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At least 343 records · Page 19

The greenhouse effect in a gray planetary atmosphere.

Hopf analytical solution for values of ratio of gray absorption coefficients for insolating and escaping radiation /greenhouse parameter/ assumed constant at all depths, presenting temperature distribution graphs

ABSORPTION COEFFICIENT↗

Optical properties and CCN activity of aerosols in a high-altitude Himalayan environment: Results from RAWEX-GVAX: CCN activity of aerosols over Himalayas

The seasonality and mutual dependence of aerosol optical properties and cloud condensation nuclei (CCN) activity under varying meteorological conditions at the high-altitude Nainital site (~2 km) in the Indo-Gangetic Plains were examined using nearly year-round measurements (June 2011 to March 2012) at the Atmospheric Radiation Measurement (ARM) mobile facility as part of the RAWEX-GVAX experiment of the Indian Space Research Organization and the U.S. Department of Energy. The results from collocated measurements provided enhanced aerosol scattering and absorption coefficients, CCN concentrations and total condensation nuclei (CN) concentrations during the dry autumn and winter months. The CCN concentration (at a supersaturation of 0.46) was higher during periods of high aerosol absorption (single-scattering albedo (SSA) < 0.80) than during periods of high aerosol scattering (SSA > 0.85), indicating that the aerosol composition seasonally changes and influences the CCN activity. The monthly mean CCN activation ratio (at a supersaturation of 0.46) was highest (> 0.7) in late autumn (November); this finding is attributed to the contribution of biomass-burning aerosols to CCN formation at high supersaturation conditions.

54 ENVIRONMENTAL SCIENCES↗

Deriving brown carbon from multiwavelength absorption measurements: Method and application to AERONET and Aethalometer observations

The radiative impact of organic aerosols (OA) is a large source of uncertainty in estimating the global direct radiative effect (DRE) of aerosols. This radiative impact includes not only light scattering but also light absorption from a subclass of OA referred to as brown carbon (BrC). However the absorption properties of BrC are poorly understood leading to large uncertainties in modelling studies. To obtain observational constraints from measurements, a simple Absorption Ångström Exponent (AAE) method is often used to separate the contribution of BrC absorption from that of black carbon (BC). However, this attribution method is based on assumptions regarding the spectral dependence of BC that are often violated in the ambient atmosphere. Here we develop a new method that decreases the uncertainties associated with estimating BrC absorption. By applying this method to multi-wavelength absorption aerosol optical depth (AAOD) measurements at AERONET sites worldwide and surface aerosol absorption measurements at multiple ambient sites, we estimate that BrC globally contributes 6-40% of the absorption at 440nm. We find that the mass absorption coefficient of OA (OA-MAC) is positively correlated with BC/OA mass ratio. Based on the variability of BC properties and BC/OA emission ratio, we estimate a range of 0.05-1.2 m 2 /g for OA-MAC at 440nm. Using the combination of AERONET and OMI UV absorption observations we estimate that the AAE 388/440nm for BrC is generally ~4 world-wide, with a smaller value in Europe (< 2). Our analyses of two surface sites (Cape Cod, to the southeast of Boston, and the GoAmazon2014/5 T3 site, to the west of Manaus, Brazil) reveal no significant relationship between BrC absorptivity and photochemical aging in typical urban influenced conditions. However, the absorption of BrC measured during the biomass burning season near Manaus is found to decrease with photochemical aging with a lifetime of ~1 day. This lifetime is comparable to previous observations within a biomass burning plume but much slower than estimated from laboratory studies.

54 ENVIRONMENTAL SCIENCES↗

Holography with surface plasma waves

New technique utilizes reflection-type diffraction grating of type generally used in grating spectrometers. Grating is coated with thin layer of high-resolution recording medium, having absorption coefficient low enough to prevent incident light absorption before it is reflected by metal layer.

Cowan, J. J.↗

Resonance absorption of solar p-modes by sunspots

Braun et al. (1987) observation that the power in outgoing p-modes in the vicinity of sunspots is less than that incoming has prompted the present consideration of the possibility that this deficit is due to resonance absorption occurring when the sunspot boundary has nonzero thickness. A simple planar analysis is used to characterize the requisite conditions for this effect, and to estimate the absorption coefficient. It is found that the resonance absorption effect is unlikely to explain the substantial loss of p-mode power observed over a substantial range of frequency and azimuthal order.

Hollweg, Joseph V.↗

Black Carbon at the Mt. Bachelor Observatory Field Campaign Report

This campaign was initiated to measure refractory black carbon (rBC, as defined in Schwarz et al. (2010)) at the Mt. Bachelor Observatory (MBO) using the U.S. Department of Energy (DOE) Atmospheric Radiation Measurement (ARM) Climate Research Facility single-particle soot photometer (SP2; unit 54). MBO is a high-elevation site located on the summit of Mt. Bachelor in central Oregon, USA (43.979°N, 121.687°W, 2,763 meters ASL). This site is operated by Professor Dan Jaffe’s group at the University of Washington Bothell and has been used continuously as an atmospheric observatory for the past 12 years (Jaffe et al., 2005; Gratz et al., 2014). The location of MBO allows frequent sampling of the free troposphere along with a wide array of plumes from regional and distant sources. MBO is currently supported with funding from the National Science Foundation (NSF) to the Principal Investigator (PI; D. Jaffe) via the project “Influence of Free Tropospheric Ozone and PM on Surface Air Quality in the Western U.S.” (#1447832) covering the period 03/15/2015 to 02/28/2018. The SP2 instrument from Droplet Measurement Technologies provides particle-resolved measurements of rBC mass loading, size and mass distributions, and mixing state. The SP2 was installed at MBO on 6/27/2016 and ran through 9/23/2016. Additional measurements at MBO during this campaign included carbon monoxide (CO), fine particulate matter (PM1), aerosol light scattering coefficients (σscat) at three wavelengths using a TSI nephelometer, aerosol absorption coefficients (σabs) with the Brechtel tricolor absorption photometer (TAP), aerosol number size distributions with a scanning mobility particle sizer spectrometer (SMPS), and black carbon (eBC) with an aethalometer. BC data from this campaign have been submitted to the ARM Data Archive. Black carbon (BC) is the predominant light-absorbing aerosol constituent in the atmosphere, and is estimated to exert a positive radiative forcing second only to CO 2 (Ramanathan and Carmichael, 2008). One of the largest sources of BC globally is biomass burning (BB). (Akagi et al., 2011; Andreae and Merlet, 2001; Bond et al., 2013; Bond et al., 2004; Reid et al., 2005b): a source that is likely to increase in the Western U.S. due to climate change (Dennison et al., 2014; Abatzoglon and Williams, 2016; Westerling et al., 2006). Given the likely increased role of BB aerosol in atmospheric forcing, we need to improve our understanding of the physical and optical properties of aged BB aerosol. During the SP2 deployment period at MBO we observed seven BB events, all of which originated from the Gap Fire in Northern California, which burned 33,867 acres in the Klamath National Forest (https://inciweb.nwcg.gov/incident/4997/). Heavy smoke plumes from this fire were transported to MBO from 8/29/2016 to 8/31/2016. We calculated back-trajectories using the National Oceanic and Atmospheric Administration (NOAA) Hybrid Single-Particle Lagrangian Integrated Trajectory (HYSPLIT) model, version 4 (Draxler, 1999; Draxler and Hess, 1997, 1998; Stein et al., 2015) to confirm transport from the fire locations to MBO. We identified the fire locations using moderate resolution imaging spectroradiometer (MODIS) satellite-derived active fire counts (Justice et al., 2002). Transport time for all of the BB events ranged from 8 to 32 hours.

54 ENVIRONMENTAL SCIENCES↗

Nephelometer PSAP, BBOP

This field campaign will address multiple uncertainties in aerosol intensive properties, which are poorly represented in climate models, by means of aircraft measurements in biomass burning plumes. Key topics to be investigated are: Aerosol mixing state and morphology Mass absorption coefficients (MACs) Chemical composition of non-refractory material associated with light-absorbing carbon (LAC) Production rate of secondary organic aerosol (SOA) Microphysical processes relevant to determining aerosol size distributions and single scattering albedo (SSA) CCN activity.

54 ENVIRONMENTAL SCIENCES↗

Beyond green with synthetic chlorophylls – Connecting structural features with spectral properties

The distinct features of chlorophylls in photosynthesis have led to the formation of numerous derivatives for applications encompassing solar energy conversion, molecular photonics, photodynamic therapy, and molecular imaging. Synthetic chlorins created de novo and bearing a geminal dimethyl group in the reduced ring have proved invaluable for fundamental studies. Four decades of research have led to accumulation of tabulated spectra for > 400 such synthetic chlorins with distinct structural frameworks (17-oxochlorins, 13 1 -oxophorbines, chlorinimides) and substituents (alkyl, aryl, ethynyl, phenylethynyl, acetyl, formyl) located at specific (meso, β) positions. In this review, spectral traces (324 absorption, 247 fluorescence) are assembled along with photophysical data including the molar absorption coefficient (ε), fluorescence quantum yield (Φ f ) and singlet excited-state lifetime (τ s ). The review uses the accumulated spectral data derived from chlorins all containing a uniform molecular scaffold to (1) highlight the effects of molecular structure on spectral features, and (2) identify trends including how ε, Φ f and τ s vary with wavelength and other features. Use of a common geminal-dimethyl-substituted chlorin scaffold – beginning with no substituents, to one substituent at designated sites, and to 2 or more substituents – provides a systematic Aufbau approach for understanding the absorption spectra of chlorins on a path to and beyond the native chlorophylls. Finally, the review provides insights concerning the rational design of potent analogues of Nature’s preeminent red-region absorbers for potential utilization in diverse applications and is aimed at multiple audiences: those interested in spectral properties, tetrapyrrole photophysics, and the molecular design of new chromophores.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Understanding the optical properties of ambient sub- and supermicron particulate matter: results from the CARES 2010 field study in northern California

Abstract. Measurements of the optical properties (absorption, scattering and extinction) of PM1, PM2.5 and PM10 made at two sites around Sacramento, CA, during the June 2010 Carbonaceous Aerosols and Radiative Effects Study (CARES) are reported. These observations are used to establish relationships between various intensive optical properties and to derive information about the dependence of the optical properties on photochemical aging and sources. Supermicron particles contributed substantially to the total light scattering at both sites, about 50 % on average. A strong, linear relationship is observed between the scattering Ångström exponent for PM10 and the fraction of the scattering that is contributed by submicron particles (fsca, PM1) at both sites and with similar slopes and intercepts (for a given pair of wavelengths), suggesting that the derived relationship may be generally applicable for understanding variations in particle size distributions from remote sensing measurements. At the more urban T0 site, the fsca, PM1 increased with photochemical age, whereas at the downwind, more rural T1 site the fsca, PM1 decreased slightly with photochemical age. This difference in behavior reflects differences in transport, local production and local emission of supermicron particles between the sites. Light absorption is dominated by submicron particles, but there is some absorption by supermicron particles ( ∼ 15 % of the total). The supermicron absorption derives from a combination of black carbon that has penetrated into the supermicron mode and from dust, and there is a clear increase in the mass absorption coefficient of just the supermicron particles with increasing average particle size. The mass scattering coefficient (MSC) for the supermicron particles was directly observed to vary inversely with the average particle size, demonstrating that MSC cannot always be treated as a constant in estimating mass concentrations from scattering measurements, or vice versa. The total particle backscatter fraction exhibited some dependence upon the relative abundance of sub- versus supermicron particles; however this was modulated by variations in the median size of particles within a given size range; variations in the submicron size distribution had a particularly large influence on the observed backscatter efficiency and an approximate method to account for this variability is introduced. The relationship between the absorption and scattering Ångström exponents is examined and used to update a previously suggested particle classification scheme. Differences in composition led to differences in the sensitivity of PM2.5 to heating in a thermodenuder to the average particle size, with more extensive evaporation (observed as a larger decrease in the PM2.5 extinction coefficient) corresponding to smaller particles; i.e., submicron particles were generally more susceptible to heating than the supermicron particles. The influence of heating on the particle hygroscopicity varied with the effective particle size, with larger changes observed when the PM2.5 distribution was dominated by smaller particles.

54 ENVIRONMENTAL SCIENCES↗

Realization of BaZrS 3 chalcogenide perovskite thin films for optoelectronics

BaZrS 3 is a prototypical chalcogenide perovskite, an emerging class of unconventional semiconductor. Recent results on powder samples reveal that it is a material with a direct band gap of 1.7–1.8 eV, a very strong light-matter interaction, and a high chemical stability. Due to the lack of quality thin films, however, many fundamental properties of chalcogenide perovskites remain unknown, hindering their applications in optoelectronics. In this work, we report the fabrication of BaZrS 3 thin films, by sulfurization of oxide films deposited by pulsed laser deposition. We show that these films are n-type with carrier densities in the range of 10 19 -10 20 cm -3 . Depending on the processing temperature, the Hall mobility ranges from 2.1 to 13.7 cm 2 /Vs. The absorption coefficient is > 10 5 cm -1 at photon energy >1.97 eV. Temperature dependent conductivity measurements suggest shallow donor levels. By assuring that BaZrS 3 is a promising candidate, these results potentially unleash the family of chalcogenide perovskites for optoelectronics such as photodetectors, photovoltaics, and light emitting diodes.

36 MATERIALS SCIENCE↗

Thermophysical properties and conduction mechanisms in As x Se 1-x chalcogenide glasses ranging from x = 0.2 to 0.5

The arsenic (As) to selenium (Se) ratio in As x Se 1-x glasses ranging from x = 0.2 to 0.5 was varied in order to examine the effect of chemical and topological ordering on the glass' thermal transport behavior. The fundamental thermal properties of glass transition temperature (T g ), thermal conductivity (k), and heat capacity (c p ) were experimentally measured using differential scanning calorimetry, transient plane source method, and ultrasonic testing. Based on topological constraint theory, inflections in T g and k were found at the structural coordination number $\langle$r$\rangle$ of 2.4, whereas a slight increase in heat capacity (c p ) with increasing $\langle$r$\rangle$ was observed. A maximum in total thermal conductivity of 0.232 W/m·K was measured for the composition with x = 0.4, which corresponds to the stoichiometric As 2 Se 3 . Gas kinetic theory was used to derive an expression for the photon (k p ) portion of thermal conductivity, which was calculated by measurements of the glass' absorption coefficient (α) and refractive index (n). Models based on Debye theory were then used to derive expressions for specific heat (c v ) and the lattice (k l ) portion of thermal conductivity. The maximum value for k p was 0.173 W/m·K for the composition with x = 0.2, and a minimum value of 0.144 W/m·K was measured for the composition with x = 0.4. Photonic conduction was found to be the dominant carrier mechanisms in all compositions, comprising 60% to 95% of the measured total thermal conductivity.

36 MATERIALS SCIENCE↗

Comprehensive review of photophysical parameters (ε, Φ f , τ s ) of tetraphenylporphyrin (H 2 TPP) and zinc tetraphenylporphyrin (ZnTPP) – Critical benchmark molecules in photochemistry and photosynthesis

Tetraphenylporphyrin (H 2 TPP) and zinc tetraphenylporphyrin (ZnTPP) are widely used benchmark molecules in diverse photochemical studies given facile synthetic access, rich visible-region spectra, and broad structural analogy to chlorophylls. Yet the literature values for each key photophysical parameter – the molar absorption coefficient (ε), fluorescence quantum yield (Φ f ), and also singlet excited-state lifetime (τ S ) – vary over an astonishing range. Here, a comprehensive literature review (~1940–September 2020) encompassing 871 publications is reported for these essential parameters. Each parameter is determined by measurement with distinct instrumentation and suffers idiosyncratic sources of error. The best values for H 2 TPP are ε = 460,000 cm -1 ·M -1 , Φ f = 0.090, and τ S = 12.8 ns in Ar- purged toluene (Φf = 0.070, τS = 9.9 ns in toluene in air); the best values for ZnTPP are ε = 560,000 cm -1 ·M -1 , Φf = 0.030, and τ S = 2.1 ns in Ar-purged toluene (Φ f = 0.029, τ S = 2.0 ns in toluene in air). The choice of values for such parameters has far-reaching consequences in photochemistry ranging from fluorescence (or Förster) resonance energy transfer (FRET) processes to assessments of molecular brightness.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Energetic, electronic and optical properties of lanthanide doped TiO{sub 2}: An ab initio LDA+U study

Substitutional energies, thermodynamic charge transition levels and optical properties of lanthanide doped anatase TiO{sub 2} has been investigated using local density approximation with the Hubbard U correction (LDA+U) within the density functional theory formalism. All the lanthanides apart from La introduced impurity states in the host band gap on doping. The calculated substitutional energies indicate that it is possible to dope TiO{sub 2} with lanthanide ions. The optimal doping percentage was predicted to be ~3% and dopant levels resulting from Ce, Nd, Sm, Gd and Tm doping were found to possess negative U characteristics. In addition the calculated thermodynamic transition levels predicted Lu as not having any possible charge transitions within the host band gap. The calculated optical absorption coefficients indicate that lanthanide doping led to optical absorption in the visible regime. - Graphical abstract: Crystal structure of doped Sm doped TiO{sub 2} (RHS). Calculated PDOS and absorption spectra of Sm doped TiO{sub 2}. - Highlights: • Lanthanide doping significantly improved the optical properties of anatase TiO{sub 2}. • Lanthanide doping led to emission in the visible regions of the optical spectrum. • La, Ce, Pm, Sm, Eu, Gd, Tm, Yb and Lu doping gave good photocatalytic properties. • The optimum doping concentration in anatase TiO{sub 2} was found to be 2.78%.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Determination of carrier concentration and compensation microprofiles in GaAs

Simultaneous microprofiling of semiconductor free carrier, donor, and acceptor concentrations was achieved for the first time from the absolute value of the free carrier absorption coefficient and its wavelength dependence determined by IR absorption in a scanning mode. Employing Ge- and Si-doped melt-grown GaAs, striking differences were found between the variations of electron concentration and those of ionized impurity concentrations. These results showed clearly that the electronic characteristics of this material are controlled by amphoteric doping and deviations from stoichiometry rather than by impurity segregation.

Jastrzebski, L.↗