Fluxes of Atmospheric Methane Using Novel Instruments, Field Measurements, and Inverse Modeling

The atmospheric concentration of methane $(CH_4)$ - the most significant non-$CO_2$ anthropogenic long-lived greenhouse gas - stabilized between 1999 and 2006 and then began to rise again. Explanations for this behavior differ but studies agree that more measurements and better modeling are needed to reliably explain the model-data discrepancies and predict future change. This dissertation focuses on measurements of $CH_4$ and inverse modeling of atmospheric $CH_4$ fluxes using field measurements at a variety of spatial scales. We first present a new fast-response instrument to measure the isotopic composition of $CH_4$ in ambient air. The instrument was used to characterize mass fluxes and isofluxes (a isotopically-weighted mass flux) from a well-studied research fen in New Hampshire. Eddy-covariance and automatic chamber techniques produced consistent estimates of both the $CH_4$ fluxes and their isotopic composition at sub-hourly resolution. We then characterize fluxes of $CH_4$ from aircraft engines using measurements made with the same instrument during the Alternative Aviation Fuel Experiment (AAFEX), a study that aimed to determine the atmospheric impacts of alternative fuel use in the growing aviation industry. Emissions of $CO_2$, $CH_4$, and $N_2O$ from different synthetic fuels were statistically indistinguishable from those of the widely used JP-8 jet fuel. We then present airborne observations of the long-lived greenhouse gas suite – $CO_2$, $CH_4$, $N_2O$, and CO – during two aircraft campaigns, HIPPO and CalNex, made using a similar instrument built specifically for the NCAR HIAPER GV aircraft. These measurements are compared to data from other onboard sensors and show excellent agreement. We discuss the details of the end-to-end calibration procedures and the data quality-assurance and quality-control (QA/QC). Lastly, we quantify a top-down estimate of California’s $CH_4$ emission inventory using the CalNex $CH_4$ observations. Observed $CH_4$ enhancements above background concentrations are simulated using a lagrangian transport model driven by validated meteorology. A priori source-specific emission inventories are optimized in a Bayesian inversion framework to show that California’s $CH_4$ budget is 1.6 ± 0.34 times larger than the current estimate of California’s Air Resources Board (CARB), the body charged with enforcing the California Global Solutions Act and tracking emission changes over time. Findings highlight large underestimates of emissions from cattle and natural gas infrastructure.Earth and Planetary Science

Mass fluxes and isofluxes of methane (CH4) at a New Hampshire fen measured by a continuous wave quantum cascade laser spectrometer

We have developed a mid‐infrared continuous‐wave quantum cascade laser direct‐absorption spectrometer (QCLS) capable of high frequency (≥1 Hz) measurements of 12CH4 and 13CH4 isotopologues of methane (CH4) with in situ 1‐s RMS image precision of 1.5 ‰ and Allan‐minimum precision of 0.2 ‰. We deployed this QCLS in a well‐studied New Hampshire fen to compare measurements of CH4 isoflux by eddy covariance (EC) to Keeling regressions of data from automated flux chamber sampling. Mean CH4 fluxes of 6.5 ± 0.7 mg CH4 m−2 hr−1 over two days of EC sampling in July, 2009 were indistinguishable from mean autochamber CH4 fluxes (6.6 ± 0.8 mgCH4 m−2 hr−1) over the same period. Mean image composition of emitted CH4 calculated using EC isoflux methods was −71 ± 8 ‰ (95% C.I.) while Keeling regressions of 332 chamber closing events over 8 days yielded a corresponding value of −64.5 ± 0.8 ‰. Ebullitive fluxes, representing ∼10% of total CH4 fluxes at this site, were on average 1.2 ‰ enriched in 13C compared to diffusive fluxes. CH4 isoflux time series have the potential to improve process‐based understanding of methanogenesis, fully characterize source isotopic distributions, and serve as additional constraints for both regional and global CH4 modeling analysis

Simultaneous Measurements of Atmospheric HONO and NO2 via Absorption Spectroscopy using Tunable Mid-Infrared Continuous-wave Quantum Cascade Lasers

Nitrous acid (HONO) is important as a significant source of hydroxyl radical (OH) in the troposphere and as a potent indoor air pollutant. It is thought to be generated in both environments via heterogeneous reactions involving nitrogen dioxide $(NO_2)$. In order to enable fast-response HONO detection suitable for eddy-covariance flux measurements and to provide a direct method that avoids interferences associated with derivatization, we have developed a 2-channel tunable infrared laser differential absorption spectrometer (TILDAS) capable of simultaneous high-frequency measurements of HONO and NO2. Beams from two mid-infrared continuous-wave mode quantum cascade lasers (cw-QCLs) traverse separate 210 m paths through a multi-pass astigmatic sampling cell at reduced pressure for the direct detection of HONO $(1660 cm^{−1})$ and $(NO_2)$ $(1604 cm^{−1})$. The resulting one-second detection limits (S/N=3) are 300 and 30 ppt (pmol/mol) for HONO and $(NO_2)$, respectively. Our HONO quantification is based on revised line-strengths and peak positions for cis-HONO in the 6-micron spectral region that were derived from laboratory measurements. An essential component of ambient HONO measurements is the inlet system and we demonstrate that heated surfaces and reduced pressure minimize sampling artifacts.Earth and Planetary SciencesEngineering and Applied Science

Speculative bubbles and the cross-sectional variation in stock returns

Evidence suggests that rational, periodically collapsing speculative bubbles may be pervasive in stock markets globally, but there is no research that considers them at the individual stock level. In this study we develop and test an empirical asset pricing model that allows for speculative bubbles to affect stock returns. We show that stocks incorporating larger bubbles yield higher returns. The bubble deviation, at the stock level as opposed to the industry or market level, is a priced source of risk that is separate from the standard market risk, size and value factors. We demonstrate that much of the common variation in stock returns that can be attributable to market risk is due to the co-movement of bubbles rather than being driven by fundamentals

CD4+ T cell surface alpha enolase is lower in older adults

To identify novel cell ageing markers in order to gain insight into ageing mechanisms, we adopted membrane enrichment and comparison of the CD4+ T cell membrane proteome (purified by cell surface labelling using Sulfo-NHS-SS-Biotin reagent) between healthy young (n=9, 20-25y) and older (n=10; 50-70y) male adults. Following two-dimensional gel electrophoresis (2DE) to separate pooled membrane proteins in triplicates, the identity of protein spots with age-dependent differences (p1.4 fold difference) was determined using liquid chromatography-mass spectrometry (LC-MS/MS). Seventeen protein spot density differences (ten increased and seven decreased in the older adult group) were observed between young and older adults. From spot intensity analysis, CD4+ T cell surface α-enolase was decreased in expression by 1.5 fold in the older age group; this was verified by flow cytometry (n=22) and qPCR with significantly lower expression of cellular α-enolase mRNA and protein compared to young adult CD4+ T cells (p<0.05). In an independent age-matched case-control study, lower CD4+ T cell surface α-enolase expression was observed in age-matched patients with cardiovascular disease (p<0.05). An immune-modulatory role has been proposed for surface α-enolase and our findings of decreased expression suggest that deficits in surface α-enolase merit investigation in the context of immune dysfunction during ageing and vascular disease

UAS Chromatograph for Atmospheric Trace Species (UCATS) – a versatile instrument for trace gas measurements on airborne platforms

UCATS (the UAS Chromatograph for Atmospheric Trace Species) was designed and built for observations of important atmospheric trace gases from unmanned aircraft systems (UAS) in the upper troposphere and lower stratosphere (UTLS). Initially it measured major chlorofluorocarbons (CFCs) and the stratospheric transport tracers nitrous oxide (N2O) and sulfur hexafluoride (SF6), using gas chromatography with electron capture detection. Compact commercial absorption spectrometers for ozone (O3) and water vapor (H2O) were added to enhance its capabilities on platforms with relatively small payloads. UCATS has since been reconfigured to measure methane (CH4), carbon monoxide (CO), and molecular hydrogen (H2) instead of CFCs and has undergone numerous upgrades to its subsystems. It has served as part of large payloads on stratospheric UAS missions to probe the tropical tropopause region and transport of air into the stratosphere; in piloted aircraft studies of greenhouse gases, transport, and chemistry in the troposphere; and in 2021 is scheduled to return to the study of stratospheric ozone and halogen compounds, one of its original goals. Each deployment brought different challenges, which were largely met or resolved. The design, capabilities, modifications, and some results from UCATS are shown and described here, including changes for future missions.Support was provided for HIPPO by NSF award no. AGS-0628452, for ATTREX by NASA Earth Venture program award no. NNA11AA55I, and for ATom by NASA award no. NNH17AE26I; additional support was provided by NASA Upper Atmosphere Research Program award no. NNH13AV69I. This work was also supported in part by the NOAA Cooperative Agreement with CIRES, NA17OAR4320101

Mendelian randomization integrating GWAS and eQTL data reveals genetic determinants of complex and clinical traits

Genome-wide association studies (GWAS) have identified thousands of variants associated with complex traits, but their biological interpretation often remains unclear. Most of these variants overlap with expression QTLs, indicating their potential involvement in regulation of gene expression. Here, we propose a transcriptome-wide summary statistics-based Mendelian Randomization approach (TWMR) that uses multiple SNPs as instruments and multiple gene expression traits as exposures, simultaneously. Applied to 43 human phenotypes, it uncovers 3,913 putatively causal gene-trait associations, 36% of which have no genome-wide significant SNP nearby in previous GWAS. Using independent association summary statistics, we find that the majority of these loci were missed by GWAS due to power issues. Noteworthy among these links is educational attainment-associated BSCL2, known to carry mutations leading to a Mendelian form of encephalopathy. We also find pleiotropic causal effects suggestive of mechanistic connections. TWMR better accounts for pleiotropy and has the potential to identify biological mechanisms underlying complex traits

Search for dark matter produced in association with bottom or top quarks in √s = 13 TeV pp collisions with the ATLAS detector

A search for weakly interacting massive particle dark matter produced in association with bottom or top quarks is presented. Final states containing third-generation quarks and miss- ing transverse momentum are considered. The analysis uses 36.1 fb−1 of proton–proton collision data recorded by the ATLAS experiment at √s = 13 TeV in 2015 and 2016. No significant excess of events above the estimated backgrounds is observed. The results are in- terpreted in the framework of simplified models of spin-0 dark-matter mediators. For colour- neutral spin-0 mediators produced in association with top quarks and decaying into a pair of dark-matter particles, mediator masses below 50 GeV are excluded assuming a dark-matter candidate mass of 1 GeV and unitary couplings. For scalar and pseudoscalar mediators produced in association with bottom quarks, the search sets limits on the production cross- section of 300 times the predicted rate for mediators with masses between 10 and 50 GeV and assuming a dark-matter mass of 1 GeV and unitary coupling. Constraints on colour- charged scalar simplified models are also presented. Assuming a dark-matter particle mass of 35 GeV, mediator particles with mass below 1.1 TeV are excluded for couplings yielding a dark-matter relic density consistent with measurements

Guidelines for the use and interpretation of assays for monitoring autophagy (4th edition)1.

In 2008, we published the first set of guidelines for standardizing research in autophagy. Since then, this topic has received increasing attention, and many scientists have entered the field. Our knowledge base and relevant new technologies have also been expanding. Thus, it is important to formulate on a regular basis updated guidelines for monitoring autophagy in different organisms. Despite numerous reviews, there continues to be confusion regarding acceptable methods to evaluate autophagy, especially in multicellular eukaryotes. Here, we present a set of guidelines for investigators to select and interpret methods to examine autophagy and related processes, and for reviewers to provide realistic and reasonable critiques of reports that are focused on these processes. These guidelines are not meant to be a dogmatic set of rules, because the appropriateness of any assay largely depends on the question being asked and the system being used. Moreover, no individual assay is perfect for every situation, calling for the use of multiple techniques to properly monitor autophagy in each experimental setting. Finally, several core components of the autophagy machinery have been implicated in distinct autophagic processes (canonical and noncanonical autophagy), implying that genetic approaches to block autophagy should rely on targeting two or more autophagy-related genes that ideally participate in distinct steps of the pathway. Along similar lines, because multiple proteins involved in autophagy also regulate other cellular pathways including apoptosis, not all of them can be used as a specific marker for bona fide autophagic responses. Here, we critically discuss current methods of assessing autophagy and the information they can, or cannot, provide. Our ultimate goal is to encourage intellectual and technical innovation in the field