescence emission bands in the binary and ternary system, respectively. The positions of peak maxima are shifted significantly to higher wavelengths compared to the free uranyl ion in perchlorate medium. HA has no influence on positions of the fluorescence emission bands. In the binary system, both surface species can be attributed to adsorbed bidentate mononuclear surface complexes, which differ in the number of water molecules in their coordination environment. In the ternary system, U(VI) prefers direct binding on kaolinite rather than via HA, but it is sorbed as a uranyl-humate complex. Consequently, the hydration shell of the U(VI) surface complexes is displaced with complexed HA, which is simultaneously distributed between kaolinite particles. Aluminol binding sites are assumed to control the sorption of U(VI) onto kaolinite.