Evidence of Low-Temperature Superparamagnetism in Mn3O_{3}O_{4}$ Nanoparticle Ensembles

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Evidence of a biodiversity crisis documented on a peritidal carbonate succession from western Tethys (Sicily): new data on the End Triassic Mass Extinction

A biodiversity crisis was observed in the latest Triassic on both macro-and micro-benthic communities from a western Tethyan carbonate platform. The studied succession represented by the Monte Sparagio section consists of a continuous Upper Triassic to Lower Jurassic peritidal limestones organized in shallowing upward cycles. The subtidal facies in the lower part of this section (Unit A) contains very abundant and highly diverse fossiliferous assemblages consisting of very large megalodontoids (up to 40 cm). Up-section, a reduction of biodiversity, abundance and shell size of megalodontoids (up to 15 cm) tipifies Unit B. Similarly, in this last Unit, the average dimensions of the benthic foraminifer T. hantkeni decreases (ca. 30%). After a short interval marked by a bloom of the problematic alga T. parvovesiculifera, the overlying Unit C accounts for the recovery of the Jurassic benthic community. The geochemical analyses of stable isotopes (C, O and S) seem correlative to the drastic reduction in the Rhaetian biodiversity between Unit A and Unit B. These biodiversity crises in the Rhaetian horizons can be interpreted as a precursor of the End Triassic Extinction and provide new insights into the existence of two extinction pulses at the end of Triassic. These data are in accordance with the environmental parameters of survival in a modern tropical shallow water platform (T-factory). In particular, the sea surface temperature (SST) of a T-factory ranges from 18 degrees C to 30.5 degrees C representing respectively the minimum SST for the carbonate factory persistence and the maximum SST that a T-factory can tolerate

Magnetodielectric coupling in Mn3O4

We have investigated the dielectric anomalies associated with spin ordering transitions in the tetragonal spinel Mn$_3$O$_4$, using thermodynamic, magnetic, and dielectric measurements. We find that two of the three magnetic ordering transitions in Mn$_3$O$_4$ lead to decreases in the temperature dependent dielectric constant at zero applied field. Applying a magnetic field to the polycrystalline sample leaves these two dielectric anomalies practically unchanged, but leads to an increase in the dielectric constant at the intermediate spin-ordering transition. We discuss possible origins for this magnetodielectric behavior in terms of spin-phonon coupling. Band structure calculations suggest that in its ferrimagnetic state, Mn$_3$O$_4$ corresponds to a semiconductor with no orbital degeneracy due to strong Jahn-Teller distortion.Comment: 6 pages, 7 figure

Single vibronic level emission spectroscopic studies of the ground state energy levels and molecular structures of jet-cooled HGeBr, DGeBr, HGeI, and DGeI

Single vibronic level dispersed fluorescence spectra of jet-cooled HGeBr, DGeBr, HGeI, and DGeI have been obtained by laser excitation of selected bands of the à A″1-X̃ A′1 electronic transition. The measured ground state vibrational intervals were assigned and fitted to anharmonicity expressions, which allowed the harmonic frequencies to be determined for both isotopomers. In some cases, lack of a suitable range of emission data necessitated that some of the anharmonicity constants and vibrational frequencies be estimated from those of HGeCl∕DGeCl and the corresponding silylenes (HSiX). Harmonic force fields were obtained for both molecules, although only four of the six force constants could be determined. The ground state effective rotational constants and force field data were combined to calculate average (rz) and approximate equilibrium (rze) structures. For HGeBr rze(GeH)=1.593(9)Å, rze(GeBr)=2.325(21)Å, and the bond angle was fixed at our CCSD(T)/aug-cc-pVTZ ab initio value of 93.6°. For HGeI we obtained rze(GeH)=1.589(1)Å, rze(GeI)=2.525(5)Å, and bond angle=93.2°. Franck-Condon simulations of the emission spectra using ab initio Cartesian displacement coordinates reproduce the observed intensity distributions satisfactorily. The trends in structural parameters in the halogermylenes and halosilylenes can be readily understood based on the electronegativity of the halogen substituent. ACKNOWLEDGMENT

Minimum Aerosol Layer Detection Sensitivities and Their Subsequent Impacts on Aerosol Optical Thickness Retrievals in CALIPSO Level 2 Data Products

Due to instrument sensitivities and algorithm detection limits, level 2 (L2) Cloud-Aerosol Lidar with Orthogonal Polarization (CALIOP) 532 nm aerosol extinction profile retrievals are often populated with retrieval fill values (RFVs), which indicate the absence of detectable levels of aerosol within the profile. In this study, using 4 years (20072008 and 20102011) of CALIOP version 3 L2 aerosol data, the occurrence frequency of daytime CALIOP profiles containing all RFVs (all-RFV profiles) is studied. In the CALIOP data products, the aerosol optical thickness (AOT) of any all-RFV profile is reported as being zero, which may introduce a bias in CALIOP-based AOT climatologies. For this study, we derive revised estimates of AOT for all-RFV profiles using collocated Moderate Resolution Imaging Spectroradiometer (MODIS) Dark Target (DT) and, where available, AErosol RObotic NEtwork (AERONET) data. Globally, all-RFV profiles comprise roughly 71 % of all daytime CALIOP L2 aerosol profiles (i.e., including completely attenuated profiles), accounting for nearly half (45 %) of all daytime cloud-free L2 aerosol profiles. The mean collocated MODIS DT (AERONET) 550 nm AOT is found to be near 0.06 (0.08) for CALIOP all-RFV profiles. We further estimate a global mean aerosol extinction profile, a so-called noise floor, for CALIOP all-RFV profiles. The global mean CALIOP AOT is then recomputed by replacing RFV values with the derived noise-floor values for both all-RFV and non-all-RFV profiles. This process yields an improvement in the agreement of CALIOP and MODIS over-ocean AOT

Minimum Aerosol Layer Detection Sensitivities and Their Subsequent Impacts on Aerosol Optical Thickness Retrievals in CALIPSO Level 2 Data Products

Due to instrument sensitivities and algorithm detection limits, level 2 (L2) Cloud-Aerosol Lidar with Orthogonal Polarization (CALIOP) 532 nm aerosol extinction profile retrievals are often populated with retrieval fill values (RFVs), which indicate the absence of detectable levels of aerosol within the profile. In this study, using 4 years (2007– 2008 and 2010–2011) of CALIOP version 3 L2 aerosol data, the occurrence frequency of daytime CALIOP profiles containing all RFVs (all-RFV profiles) is studied. In the CALIOP data products, the aerosol optical thickness (AOT) of any all-RFV profile is reported as being zero, which may introduce a bias in CALIOP-based AOT climatologies. For this study, we derive revised estimates of AOT for all-RFV profiles using collocated Moderate Resolution Imaging Spectroradiometer (MODIS) Dark Target (DT) and, where available, AErosol RObotic NEtwork (AERONET) data. Globally, all-RFV profiles comprise roughly 71 % of all daytime CALIOP L2 aerosol profiles (i.e., including completely attenuated profiles), accounting for nearly half (45 %) of all daytime cloud-free L2 aerosol profiles. The mean collocated MODIS DT (AERONET) 550 nm AOT is found to be near 0.06 (0.08) for CALIOP all-RFV profiles. We further estimate a global mean aerosol extinction profile, a so-called “noise floor”, for CALIOP all-RFV profiles. The global mean CALIOP AOT is then recomputed by replacing RFV values with the derived noise-floor values for both all-RFV and nonall-RFV profiles. This process yields an improvement in the agreement of CALIOP and MODIS over-ocean AOT

Characterizing the Vertical Profile of Aerosol Particle Extinction and Linear Depolarization over Southeast Asia and the Maritime Continent: The 2007-2009 View from CALIOP

Vertical profiles of 0.532 m aerosol particle extinction coefficient and linear volume depolarization ratio are described for Southeast Asia and the Maritime Continent. Quality-screened and cloud-cleared Version 3.01 Level 2 NASA Cloud Aerosol Lidar with Orthogonal Polarization (CALIOP) 5-km Aerosol Profile datasets are analyzed from 2007 to 2009. Numerical simulations from the U.S. Naval Aerosol Analysis and Predictive System (NAAPS), featuring two-dimensional variational assimilation of NASA Moderate Resolution Imaging Spectroradiometer and Multi-angle Imaging Spectro- Radiometer quality-assured datasets, combined with regional ground-based lidar measurements, are considered for assessing CALIOP retrieval performance, identifying bias, and evaluating regional representativeness. CALIOP retrievals of aerosol particle extinction coefficient and aerosol optical depth (AOD) are high over land and low over open waters relative to NAAPS (0.412/0.312 over land for all data points inclusive, 0.310/0.235 when the per bin average is used and each is treated as single data points; 0.102/0.151 and 0.086/0.124, respectively, over ocean). Regional means, however, are very similar (0.180/0.193 for all data points and 0.155/0.159 when averaged per normalized bin), as the two factors offset one another. The land/ocean offset is investigated, and discrepancies attributed to interpretation of particle composition and a-priori assignment of the extinction-to-backscatter ratio ("lidar ratio") necessary for retrieving the extinction coefficient from CALIOP signals. Over land, NAAPS indicates more dust present than CALIOP algorithms are identifying, indicating a likely assignment of a higher lidar ratio representative of more absorptive particles. NAAPS resolvesmore smoke overwater than identified with CALIOP, indicating likely usage of a lidar ratio characteristic of less absorptive particles to be applied that biases low AOD there. Over open waters except within the Bay of Bengal, aerosol particle scattering is largely capped below 1.5 km MSL, though ground-based lidar measurements at Singapore differ slightly from this finding. Significant aerosol particle presence over land is similarly capped near 3.0 km MSL over most regions. Particle presence at low levels regionally, except over India, is dominated by relatively non-depolarizing particles. Industrial haze, sea salt droplets and fresh smoke are thus most likely present

Extinction and optical depth retrievals for CALIPSO's Version 4 data release

The Cloud–Aerosol Lidar with Orthogonal Polarization (CALIOP) on board the Cloud–Aerosol Lidar Infrared Pathfinder Satellite Observations (CALIPSO) satellite has been making near-global height-resolved measurements of cloud and aerosol layers since mid-June 2006. Version 4.10 (V4) of the CALIOP data products, released in November 2016, introduces extensive upgrades to the algorithms used to retrieve the spatial and optical properties of these layers, and thus there are both obvious and subtle differences between V4 and previous data releases. This paper describes the improvements made to the extinction retrieval algorithms and illustrates the impacts of these changes on the extinction and optical depth estimates reported in the CALIPSO lidar level 2 data products. The lidar ratios for both aerosols and ice clouds are generally higher than in previous data releases, resulting in generally higher extinction coefficients and optical depths in V4. A newly implemented algorithm for retrieving extinction coefficients in opaque layers is described and its impact examined. Precise lidar ratio estimates are also retrieved in these opaque layers. For semi-transparent cirrus clouds, comparisons between CALIOP V4 optical depths and the optical depths reported by MODIS collection 6 show substantial improvements relative to earlier comparisons between CALIOP version 3 and MODIS collection 5.</p

Evaluating nighttime CALIOP 0.532 μm aerosol optical depth and extinction coefficient retrievals

NASA Cloud Aerosol Lidar with Orthogonal Polarization (CALIOP) Version 3.01 5-km nighttime 0.532 μm aerosol optical depth (AOD) datasets from 2007 are screened, averaged and evaluated at 1&amp;deg; × 1&amp;deg; resolution versus corresponding/co-incident 0.550 μm AOD derived using the &lt;i&gt;US Navy Aerosol Analysis and Prediction System&lt;/i&gt; (NAAPS), featuring two-dimensional variational assimilation of quality-assured NASA Moderate Resolution Imaging Spectroradiometer (MODIS) and Multi-angle Imaging Spectroradiometer (MISR) AOD. In the absence of sunlight, since passive radiometric AOD retrievals rely overwhelmingly on scattered radiances, the model represents one of the few practical global estimates available from which to attempt such a validation. Daytime comparisons, though, provide useful context. Regional-mean CALIOP vertical profiles of night/day 0.532 μm extinction coefficient are compared with 0.523/0.532 μm ground-based lidar measurements to investigate representativeness and diurnal variability. In this analysis, mean nighttime CALIOP AOD are mostly lower than daytime (0.121 vs. 0.126 for all aggregated data points, and 0.099 vs. 0.102 when averaged globally per normalised 1&amp;deg; × 1&amp;deg; bin), though the relationship is reversed over land and coastal regions when the data are averaged per normalised bin (0.134/0.108 vs. 0140/0.112, respectively). Offsets assessed within single bins alone approach ±20%. CALIOP AOD, both day and night, are higher than NAAPS over land (0.137 vs. 0.124) and equal over water (0.082 vs. 0.083) when averaged globally per normalised bin. However, for all data points inclusive, NAAPS exceeds CALIOP over land, coast and ocean, both day and night. Again, differences assessed within single bins approach 50% in extreme cases. Correlation between CALIOP and NAAPS AOD is comparable during both day and night. Higher correlation is found nearest the equator, both as a function of sample size and relative signal magnitudes inherent at these latitudes. Root mean square deviation between CALIOP and NAAPS varies between 0.1 and 0.3 globally during both day/night. Averaging of CALIOP along-track AOD data points within a single NAAPS grid bin improves correlation and RMSD, though day/night and land/ocean biases persist and are believed systematic. Vertical profiles of extinction coefficient derived in the Caribbean compare well with ground-based lidar observations, though potentially anomalous selection of a priori lidar ratios for CALIOP retrievals is likely inducing some discrepancies. Mean effective aerosol layer top heights are stable between day and night, indicating consistent layer-identification diurnally, which is noteworthy considering the potential limiting effects of ambient solar noise during day