High Resolution Transmission Spectroscopy as a Diagnostic for Jovian Exoplanet Atmospheres: Constraints from Theoretical Models

We present high resolution transmission spectra of giant planet atmospheres from a coupled 3-D atmospheric dynamics and transmission spectrum model that includes Doppler shifts which arise from winds and planetary motion. We model jovian planets covering more than two orders of magnitude in incident flux, corresponding to planets with 0.9 to 55 day orbital periods around solar-type stars. The results of our 3-D dynamical models reveal certain aspects of high resolution transmission spectra that are not present in simple 1-D models. We find that the hottest planets experience strong substellar to anti-stellar (SSAS) winds, resulting in transmission spectra with net blue shifts of up to 3 km s−1, whereas less irradiated planets show almost no net Doppler shifts. Compared to 1-D models, peak line strengths are significantly reduced for the hottest atmospheres owing to Doppler broadening from a combination of rotation (which is faster for close-in planets under the assumption of tidal locking) and atmospheric winds. Finally, high resolution transmission spectra may be useful in studying the atmospheres of exoplanets with optically thick clouds since line cores for very strong transitions should remain optically thick to very high altitude. High resolution transmission spectra are an excellent observational test for the validity of 3-D atmospheric dynamics models, because they provide a direct probe of wind structures and heat circulation. Ground-based exoplanet spectroscopy is currently on the verge of being able to verify some of our modeling predictions, most notably the dependence of SSAS winds on insolation. We caution that interpretation of high resolution transmission spectra based on 1-D atmospheric models may be inadequate, as 3-D atmospheric motions can produce a noticeable effect on the absorption signatures.

Independent measurement of biogenic silica in sediments by FTIR spectroscopy and PLS regression

We present an independent calibration model for the determination of biogenic silica (BSi) in sediments, developed from analysis of synthetic sediment mixtures and application of Fourier transform infrared spectroscopy (FTIRS) and partial least squares regression (PLSR) modeling. In contrast to current FTIRS applications for quantifying BSi, this new calibration is independent from conventional wet-chemical techniques and their associated measurement uncertainties. This approach also removes the need for developing internal calibrations between the two methods for individual sediments records. For the independent calibration, we produced six series of different synthetic sediment mixtures using two purified diatom extracts, with one extract mixed with quartz sand, calcite, 60/40 quartz/calcite and two different natural sediments, and a second extract mixed with one of the natural sediments. A total of 306 samples—51 samples per series—yielded BSi contents ranging from 0 to 100 %. The resulting PLSR calibration model between the FTIR spectral information and the defined BSi concentration of the synthetic sediment mixtures exhibits a strong cross-validated correlation ( R2cv = 0.97) and a low root-mean square error of cross-validation (RMSECV = 4.7 %). Application of the independent calibration to natural lacustrine and marine sediments yields robust BSi reconstructions. At present, the synthetic mixtures do not include the variation in organic matter that occurs in natural samples, which may explain the somewhat lower prediction accuracy of the calibration model for organic-rich samples.

Visible near infra-red (VisNIR) spectroscopy for predicting soil organic carbon in Ethiopia

Over the past few decades, the advantages of the visible-near infra-red (VisNIR) diffuse reflectance spectrometer (DRS) method have enabled prediction of soil organic carbon (SOC). In this study, SOC was predicted using regression models for samples taken from three sites (Gununo, Maybar and Anjeni) in Ethiopia. SOC was characterized in laboratory using conventional wet chemistry and VisNIR-DRS methods. Principal component analysis (PCA), principal component regression (PCR) and partial least square regression (PLS) models were developed using Unscrambler X 10.2. PCA results show that the first two components accounted for a minimum of 96% variation which increased for individual sites and with data treatments. Correlation (r), coefficient of determination (R2) and residual prediction deviation (RPD) were used to rate four models built. PLS model (r, R2, RPD) values for Anjeni were 0.9, 0.9 and 3.6; for Gununo values 0.6, 0.3 and 1.2; for Maybar values 0.6, 0.3 and 0.9, and for the three sites values 0.7, 0.6 and 1.5, respectively. PCR model values (r, R2, RPD) for Anjeni were 0.9, 0.8 and 2.7; for Gununo values 0.5, 0.3 and 1; for Maybar values 0.5, 0.1 and 0.7, and for the three sites values 0.7, 0.5 and 1.2, respectively. Comparison and testing of models shows superior performance of PLS to PCR. Models were rated as very poor (Maybar), poor (Gununo and three sites) and excellent (Anjeni). A robust model, Anjeni, is recommended for prediction of SOC in Ethiopia.

Liquid–Vapor Interface of Formic Acid Solutions in Salt Water: A Comparison of Macroscopic Surface Tension and Microscopic in Situ X-ray Photoelectron Spectroscopy Measurements

The liquid–vapor interface is difficult to access experimentally but is of interest from a theoretical and applied point of view and has particular importance in atmospheric aerosol chemistry. Here we examine the liquid–vapor interface for mixtures of water, sodium chloride, and formic acid, an abundant chemical in the atmosphere. We compare the results of surface tension and X-ray photoelectron spectroscopy (XPS) measurements over a wide range of formic acid concentrations. Surface tension measurements provide a macroscopic characterization of solutions ranging from 0 to 3 M sodium chloride and from 0 to over 0.5 mole fraction formic acid. Sodium chloride was found to be a weak salting out agent for formic acid with surface excess depending only slightly on salt concentration. In situ XPS provides a complementary molecular level description about the liquid–vapor interface. XPS measurements over an experimental probe depth of 51 Å gave the C 1s to O 1s ratio for both total oxygen and oxygen from water. XPS also provides detailed electronic structure information that is inaccessible by surface tension. Density functional theory calculations were performed to understand the observed shift in C 1s binding energies to lower values with increasing formic acid concentration. Part of the experimental −0.2 eV shift can be assigned to the solution composition changing from predominantly monomers of formic acid to a combination of monomers and dimers; however, the lack of an appropriate reference to calibrate the absolute BE scale at high formic acid mole fraction complicates the interpretation. Our data are consistent with surface tension measurements yielding a significantly more surface sensitive measurement than XPS due to the relatively weak propensity of formic acid for the interface. A simple model allowed us to replicate the XPS results under the assumption that the surface excess was contained in the top four angstroms of solution.

Electronic band dispersion of graphene nanoribbons via Fourier-transformed scanning tunneling spectroscopy

The electronic structure of atomically precise armchair graphene nanoribbons of width N=7 (7-AGNRs) are investigated by scanning tunneling spectroscopy (STS) on Au(111). We record the standing waves in the local density of states of finite ribbons as a function of sample bias and extract the dispersion relation of frontier electronic states by Fourier transformation. The wave-vector-dependent contributions from these states agree with density functional theory calculations, thus enabling the unambiguous assignment of the states to the valence band, the conduction band, and the next empty band with effective masses of 0.41±0.08me,0.40±0.18me, and 0.20±0.03me, respectively. By comparing the extracted dispersion relation for the conduction band to corresponding height-dependent tunneling spectra, we find that the conduction band edge can be resolved only at small tip-sample separations and has not been observed before. As a result, we report a band gap of 2.37±0.06 eV for 7-AGNRs adsorbed on Au(111).