Techniques for the Optimization of Supercritical Fluid Chromatographic Separations.

Although supercritical fluid chromatography (SFC) is now well established and still growing rapidly, it must offer clear advantages over other techniques. Thus proper method development in SFC is a necessity. There are many diverse and synergetic parameters controlling SFC separations, resulting in complex retention behavior. This work describes the proper approach to method development, including investigations into unique mobile phases and some techniques which can be used for optimization of SFC separations. In Chapter One, the concepts of chromatography with supercritical fluids are first introduced, including method development and optimization. Chapter Two focuses on mobile phase method development, and examines the effects of adding a small amount of formic acid (0.3, 0.5, and 0.7%) to a carbon dioxide mobile phase. Chosen in part because it does not respond to the flame ionization detector (FID), the formic acid is observed to increase the solvation of polar analytes, and improve selectivity and peak shape. Thermodynamic measurements are made in order to quantitatively compare the modified and pure mobile phases. In the lower temperature and pressure ranges, preferential solvation of polar compounds by the formic acid modifier results in more dramatic thermodynamic differences for the two mobile phases. Chapter Three illustrates the usefulness of short capillary columns for the reduction of method development time and for rapid analysis of simple mixtures. In Chapters Four and Five, the simplex algorithm is evaluated for rapid optimization of SFC separations, and is a preferred technique that can be applied to any number of variables, requiring little knowledge of the sample. Chapter Six introduces simultaneous interpretive methods of optimization, in which response surfaces are generated by retention mapping. Using very few data and an appropriate model, retention surfaces are used to produce a response surface, which is then searched for the optimum. Chapter Seven summarizes SFC method development, and provides a comparison of optimization techniques. Appendix A gives useful hints in the operation of SFC instrumentation, while Appendices B and C list important computer programs for the optimization of separations in supercritical fluid chromatography

Subspace Correction for Constraints

We demonstrate that it is possible to construct operators that stabilize the constraint-satisfying subspaces of computational problems in their Ising representations. We provide an explicit recipe to construct unitaries and associated measurements for some such constraints. The stabilizer measurements allow the detection of constraint violations, and provide a route to recovery back into the constrained subspace. We call this technique ``subspace correction". As an example, we explicitly investigate the stabilizers using the simplest local constraint subspace: Independent Set. We find an algorithm that is guaranteed to produce a perfect uniform or weighted distribution over all constraint-satisfying states when paired with a stopping condition: a quantum analogue of partial rejection sampling. The stopping condition can be modified for sub-graph approximations. We show that it can prepare exact Gibbs distributions on $d-$regular graphs below a critical hardness $\lambda_d^*$ in sub-linear time. Finally, we look at a potential use of subspace correction for fault-tolerant depth-reduction. In particular we investigate how the technique detects and recovers errors induced by Trotterization in preparing maximum independent set using an adiabatic state preparation algorithm.Comment: 12 + 4 pages, 6 figure

Decomposability of soil organic matter over time: the Soil Incubation Database (SIDb, version 1.0) and guidance for incubation procedures

The magnitude of carbon (C) loss to the atmosphere via microbial decomposition is a function of the amount of C stored in soils, the quality of the organic matter, and physical, chemical, and biological factors that comprise the environment for decomposition. The decomposability of C is commonly assessed by laboratory soil incubation studies that measure greenhouse gases mineralized from soils under controlled conditions. Here, we introduce the Soil Incubation Database (SIDb) version 1.0, a compilation of time series data from incubations, structured into a new, publicly available, open-access database of C flux (carbon dioxide, CO2, or methane, CH4). In addition, the SIDb project also provides a platform for the development of tools for reading and analysis of incubation data as well as documentation for future use and development. In addition to introducing SIDb, we provide reporting guidance for database entry and the required variables that incubation studies need at minimum to be included in SIDb. A key application of this synthesis effort is to better characterize soil C processes in Earth system models, which will in turn reduce our uncertainty in predicting the response of soil C decomposition to a changing climate. We demonstrate a framework to fit curves to a number of incubation studies from diverse ecosystems, depths, and organic matter content using a built-in model development module that integrates SIDb with the existing SoilR package to estimate soil C pools from time series data. The database will help bridge the gap between point location measurements, which are commonly used in incubation studies, and global remote-sensed data or data products derived from models aimed at assessing global-scale rates of decomposition and C turnover. The SIDb version 1.0 is archived and publicly available at https://doi.org/10.5281/zenodo.3871263 (Sierra et al., 2020), and the database is managed under a version-controlled system and centrally stored in GitHub (https://github.com/SoilBGC-Datashare/sidb, last access: 26 June 2020)

Technology Development Roadmap: A Technology Development Roadmap for a Future Gravitational Wave Mission

Humankind will detect the first gravitational wave (GW) signals from the Universe in the current decade using ground-based detectors. But the richest trove of astrophysical information lies at lower frequencies in the spectrum only accessible from space. Signals are expected from merging massive black holes throughout cosmic history, from compact stellar remnants orbiting central galactic engines from thousands of close contact binary systems in the Milky Way, and possibly from exotic sources, some not yet imagined. These signals carry essential information not available from electromagnetic observations, and which can be extracted with extraordinary accuracy. For 20 years, NASA, the European Space Agency (ESA), and an international research community have put considerable effort into developing concepts and technologies for a GW mission. Both the 2000 and 2010 decadal surveys endorsed the science and mission concept of the Laser Interferometer Space Antenna (LISA). A partnership of the two agencies defined and analyzed the concept for a decade. The agencies partnered on LISA Pathfinder (LPF), and ESA-led technology demonstration mission, now preparing for a 2015 launch. Extensive technology development has been carried out on the ground. Currently, the evolved Laser Interferometer Space Antenna (eLISA) concept, a LISA-like concept with only two measurement arms, is competing for ESA's L2 opportunity. NASA's Astrophysics Division seeks to be a junior partner if eLISA is selected. If eLISA is not selected, then a LISA-like mission will be a strong contender in the 2020 decadal survey. This Technology Development Roadmap (TDR) builds on the LISA concept development, the LPF technology development, and the U.S. and European ground-based technology development. The eLISA architecture and the architecture of the Mid-sized Space-based Gravitational-wave Observatory (SGO Mid)-a competitive design with three measurement arms from the recent design study for a NASA-led mission after 2020-both use the same technologies. Further, NASA participation in an ESA-led mission would likely augment the eLISA architecture with a third arm to become the SGO Mid architecture. For these reasons, this TDR for a future GW mission applies to both designs and both programmatic paths forward. It is adaptable to the different timelines and roles for an ESA-led or a NASA-led mission, and it is adaptable to available resources. Based on a mature understanding of the interaction between technology and risk, the authors of this TDR have chosen a set of objectives that are more expansive than is usual. The objectives for this roadmap are: (1) reduce technical and development risks and costs; (2) understand and, where possible, relieve system requirements and consequences; (3) increase technical insight into critical technologies; and (4) validate the design at the subsystem level. The emphasis on these objectives, particularly the latter two, is driven by outstanding programmatic decisions, namely whether a future GW mission is ESA-led or NASA-led, and availability of resources. The relative emphasis is best understood in the context of prioritization

Ad Astra Academy: Using Space Exploration to Promote Student Learning and Motivation in the City of God, Rio de Janeiro, Brazil

Motivation is a primary determinant of a student&rsquo;s academic success, but in many under-resourced educational contexts around the world, opportunities to develop motivation are lacking. In the City of God neighborhood of Rio de Janeiro, Brazil, we (a group of scientists and science educators) enacted brief, interactive interventions targeting teenage students at risk of dropping out of school. Students participated in an immersive 5-day program, followed by a six-month break, before completing the second, 3-day program. Participants learned how to use the scientific method in real-world settings to generate new knowledge. In order to consolidate these knowledge gains and bolster the program&rsquo;s inspirational power, capstone projects empowered participants to speak with NASA mission managers and, in some cases, acquire never-before-seen images of Mars. While longitudinal study and a more robust sample size are required to bolster conclusions about the efficacy of our approach, initial results suggest that Ad Astra programs significantly enhance self-efficacy and science-oriented career ambitions.</p

BioTIME: A database of biodiversity time series for the Anthropocene.

MotivationThe BioTIME database contains raw data on species identities and abundances in ecological assemblages through time. These data enable users to calculate temporal trends in biodiversity within and amongst assemblages using a broad range of metrics. BioTIME is being developed as a community-led open-source database of biodiversity time series. Our goal is to accelerate and facilitate quantitative analysis of temporal patterns of biodiversity in the Anthropocene.Main types of variables includedThe database contains 8,777,413 species abundance records, from assemblages consistently sampled for a minimum of 2 years, which need not necessarily be consecutive. In addition, the database contains metadata relating to sampling methodology and contextual information about each record.Spatial location and grainBioTIME is a global database of 547,161 unique sampling locations spanning the marine, freshwater and terrestrial realms. Grain size varies across datasets from 0.0000000158 km2 (158 cm2) to 100 km2 (1,000,000,000,000 cm2).Time period and grainBioTIME records span from 1874 to 2016. The minimal temporal grain across all datasets in BioTIME is a year.Major taxa and level of measurementBioTIME includes data from 44,440 species across the plant and animal kingdoms, ranging from plants, plankton and terrestrial invertebrates to small and large vertebrates.Software format.csv and .SQL

The importance of monsoon precipitation for foundation tree species across the semiarid Southwestern U.S.

Forest dynamics in arid and semiarid regions are sensitive to water availability, which is becoming increasingly scarce as global climate changes. The timing and magnitude of precipitation in the semiarid southwestern U.S. (“Southwest”) has changed since the 21st century began. The region is projected to become hotter and drier as the century proceeds, with implications for carbon storage, pest outbreaks, and wildfire resilience. Our goal was to quantify the importance of summer monsoon precipitation for forested ecosystems across this region. We developed an isotope mixing model in a Bayesian framework to characterize summer (monsoon) precipitation soil water recharge and water use by three foundation tree species (Populus tremuloides [aspen], Pinus edulis [piñon], and Juniperus osteosperma [Utah juniper]). In 2016, soil depths recharged by monsoon precipitation and tree reliance on monsoon moisture varied across the Southwest with clear differences between species. Monsoon precipitation recharged soil at piñon-juniper (PJ) and aspen sites to depths of at least 60 cm. All trees in the study relied primarily on intermediate to deep (10-60 cm) moisture both before and after the onset of the monsoon. Though trees continued to primarily rely on intermediate to deep moisture after the monsoon, all species increased reliance on shallow soil moisture to varying degrees. Aspens increased reliance on shallow soil moisture by 13% to 20%. Utah junipers and co-dominant ñons increased their reliance on shallow soil moisture by about 6% to 12%. Nonetheless, approximately half of the post-monsoon moisture in sampled piñon (38-58%) and juniper (47-53%) stems could be attributed to the monsoon. The monsoon contributed lower amounts to aspen stem water (24-45%) across the study area with the largest impacts at sites with recent precipitation. Therefore, monsoon precipitation is a key driver of growing season moisture that semiarid forests rely on across the Southwest. This monsoon reliance is of critical importance now more than ever as higher global temperatures lead to an increasingly unpredictable and weaker North American Monsoon