Towards a merged satellite and in situ fluorescence ocean chlorophyll product

Understanding the ocean carbon cycle requires a precise assessment of phytoplankton biomass in the oceans. In terms of numbers of observations, satellite data represent the largest available data set. However, as they are limited to surface waters, they have to be merged with in situ observations. Amongst the in situ data, fluorescence profiles constitute the greatest data set available, because fluorometers have operated routinely on oceanographic cruises since the 1970s. Nevertheless, fluorescence is only a proxy of the total chlorophyll <i>a</i> concentration and a data calibration is required. Calibration issues are, however, sources of uncertainty, and they have prevented a systematic and wide range exploitation of the fluorescence data set. In particular, very few attempts to standardize the fluorescence databases have been made. Consequently, merged estimations with other data sources (e.g. satellite) are lacking. <br><br> We propose a merging method to fill this gap. It consists firstly in adjusting the fluorescence profile to impose a zero chlorophyll <i>a</i> concentration at depth. Secondly, each point of the fluorescence profile is then multiplied by a correction coefficient, which forces the chlorophyll <i>a</i> integrated content measured on the fluorescence profile to be consistent with the concomitant ocean colour observation. The method is close to the approach proposed by Boss et al. (2008) to correct fluorescence data of a profiling float, although important differences do exist. To develop and test our approach, in situ data from three open ocean stations (BATS, HOT and DYFAMED) were used. Comparison of the so-called "satellite-corrected" fluorescence profiles with concomitant bottle-derived estimations of chlorophyll <i>a</i> concentration was performed to evaluate the final error (estimated at 31%). Comparison with the Boss et al. (2008) method, using a subset of the DYFAMED data set, demonstrated that the methods have similar accuracy. The method was applied to two different data sets to demonstrate its utility. Using fluorescence profiles at BATS, we show that the integration of "satellite-corrected" fluorescence profiles in chlorophyll <i>a</i> climatologies could improve both the statistical relevance of chlorophyll <i>a</i> averages and the vertical structure of the chlorophyll <i>a</i> field. We also show that our method could be efficiently used to process, within near-real time, profiles obtained by a fluorometer deployed on autonomous platforms, in our case a bio-optical profiling float. The application of the proposed method should provide a first step towards the generation of a merged satellite/fluorescence chlorophyll <i>a</i> product, as the "satellite-corrected" profiles should then be consistent with satellite observations. Improved climatologies with more consistent satellite and in situ data are likely to enhance the performance of present biogeochemical models

Social media use, connectedness, and depression in graduate students

This study will examine the relationship between social media use, sense of connectedness, and depression among graduate students. Graduate students are often disconnected from their social supports due to their program\u27s demands; additionally, the risk of depression in this population has been established in the literature. The impact of social media on depression has been investigated, and the results are discrepant. The relationship between a sense of connection, the use of social media, and depression in a graduate student population has not yet been explored. Graduate students at The Philadelphia College of Osteopathic Medicine (PCOM) and other universities studying psychology, medicine, biomedical science, or physician assistant studies will be included. Participants will be recruited through email and social media platforms. A control group of participants that do not use social media will be included. The following measures will be used: The Social Connectedness Scale-Revised (SCS-R), The Generalized Problematic Internet Use Scale 2 (GPIUS2), and The Patient Health Questionnaire-9 (PHQ-9). An inverse relationship is predicted between connectedness and depression. Participants with high scores on problematic internet use are anticipated to have elevated levels of depression and a low sense of connection compared to participants with low scores on problematic use. The subscales from the GPIUS2 are hypothesized to be predictive of participants\u27 sense of connection

Theoretical study of finite temperature spectroscopy in van der Waals clusters. I. Probing phase changes in CaAr_n

The photoabsorption spectra of calcium-doped argon clusters CaAr_n are investigated at thermal equilibrium using a variety of theoretical and numerical tools. The influence of temperature on the absorption spectra is estimated using the quantum superposition method for a variety of cluster sizes in the range 6<=n<=146. At the harmonic level of approximation, the absorption intensity is calculated through an extension of the Gaussian theory by Wadi and Pollak [J. Chem. Phys. vol 110, 11890 (1999)]. This theory is tested on simple, few-atom systems in both the classical and quantum regimes for which highly accurate Monte Carlo data can be obtained. By incorporating quantum anharmonic corrections to the partition functions and respective weights of the isomers, we show that the superposition method can correctly describe the finite-temperature spectroscopic properties of CaAr_n systems. The use of the absorption spectrum as a possible probe of isomerization or phase changes in the argon cluster is discussed at the light of finite-size effects.Comment: 17 pages, 9 figure

Correction of profiles of in-situ chlorophyll fluorometry for the contribution of fluorescence originating from non-algal matter

In situ chlorophyll fluorometers have been widely employed for more than half a century, and to date, it still remains the most used instrument to estimate chlorophyll-a concentration in the field, especially for measurements onboard autonomous observation platforms, e.g., Bio-Argo floats and gliders. However, in deep waters (> 300 m) of some specific regions, e.g., subtropical gyres and the Black Sea, the chlorophyll fluorescence profiles frequently reveal “deep sea red fluorescence” features. In line with previous studies and through the analysis of a large data set (cruise transect in the South East Pacific and data acquired by 82 Bio- Argo floats), we show that the fluorescence signal measured by a humic-like DOM fluorometer is highly correlated to the “deep sea red fluorescence.” Both fluorescence signals are indeed linearly related in deep waters. To remove the contribution of non-algal organic matter from chlorophyll fluorescence profiles, we introduce a new correction. Rather that removing a constant value (generally the deepest chlorophyll a fluorescence value from the profile, i.e., so-called “deep-offset correction”), we propose a correction method which relies on DOM fluorometry and on its variation with depth. This new method is validated with chlorophyll concentration extracted from water samples and further applied on the Bio-Argo float data set. More generally, we discuss the potential of the proposed method to become a standard and routine procedure in quality-control and correction of chlorophyll a fluorescence originating from Bio-Argo network

Organic carbon export and loss rates in the Red Sea

The export and fate of organic carbon in the mesopelagic zone are still poorly understood and quantified due to lack of observations. We exploited data from a BGC‐Argo float that was deployed in the Red Sea to study how a warm and hypoxic environment can affect the fate of the organic carbon in the ocean’s interior. We observed that only 10% of the particulate organic carbon (POC) exported survived at depth due to remineralization processes in the upper mesopelagic zone. We also found that POC exported was rapidly degraded in a first stage and slowly in a second one, which may be dependent on the palatability of the organic matter. We observed that AOU‐based loss rates (a proxy of the remineralization of total organic matter) were significantly higher than the POC‐based loss rates, likely because changes in AOU are mainly attributed to changes in dissolved organic carbon. Finally, we showed that POC‐ and AOU‐based loss rates could be expressed as a function of temperature and oxygen concentration. These findings advance our understanding of the biological carbon pump and mesopelagic ecosystem

Thermodynamics of Na_8 and Na_{20} clusters studied with ab-initio electronic structure methods

We study the thermodynamics of Na_8 and Na_{20} clusters using multiple-histogram methods and an ab initio treatment of the valence electrons within density functional theory. We consider the influence of various electron kinetic-energy functionals and pseudopotentials on the canonical ionic specific heats. The results for all models we consider show qualitative similarities, but also significant temperature shifts from model to model of peaks and other features in the specific-heat curves. The use of phenomenological pseudopotentials shifts the melting peak substantially (~ 50--100 K) when compared to ab-initio results. It is argued that the choice of a good pseudopotential and use of better electronic kinetic-energy functionals has the potential for performing large time scale and large sized thermodynamical simulations on clusters.Comment: LaTeX file and EPS figures. 24 pages, 13 figures. Submitted to Phys. Rev.

Thermal expansion in small metal clusters and its impact on the electric polarizability

The thermal expansion coefficients of $\mathrm{Na}_{N}$ clusters with $8 \le N \le 40$ and $\mathrm{Al}_{7}$, $\mathrm{Al}_{13}^-$ and $\mathrm{Al}_{14}^-$ are obtained from {\it ab initio} Born-Oppenheimer LDA molecular dynamics. Thermal expansion of small metal clusters is considerably larger than that in the bulk and size-dependent. We demonstrate that the average static electric dipole polarizability of Na clusters depends linearly on the mean interatomic distance and only to a minor extent on the detailed ionic configuration when the overall shape of the electron density is enforced by electronic shell effects. The polarizability is thus a sensitive indicator for thermal expansion. We show that taking this effect into account brings theoretical and experimental polarizabilities into quantitative agreement.Comment: 4 pages, 2 figures, one table. Accepted for publication in Physical Review Letters. References 10 and 23 update

Recommendations for obtaining unbiased chlorophyll estimates from in situ chlorophyll fluorometers: A global analysis of WET Labs ECO sensors

Chlorophyll fluorometers provide the largest in situ global data set for estimating phytoplankton biomass because of their ease of use, size, power consumption, and relatively low price. While in situ chlorophyll a (Chl) fluorescence is proxy for Chl a concentration, and hence phytoplankton biomass, there exist large natural variations in the relationship between in situ fluorescence and extracted Chl a concentration. Despite this large natural variability, we present here a global validation data set for the WET Labs Environmental Characterization Optics (ECO) series chlorophyll fluorometers that suggests a factor of 2 overestimation in the factory calibrated Chl a estimates for this specific manufacturer and series of sensors. We base these results on paired High Pressure Liquid Chromatography (HPLC) and in situ fluorescence match ups for which non-photochemically quenched fluorescence observations were removed. Additionally, we examined matches between the factory-calibrated in situ fluorescence and estimates of chlorophyll concentration determined from in situ radiometry, absorption line height, NASA’s standard ocean color algorithm as well as laboratory calibrations with phytoplankton monocultures spanning diverse species that support the factor of 2 bias. We therefore recommend the factor of 2 global bias correction be applied for the WET Labs ECO sensors, at the user level, to improve the global accuracy of chlorophyll concentration estimates and products derived from them. We recommend that other fluorometer makes and models should likewise undergo global analyses to identify potential bias in factory calibration

Catalysis to discriminate single atoms from subnanometric ruthenium particles in ultra-high loading catalysts

We report a procedure for preparing ulta-high metal loading (10-20 % w/w Ru) Ru@C60 nanostructured catalysts comprising exclusively Ru single atoms. We show that by changing the Ru/C60 ratio and the nature of the solvent used during the synthesis, it is possible to increase the Ru loading up to 50% w/w, and to produce hetero-structures containing subnanometric Ru nanoparticles. Several techniques such as high-resolution transmission electron microscopy (HRTEM), scanning transmission electron microscopy – high angle annular dark field (STEM-HAADF), Raman spectroscopy, wideangle X-ray scattering (WAXS), extended X-ray absorption fine structure (EXAFS) and X-ray photoelectron spectroscopy (XPS) together with theoretical calculations were used to characterize these materials. At such high metal loading, the distinction between Ru single atoms and clusters is not trivial, even with this combination of techniques. We evaluated the catalytic properties of these materials for the hydrogenation of nitrobenzene and 2,3-dimethyl-2-butene. The catalysts containing only Ru single atoms are much less active for these reactions than the ones containing clusters. For nitrobenzene hydrogenation, this is because electro-deficient Ru single atoms and few atom Run clusters are not performant for H2 activation compared to larger clusters (n ≥ 13), as shown by density functional theory (DFT) calculations. For the more crowded substrate 2,3-dimethyl-2-butene, DFT calculations have shown that this is due to steric hindrance. These simple tests can thus been used to distinguish samples containing metallic sub-nanometer nanoparticles. These novel catalysts are also extremely active for the hydrogenation of -substituted 2,3-dimethyl-2-butene