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New Generation Flask Sampling Technology Final Report

Scientists are turning their focus to the Arctic, site of one of the strongest climate change signals. A new generation of technologies is required to function within that harsh environment, chart evolution of its trace gases and provide new kinds of information for models of the atmosphere. Our response to the solicitation tracks how global atmospheric monitoring was launched more than a half century ago; namely, acquisition of discrete samples of air by flask and subsequent analysis in the laboratory. AOS is proposing to develop a new generation of flask sampling technology. It will enable the new Arctic programs to begin with objective high density sampling of the atmosphere by UAS. The Phase I program will build the prototype flask technology and show that it can acquire and store mol fractions of CH4 and CO2 and value of δ13C with good fidelity. A CAD model will be produced for the entire platform including a package with 100 flasks and the airframe with auto-pilot, electronic propulsion and ground-to-air communications. A mobile flask analysis station will be prototyped in Phase I and designed to final form in Phase II. It expends very small sample per analysis and will interface directly to the flask package integrated permanently into the UAS fuselage. Commercial Applications and Other Benefits: • The New Generation Flask Sampling Technology able to provide a hundred or more samples of air per UAS mission. • A mobile analysis station expending far less sample than the existing ones and small enough to be stationed at the remote sites of Arctic operations. • A new form of validation for continuous trace gas observations from all platforms including the small UAS. • Further demonstration to potential customers of the AOS capabilities to invent, build, deploy and exploit entire platforms for observations of Earth’s atmosphere and ocean. Key Words: Flask Sampler, Mobile Analysis Station, Trace Gas, CO2, CH4, δC13, UAS, Baseline Airborne Observatory, Arctic, Climate Change. Summary for Members of Congress: The air, land and sea of the Arctic combine to produce a large climate change signal. AOS is proposing to develop unmanned airborne technologies able to begin prompt, objective observations of the signal’s atmospheric component.

54 ENVIRONMENTAL SCIENCES↗

Chemical and structural investigation of the paroxetine-human serotonin transporter complex

Antidepressants target the serotonin transporter (SERT) by inhibiting serotonin reuptake. Structural and biochemical studies aiming to understand binding of small-molecules to conformationally dynamic transporters like SERT often require thermostabilizing mutations and antibodies to stabilize a specific conformation, leading to questions about relationships of these structures to the bonafide conformation and inhibitor binding poses of wild-type transporter. To address these concerns, we determined the structures of ΔN72/ΔC13 and ts2-inactive SERT bound to paroxetine analogues using single-particle cryo-EM and x-ray crystallography, respectively. We synthesized enantiopure analogues of paroxetine containing either bromine or iodine instead of fluorine. We exploited the anomalous scattering of bromine and iodine to define the pose of these inhibitors and investigated inhibitor binding to Asn177 mutants of ts2-active SERT. These studies provide mutually consistent insights into how paroxetine and its analogues bind to the central substrate-binding site of SERT, stabilize the outward-open conformation, and inhibit serotonin transport.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Revisiting the Origin of Macromolecular Carbon (MMC) in Lunar Basalts 15556 & 10044

Volatile elements influence the geo-chemical evolution of planetary bodies and they are in magmas at every stage, from melting within planetary interiors to eruption at the surface. Analyses of lunar mare basalts supported the hypothesis that lunar mag-mas were depleted in volatiles (H-C-F-Cl-S), relative to their terrestrial analogs [1]. Nevertheless, several early studies of samples returned during the Apollo program proposed that the mare basalt eruptions, including the “fire fountain” eruptions, were propelled by the oxidation of magmatic graphite to CO (and/or CO2) gas [2, 3]. Seminal studies during the 1970’s measured the bulk concentration and isotopic compositions of C from Apollo 11 samples, and identified several carbonaceous compounds, including: (a) gaseous (CO, CO2, and traces of CH4), (b) metallic carbide, and (c) potentially elemental carbon [4-6]. These studies reported a relatively broad range of C contents (~100-400 μg/g) and isotopic values (δC13 = -30 to +20), and suggested that these heterogeneities can be explained by contribution from multiple factors, including: (a) indigenous carbon, (b) solar wind implantation, (c) bombardment and/or meteorite impact, and (d) terrestrial contamination [5,6]. However, unequivocal observations of magmatic graphite in lunar basalts have never been made. Macromolecular carbon (MMC)—graphitic carbon varying from nearly amorphous to highly crystalline varieties—was identified as inclusions hosted by igneous pyroxenes from Martian meteorites and were attributed to being indigenous to Mars [8]. The authors carefully considered the textural and mineralogical relationship of the MMC phases, and concluded that the subset of MMC located within and/or adjacent to cracks, or at a disrupted surface (e.g., cut) were most consistent with terrestrial contamination. The near absence of con-firmed instances of lunar magmatic MMC within the literature [9], combined with the wide range of isotopic values and bulk carbon contents measured in lunar bas-alts begs the question as to whether previously measured carbon is of an indigenous origin, or the result of terrestrial contamination. Using Raman spectroscopy, we have observed MMC in lunar basalts subjected to different forms of anthropogenic modification related to sample preparation including polished sections, sawn surfaces, and fractured surfaces adjacent to sawn sur-faces. We have observed MMC of unknown origin in all of these settings. Here we report the preliminary textural and spectroscopic characteristics of MMC hosted within the groundmass of Apollo 15 (15556) and Apollo 11 basalts (10044) as part of our ongoing investigation of the origin of these carbonaceous materials.

lunar↗