Time-resolved Microwave Conductivity. Part 2.-Quantum-sized TiO_2 and the Effect of Adsorbates and Light Intensity on Charge-carrier Dynamics

Charge-carrier recombination dynamics after a pulsed laser excitation are investigated by time-resolved microwave conductivity (TRMC) for quantum-sized (Q-) TiO_2 and P25, a bulk-phase TiO_2. Adsorbed scavengers such as HNO_3, HC, HCIO_4, isopropyl alcohol, trans-decalin, tetranitromethane, and methyl viologen dichloride result in different charge-carrier recombination dynamics for Q-TiO_2 and P25. The differences include a current doubling with isopropyl alcohol for which electron injection into Q-TiO_2 is much slower than into P25 and relaxation of the selection rules of an indirect-bandgap semiconductor due to size quantization. However, the faster interfacial charge transfer predicted for Q-TiO_2 due to a 0. 2 eV gain in redox overpotentials is not observed. The effect of light intensity is also investigated. Above a critical injection level, fast recombination channels are opened, which may be a major factor resulting in the dependence of the steady-state photolysis quantum yields on l^(–1/2). The fast recombination channels are opened at lower injection levels for P25 than for Q-TiO_2, and a model incorporating the heterogeneity of surface-hole traps is presented

Time-resolved Microwave Conductivity. Part 1.—TiO_2 Photoreactivity and Size Quantization

Charge-carrier recombination dynamics after laser excitation are investigated by time-resolved microwave conductivity (TRMC) measurements of quantum-sized (Q-) TiO_2, Fe^(III)-doped Q-TiO_2, ZnO and CdS, and several commercial bulk-sized TiO2 samples. After pulsed laser excitation of charge carriers, holes that escape recombination react with sorbed trans-decalin within ns while the measured conductivity signal is due to conduction-band electrons remaining in the semiconductor lattice. The charge-carrier recombination lifetime and the interfacial electron-transfer rate constant that are derived from the TRMC measurements correlate with the CW photo-oxidation quantum efficiency obtained for aqueous chloroform in the presence of TiO_2. The quantum efficiencies are 0. 4 % for Q-TiO_2, 1. 6 % for Degussa P25, and 2. 0 % for Fe^(III)-doped Q-TiO_2. The lower quantum efficiencies for Q-TiO_2 are consistent with the relative interfacial electron-transfer rates observed by TRMC for Q-TiO_2 and Degussa P25. The increased quantum efficiencies of Fe^(III)-doped Q-TiO_2 and the observed TRMC decays are consistent with a mechanism involving fast trapping of valence-band holes as Fe^(IV) and inhibition of charge-order recombination

Sensitivity of sulfate direct climate forcing to the hysteresis of particle phase transitions

The effects of solid-aqueous phase transitions on sulfate direct climate forcing (SDCF) are investigated by using both a column model and a global chemical transport model. Aqueous particles have a larger mass extinction efficiency but a smaller backscattered fraction than their solid counterparts. The column model shows that the hysteresis of the phase transition can result in an uncertainty in the SDCF of 20%. The global chemical transport model explicitly accounts for the relative humidity processing of particles and the associated hysteresis. The model also treats the extent of sulfate neutralization by ammonia. For the anthropogenic sulfate, the base case simulation finds that solid particles contribute 41% of the global burden, 26% of the clear-sky optical thickness, 31% of the clear-sky SDCF, and 37% of the full-sky SDCF, a trend that reflects the correlation of solid particles with clear skies. A perturbation to the model, omitting hysteresis by assuming that all particles are aqueous, results in an overestimate of the SDCF by +8% compared to the base case. A converse assumption that crystallization occurs at the deliquescence relative humidity underestimates the SDCF by -8%. A case that assumes that aqueous particles occur whenever the ambient relative humidity exceeds the crystallization relative humidity biases the SDCF by +5%. A case that includes hysteresis but omits the difference in the fraction of radiation backscattered to space by aqueous compared to solid particles changes the SDCF by +15%. Seasonal and regional differences can be much larger. We recommend that the ratio of the sulfate aerosol optical thickness calculated with versus without consideration of particle hygroscopicity be reported as a standard output of SDCF models to facilitate meaningful intercomparisons among different models

Growth and Dissolution of Iron and Manganese Oxide Films

Growth and dissolution of Fe and Mn oxide films are key regulators of the fate and transport of heavy metals in the environment, especially during changing seasonal conditions of pH and dissolved oxygen. The Fe and Mn are present at much higher concentrations than the heavy metals, and, when Fe and Mn precipitate as oxide films, heavy metals surface adsorb or co-precipitate and are thus essentially immobilized. Conversely, when the Fe and Mn oxide films dissolve, the heavy metals are released to aqueous solution and are thus mobilized for transport. Therefore, understanding the dynamics and properties of Fe and Mn oxide films and thus on the uptake and release of heavy metals is critically important to any attempt to develop mechanistic, quantitative models of the fate, transport, and bioavailablity of heavy metals. A primary capability developed in our earlier work was the ability to grow manganese oxide (MnO{sub x}) films on rhodochrosite (MnCO{sub 3}) substrate in presence of dissolved oxygen under mild alkaline conditions. The morphology of the films was characterized using contact-mode atomic force microscopy. The initial growth began by heteroepitaxial nucleation. The resulting films had maximum heights of 1.5 to 2 nm as a result of thermodynamic constraints. Over the three past years, we have investigated the effects of MnO{sub x} growth on the interactions of MnCO{sub 3} with charged ions and microorganisms, as regulated by the surface electrical properties of the mineral. In 2006, we demonstrated that MnO{sub x} growth could induce interfacial repulsion and surface adhesion on the otherwise neutral MnCO{sub 3} substrate under environmental conditions. Using force-volume microscopy (FVM), we measured the interfacial and adhesive forces on a MnO{sub x}/MnCO{sub 3} surface with a negatively charged silicon nitride tip in a 10-mM NaNO3 solution at pH 7.4. The interfacial force and surface adhesion of MnOx were approximately 40 pN and 600 pN, respectively, whereas those of MnCO{sub 3} were essentially zero. The force differences between MnO{sub x} and MnCO{sub 3} suggest that oxide film growth can focus adsorbates to certain parts of the surface and thereby templating a heterogeneous layout of them. We suspected that the force differences were in part due to the differences in surface electrical properties. In 2007, we investigated two important electrical properties of MnO{sub x} and MnCO{sub 3} surfaces, namely surface potential and ion mobility. Surface potential is a composite quantity that can be linked to the local lattice structure of the reconstructed surface and the adsorption of water layers. The mobile surface ions formed by dissolution can also contribute to surface potential. Using Kelvin probe force microscopy (KPFM) and scanning polarization force microscopy (SPFM), we found that MnOx possessed excess surface potentials of over +200 mV in humid nitrogen and the excess surface potential decreased with increasing relative humidity (i.e., increasing adsorbed water layers on the mineral surface). The dependence of the excess surface potential was attributed to the change of the contributions from mobile ions. These results supported our earlier hypothesis that MnO{sub x} and MnCO{sub 3} had different surface electrical properties. In the third year, we systematically characterized that the change of the electrical double layer (EDL) structure of MnCO{sub 3} surface due to MnO{sub x} growth in aqueous solution and its dependence on pH. The structure of the electrical double layer determines the electrostatic interactions between the mineral surface and charged adsorbates. As described by the Derjaguin-Landau-Verwey-Overbeek (DLVO) theory, the electrostatic force, together with van der Waals interaction, regulates surface adsorption and bacterial attachment. Once adsorbates establish contact with the surface, they must resist hydraulic shear forces through surface adhesion. The adhesion of mineral surfaces is also affected by their electrostatic interactions with adsorbates. To probe the EDL structure, we applied force-volume microscopy coupled with physical and chemical models of the SPM system

Photocatalyzed Destruction of Chlorinated Hydrocarbons

Semiconductor photocatalysis with a primary focus on TiO₂ as a durable photocatalyst has been applied as a method for water and air purification. In this thesis, the basic electronic and chemical processes underlying the quantum efficiencies of the TiO₂/UV process are investigated. Time-resolved microwave conductivity experiments provide the recombination lifetimes and interfacial charge transfer rate constants of eight different TiO₂ catalysts. Their quantum efficiencies towards the photooxidation of chlorinated hydrocarbons vary from 0.04 to 0.44%. A direct correlation between (1) the quantum efficiencies and (2) the recombination lifetimes and the interfacial charge transfer rate constants is observed. The charge-carrier recombination rate in size-quantized particles ( 1-4 nm) is increased due to the mixing of states that relaxes the selections rules of an indirect bandgap semiconductor. The effects of protonation (i.e., pH 7-12) of amphoteric ZnO surface states on cross-sections for electron capture at the surface are studied by time-resolved radio frequency conductivity. Electrostatic repulsion due to a negatively-charged ZnO-surface leads to decreasing surf ace recombination rates with increasing pH. Vanadium doped into TiO₂ affects the quantum efficiency. Depending on the preparation method, vanadium plays three distinct roles. First, vanadium is present as surficial &#62; VO₂⁺ and promotes charge-carrier recombination through electron-trapping followed by hole elimination. Second, V(IV) impurities in surficial V₂O₅ islands result in enhanced charge-carrier recombination through hole-trapping followed by electron elimination. Third, V(IV) is substitutional in the TiO₂ lattice in the form of a solid solution, Vₓ Ti₁₋ₓO₂. The V(IV) centers trap both electrons and holes and thus yield enhanced charge-carrier recombination. The addition of inorganic oxidants such as HSO₅⁻, ClO₃⁻, IO₄⁻, and BrO₃⁻ increases the quantum efficiency. BrO₃⁻ acts by scavenging conduction-band electrons and reducing charge-carrier recombination. When ClO₃⁻ is present, however, competitive adsorption for the TiO₂ surface occurs among 4-CP, ClO₃⁻, and O₂, and the heterogeneous photodegradation of 4-chlorophenol follows three parallel pathways. ClO₃⁻ favors a reaction pathway involving the thermal oxidation of the reactive intermediates.</p

Hygroscopic Behavior of NaCl-Bearing Natural Aerosol Particles Using Environmental Transmission Electron Microscopy

We used conventional and environmental transmission electron microscopes to determine morphology, composition, and water uptake of individual natural inorganic aerosol particles collected from industrial pollution plumes and from clean and polluted marine environments. Five particle types are described in detail. They range from relatively insoluble mineral grains to internally mixed particles containing NaCl with other soluble or relatively insoluble material. We studied the hygroscopic behavior of these particles from 0 to 100% relative humidity (RH). Relatively insoluble materials do not take up water over the experimental RH range. Single crystals of NaCl from both natural and laboratory sources have a well-defined deliquescence point of approximately 76% RH at 291 K. NaCl-bearing aggregate particles appear to deliquesce between 74 and 76% RH (same RH within error) when NaCl is internally mixed with relatively insoluble phases, but the particles deliquesce at lower RH when aggregated with other soluble phases such as NaNO3. For all NaCl-bearing particles studied, hygroscopic growth is pronounced above 76% RH, and water uptake by the particles is dominated by the soluble phase. Furthermore, the soluble phase initiating deliquescence controls the locus of further hygroscopic growth of the aggregate particle. Our results demonstrate that composition and mixing state affect water uptake of natural aerosol particles. Furthermore, internally mixed particles are confirmed to deliquesce at lower RH values than predicted from the individual components

Exploring the diversity of Gardnerella vaginalis in the genitourinary tract microbiota of monogamous couples through subtle nucleotide variation

© The Author(s), 2011. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in PLoS One 6 (2011): e26732, doi:10.1371/journal.pone.0026732.Bacterial vaginosis (BV) is an enigmatic disease of unknown origin that affects a large percentage of women. The vaginal microbiota of women with BV is associated with serious sequelae, including abnormal pregnancies. The etiology of BV is not fully understood, however, it has been suggested that it is transmissible, and that G. vaginalis may be an etiological agent. Studies using enzymatic assays to define G. vaginalis biotypes, as well as more recent genomic comparisons of G. vaginalis isolates from symptomatic and asymptomatic women, suggest that particular G. vaginalis strains may play a key role in the pathogenesis of BV. To explore G. vaginalis diversity, distribution and sexual transmission, we developed a Shannon entropy-based method to analyze low-level sequence variation in 65,710 G. vaginalis 16S rRNA gene segments that were PCR-amplified from vaginal samples of 53 monogamous women and from urethral and penile skin samples of their male partners. We observed a high degree of low-level diversity among G. vaginalis sequences with a total of 46 unique sequence variants (oligotypes), and also found strong correlations of these oligotypes between sexual partners. Even though Gram stain-defined normal and some Gram stain-defined intermediate oligotype profiles clustered together in UniFrac analysis, no single G. vaginalis oligotype was found to be specific to BV or normal vaginal samples. This study describes a novel method for investigating G. vaginalis diversity at a low level of taxonomic discrimination. The findings support cultivation-based studies that indicate sexual partners harbor the same strains of G. vaginalis. This study also highlights the fact that a few, reproducible nucleotide variations within the 16S rRNA gene can reveal clinical or epidemiological associations that would be missed by genus-level or species-level categorization of 16S rRNA data.This work is supported by funding from the Research Institute for Children in New Orleans and NIH grant 5RO1AI79071-2

Modeling the variations of Dose Rate measured by RAD during the first MSL Martian year: 2012-2014

The Radiation Assessment Detector (RAD), on board Mars Science Laboratory's (MSL) rover Curiosity, measures the {energy spectra} of both energetic charged and neutral particles along with the radiation dose rate at the surface of Mars. With these first-ever measurements on the Martian surface, RAD observed several effects influencing the galactic cosmic ray (GCR) induced surface radiation dose concurrently: [a] short-term diurnal variations of the Martian atmospheric pressure caused by daily thermal tides, [b] long-term seasonal pressure changes in the Martian atmosphere, and [c] the modulation of the primary GCR flux by the heliospheric magnetic field, which correlates with long-term solar activity and the rotation of the Sun. The RAD surface dose measurements, along with the surface pressure data and the solar modulation factor, are analysed and fitted to empirical models which quantitatively demonstrate} how the long-term influences ([b] and [c]) are related to the measured dose rates. {Correspondingly we can estimate dose rate and dose equivalents under different solar modulations and different atmospheric conditions, thus allowing empirical predictions of the Martian surface radiation environment

Hygroscopic Behavior and Liquid-Layer Composition of Aerosol Particles Generated from Natural and Artificial Seawater

Sea-salt aerosol (SSA) particles affect the Earth\u27s radiative balance and moderate heterogeneous chemistry in the marine boundary layer. Using conventional and environmental transmission electron microscopes (ETEM), we investigated the hygroscopic growth and liquid-layer compositions of particles generated from three types of aqueous salt solutions: sodium chloride, laboratory-synthesized seawater (S-SSA particles), and natural seawater (N-SSA particles). Three levels of morphological change were observed with the ETEM as the laboratory-generated particles were exposed to increasing relative humidity (RH). The first level, onset of observable morphological changes, occurred on average at 70, 48, and 35% RH for the NaCl, S-SSA, and N-SSA particles, respectively. The second level, rounding, occurred at 74, 66, and 57% RH for NaCl, S-SSA, and N-SSA particles, respectively. The third level, complete deliquescence, occurred at 75% RH for all particles. Collected ambient SSA particles were also examined. With the exception of deliquescence, they did not exhibit the same hygroscopic characteristics as the NaCl particles. The ambient particles, however, behaved most similarly to the synthesized and natural SSA particles, although the onset of morphological change was slightly higher for the S-SSA particles. We used energy-dispersive X-ray spectrometry to study the composition of the liquid layer formed on the S-SSA and N-SSA particles. The layer was enriched in Mg, S, and O relative to the solid particle core. An important implication of these results is that MgSO4-enriched solutions on the surface of SSA particles may be the solvents of many heterogeneous reactions