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At least 199 records · Page 11

Joint Test Plan for Gas Dynamic Spray Technology Demonstration

Air Force Space Command (AFSPC) and NASA have similar missions, facilities, and structures located in similar harsh environments. Both are responsible for a number of facilities/structures with metallic structural and non-structural components in highly and moderately corrosive environments. Regardless of the corrosivity of the environment, all metals require periodic maintenance activity to guard against the insidious effects of corrosion and thus ensure that structures meet or exceed design or performance life. The standard practice for protecting metallic substrates in atmospheric environments is the use of an applied coating system. Current coating systems used across AFSPC and NASA contain volatile organic compounds (VOCs) and hazardous air pollutants (HAPs). These coatings are subject to environmental regulations at the Federal and State levels that limit their usage. In addition, these coatings often cannot withstand the high temperatures and exhaust that may be experienced by AFSPC and NASA structures. In response to these concerns, AFSPC and NASA have approved the use of thermal spray coatings (TSCs). Thermal spray coatings are extremely durable and environmentally friendly coating alternatives, but utilize large cumbersome equipment for application that make the coatings difficult and time consuming to repair. Other concerns include difficulties coating complex geometries and the cost of equipment, training, and materials. Gas Dynamic Spray (GDS) technology (also known as Cold Spray) will be evaluated as a smaller, more maneuverable repair method as well as for areas where thermal spray techniques are not as effective. The technology can result in reduced maintenance and thus reduced hazardous materials/wastes associated with current processes. Thermal spray and GDS coatings also have no VOCs and are environmentally preferable coatings. To achieve a condition suitable for the application of a coating system, including GDS coatings, the substrate must undergo some type of surface preparation and/or depainting operation to ensure adhesion of the new coating system. The GDS unit selected for demonstration has a powder feeding system that can be used for surface preparation or coating application. The surface preparation feature will also be examined. The primary objective of this effort is to demonstrate GDS technology as a repair method for TSCs. The project will also determine the optimal GDS coating thickness for acceptable performance. Successful completion of this project will result in approval of GDS technology as a repair method for TSCs at AFSPC and NASA installations and will improve corrosion protection at critical systems, facilitate easier maintenance activity, extend maintenance cycles, eliminate flight hardware contamination, and reduce the amount of hazardous waste generated.

Lewis, Pattie↗

Demonstration/Validation of Environmentally-Preferable Coatings for Launch Facilities

Kennedy Space Center (KSC) is responsible for a number of facilities/structures with metallic structural and non-structural components in a highly corrosive environment. Metals require periodic maintenance activity to guard against the insidious effects of corrosion and thus ensure that structures meet or exceed design or performance life. The standard practice for protecting metallic substrates in atmospheric environments is the application of an applied coating system. Applied coating systems work via a variety of methods (barrier, galvanic and/or inhibitor) and adhere to the substrate through a combination of chemical and physical bonds. Maintenance at KSC and other NASA Centers is governed by NASA-STD-50088 (Protective Coating of Carbon Steel, Stainless Steel, and Aluminum on Launch Structures, Facilities, and Ground Support Equipment) which establishes practices for the protective coating of ground support equipment and related facilities used by or for NASA programs and projects. The Standard is for the design of non-flight hardware used to support the operations of receiving, transportation, handling, assembly, inspection, test, checkout, service, and launch of space vehicles and payloads at NASA launch, landing, or retrieval sites. These criteria and practices contained within the Standard may be used for items used at the manufacturing, development, and test sites upstream of the launch, landing, or retrieval sites. The objective of this effort is to demonstrate and validate environmentally-preferable alternatives in accordance with NASA-STD-50088 and KSC requirements which can then be added to the Approved Products List. This Test Protocol contains the critical requirements and tests necessary to qualify alternatives for structural steel applications. These tests were derived from engineering, performance, and operational impact (supportability) requirements defined by a consensus of KSC participants. A Test Report will document the results of the testing as well as any test modifications made during the execution of the testing. Users of this Test Protocol should check the project's Test Report for additional test details or minor modifications that may have been necessary in the execution of the testing. The technical stakeholders will have agreed upon test procedures modifications documented in the Test Report.

Lewis, Pattie↗

Hexavalent Chrome Free Coatings for Electronics Applications: Joint Test Report

Regardless of the corrosivity of the environment, all metals require periodic maintenance activity to guard against the insidious effects of corrosion and thus ensure that alloys meet or exceed design or performance life. The standard practice for protecting metallic substrates is the application of a coating system. Applied coating systems work via a variety of methods (barrier, galvanic, and/or inhibitor) and adhere to the substrate through a combination of chemical and physical bonds. For years hexavalent chromium has been a widely used element within applied coating systems because of its self healing and corrosion resistant properties. Occupational Safety and Health Administration (OSHA) studies have concluded that hexavalent chromium (hex chrome) is carcinogenic and poses significant risk to human health. On May 5, 2011 amendments to the Defense Federal Acquisition Regulation Supplement (DFARS) were issued in the Federal Register. Subpart 223.73 prohibits contracts from requiring hexavalent chromium in deliverables unless certain exceptions apply. These exceptions include authorization from a general or flag officer and members of the Senior Executive Service from a Program Executive Office, and unmodified legacy systems. Otherwise, Subpart 252.223-7008 provides the contract clause prohibiting contractors from using or delivering hexavalent chromium in a concentration greater than 0.1 percent by weight for all new contracts and to be included down to subcontractors for supplies, maintenance and repair services, and construction materials. National Aeronautics and Space Administration (NASA), Department of Defense (DoD), and industry stakeholders continue to search for alternatives to hex chrome in coatings applications that meet their performance requirements in corrosion protection, cost, operability, and health and safety, while typically specifying that performance must be equal to or greater than existing systems.

Kessel, Kurt↗

Environmentally Preferable Coatings for Structural Steel Project

The Ground Systems Development and Operations (GSDO) Program at NASA John F. Kennedy Space Center (KSC) has the primary objective of modernizing and transforming the launch and range complex at KSC to benefit current and future NASA programs along with other emerging users. Described a the "launch support and infrastructure modernization program" in the NASA Authorization Act of 2010, the GSDO Program will develop and implement shared infrastructure and process improvements to provide more flexible, affordable, and responsive capabilities to a multi-user community. In support of the GSDO Program, the objective of this project is to determine the feasibility of environmentally friendly corrosion resistant coatings for launch facilities and ground support equipment. The focus of the project is corrosion resistance and survivability with the goal to reduce the amount of maintenance required to preserve the performance of launch facilities while reducing mission risk. Number of facilities/structures with metallic structural and non-structural components in a highly corrosive environment. Metals require periodic maintenance activity to guard against the insidious effects of corrosion and thus ensure that structures meet or exceed design or performance life. The standard practice for protecting metallic substrates in atmospheric environments is the application of corrosion protective coating system.

Technology Portfolio System↗

TGF-beta1 release from biodegradable polymer microparticles: its effects on marrow stromal osteoblast function

BACKGROUND: Controlled release of transforming growth factor-beta1 (TGF-beta1) to a bone defect may be beneficial for the induction of a bone regeneration cascade. The objectives of this work were to assess the feasibility of using biodegradable polymer microparticles as carriers for controlled TGF-beta1 delivery and the effects of released TGF-beta1 on the proliferation and differentiation of marrow stromal cells in vitro. METHODS: Recombinant human TGF-beta1 was incorporated into microparticles of blends of poly(DL-lactic-co-glycolic acid) (PLGA) and poly(ethylene glycol) (PEG). Fluorescein isothiocynate-labeled bovine serum albumin (FITC-BSA) was co-encapsulated as a porogen. The effects of PEG content (0, 1, or 5% by weight [wt%]) and buffer pH (3, 5, or 7.4) on the protein release kinetics and the degradation of PLGA were determined in vitro for as long as 28 days. Rat marrow stromal cells were seeded on a biodegradable poly(propylene fumarate) (PPF) substrate. The dose response and biological activity of released TGF-beta1 was determined after 3 days in culture. The effects of TGF-beta1 released from PLGA/PEG microparticles on marrow stromal cell proliferation and osteoblastic differentiation were assessed during a 21-day period. RESULTS: TGF-beta1 was encapsulated along with FITC-BSA into PLGA/PEG blend microparticles and released in a multiphasic fashion including an initial burst for as long as 28 days in vitro. Increasing the initial PEG content resulted in a decreased cumulative mass of released proteins. Aggregation of FITC-BSA occurred at lower buffer pH, which led to decreased release rates of both proteins. The degradation of PLGA was increased at higher PEG content and significantly accelerated at acidic pH conditions. Rat marrow stromal cells cultured on PPF substrates showed a dose response to TGF-beta1 released from the microparticles similar to that of added TGF-beta1, indicating that the activity of TGF-beta1 was retained during microparticle fabrication and after growth factor release. At an optimal TGF-beta1 dosage of 1.0 ng/ml after 3 days, the released TGF-beta1 enhanced the proliferation and osteoblastic differentiation of marrow stromal cells over 21 days of culture, with increased total cell number, alkaline phosphatase activity, and osteocalcin production. CONCLUSIONS: PLGA/PEG blend microparticles can serve as delivery vehicles for controlled release of TGF-beta1, and the released growth factor enhances marrow stromal cell proliferation and osteoblastic differentiation in vitro. CLINICAL RELEVANCE: Controlled release of TGF-beta1 from PLGA/PEG microparticles is representative of emerging tissue engineering technologies that may modulate cellular responses to encourage bone regeneration at a skeletal defect site.

Non-NASA Center↗

Laterally Modulating Carrier Concentration by Ion Irradiation in CdO Thin Films for Mid‐IR Plasmonics

This report demonstrates tunable carrier densities in CdO thin films through local ion irradiation, providing lateral control of mid‐IR optical properties. Ion‐solid interactions produce donor‐like defects that boost electron concentrations from the practical minimum of 2.5 × 10 19 cm −3 to a maximum of 2.5 × 10 20 cm −3 by metered ion exposure. This range is achieved using He, N, Ar, or Au ions at 1–2.8 MeV; when normalized by displacements per atom, all ion species produce comparable results. Since CdO is well‐described by the Drude model, irradiation‐tuned carrier densities directly alter the infrared dielectric function, and in turn, mid‐infrared optical properties. Further, it is demonstrated that by combining irradiation with traditional lithography, CdO films expose to ions in the presence of 3‐µm thick, patterned photoresist exhibit lateral carrier density profiles with ≈400‐nm resolution. Scanning near‐field optical microscopy reveals sharp optical interfaces with almost no companion contrast in surface morphology, microstructure, or crystallinity. Finally, CdO lateral homostructures supporting surface plasmon polaritons (SPPs) are demonstrated whose dispersion relation can be tuned through periodic patterning in a monolithic platform by simple nanofabrication. Numerical simulations show these polaritons result from strong coupling between excitations at CdO plasma frequencies and SPPs supported by the platinum substrate.

cadmium oxide↗

SERS and the scientific career of Richard P. Van Duyne (1945–2019)

This article describes the scientific career of our dear friend Richard P. Van Duyne. Rick was the discoverer of surface-enhanced Raman spectroscopy (SERS), and over the period from the mid-1970s until his death in 2019, he served as both the intellectual leader of the field, and the technical genius who pushed the field forward through his numerous inventions and discoveries. Rick's work went through many phases, and even involved a significant period of inactivity that Rick was able to break out of, but especially after 2000, there was a period of incredible creativity that ultimately led to a detailed understanding of what the SERS enhancement factor is all about and also led to fabrication techniques for making optimum SERS substrates such that applications of SERS to a wide variety of real-world problems in sensing became possible. In addition, Rick's SERS work spawned numerous related technologies, including index of refraction sensing based on localized surface plasmon resonance (LSPR) measurements, and the extension of SERS to its tip-enhanced cousin TERS, to electrochemical versions of SERS and TERS, and to ultrafast nonlinear techniques. The practical applications he pursued included diagnostics for diseases such as cancer, hand-held glucose sensing, and SERS studies related to art conservation. Furthermore, Rick's legacy will probably be best known through the numerous students, postdocs, and collaborators that passed through his lab and who are now active researchers in areas related to SERS at universities and industrial labs around the world.

47 OTHER INSTRUMENTATION↗

Thermodynamics and Mechanism of a Photocatalyzed Stereoselective [2 + 2] Cycloaddition on a CdSe Quantum Dot

Colloidal quantum dots (QDs) have shown promise over the last few decades for a range of applications including single photon emission, in vivo imaging and photocatalysis. Recent experiments demonstrated that QDs impart stereoselectivity to triplet excited-state [2+2] cycloaddition reactions of alkenes photocatalyzed by the QD through self-assembly of the reagent molecules on the QD surface, but these experiments did not reveal the precise geometries of surface-bound molecules or their interactions with surface atoms. Here, a theoretical mechanistic approach is used to study such interactions for [2+2] cycloadditions of 4-vinylbenzoic acid derivatives on CdSe QDs. Spin-polarized periodic density functional theory (DFT) and non-periodic DFT calculations are deployed to determine the origin of the selectivity for the syn diastereomer of the resultant tetrasubstituted cyclobutane product via atomistic modelling of the CdSe surface and substrates, and determination of the thermodynamic energies of reactions for each step, the intermolecular interactions between the substrates, and the triplet state reaction paths. The calculations indicate that reaction selectivity arises from preferred binding of pairs through intermolecular interactions of substrate molecules on the QD surface in a syn-precursor structure followed by dimerization after triplet excitation. Further, these mechanisms are generalizable to other metal-enriched QD surfaces that have a similar surface structure to CdSe, such as InSe or CdTe. Design principles for anti diastereomer derivatives are also discussed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Diode effect for skyrmions interacting with linear protrusion defects

We simulate collectively interacting skyrmions in a channel with periodic asymmetry, and find a strong diode effect for the skyrmion flow. There is also an asymmetry in the skyrmion annihilation rate for currents applied along the hard or easy substrate asymmetry direction, with a higher annihilation rate for hard direction currents. We map out the diode efficiency as a function of magnetic field and substrate asymmetry angle. We also show that the Magnus force impacts the diode motion and annihilation rate asymmetry by forcing skyrmions into corners of the protrusion geometry.

36 MATERIALS SCIENCE↗

Fungal elemental profiling unleashed through rapid laser-induced breakdown spectroscopy (LIBS)

ABSTRACT Elemental profiling of fungal species as a phenotyping tool is an understudied topic and is typically performed to examine plant tissue or non-biological materials. Traditional analytical techniques such as inductively coupled plasma–optical emission spectroscopy (ICP-OES) and inductively coupled plasma–mass spectrometry (ICP-MS) have been used to identify elemental profiles of fungi; however, these techniques can be cumbersome due to the difficulty of preparing samples. Additionally, the instruments used for these techniques can be expensive to procure and operate. Laser-induced breakdown spectroscopy (LIBS) is an alternative elemental analytical technique—one that is sensitive across the periodic table, easy to use on various sample types, and is cost-effective in both procurement and operation. LIBS has not been used on axenic filamentous fungal isolates grown in substrate media. In this work, as a proof of concept, we used LIBS on two genetically distinct fungal species grown on a nutrient-rich and nutrient-poor substrate media to determine whether robust elemental profiles can be detected and whether differences between the fungal isolates can be identified. Our results demonstrate a distinct correlation between fungal species and their elemental profile, regardless of the substrate media, as the same strains shared a similar uptake of carbon, zinc, phosphorus, manganese, and magnesium, which could play a vital role in their survival and propagation. Independently, each fungal species exhibited a unique elemental profile. This work demonstrates a unique and valuable approach to rapidly phenotype fungi through optical spectroscopy, and this approach can be critical in understanding these fungi's behavior and interactions with the environment. IMPORTANCE Historically, ionomics, the elemental profiling of an organism or materials, has been used to understand the elemental composition in waste materials to identify and recycle heavy metals or rare earth elements, identify the soil composition in space exploration on the moon or Mars, or understand human disorders or disease. To our knowledge, ionomic profiling of microbes, particularly fungi, has not been investigated to answer applied and fundamental biological questions. The reason is that current ionomic analytical techniques can be laborious in sample preparation, fail to measure all potential elements accurately, are cost-prohibitive, or provide inconsistent results across replications. In our previous efforts, we explored whether laser-induced breakdown spectroscopy (LIBS) could be used in determining the elemental profiles of poplar tissue, which was successful. In this proof-of-concept endeavor, we undertook a transdisciplinary effort between applied and fundamental mycology and elemental analytical techniques to address the biological question of how LIBS can used for fungi grown axenically in a nutrient-rich and nutrient-poor environment.

59 BASIC BIOLOGICAL SCIENCES↗

Fungal elemental profiling unleashed through rapid laser-induced breakdown spectroscopy (LIBS)

Elemental profiling of fungal species as a phenotyping tool is an understudied topic and is typically performed to examine plant tissue or non-biological materials. Traditional analytical techniques such as inductively coupled plasma–optical emission spectroscopy (ICP-OES) and inductively coupled plasma–mass spectrometry (ICP-MS) have been used to identify elemental profiles of fungi; however, these techniques can be cumbersome due to the difficulty of preparing samples. Additionally, the instruments used for these techniques can be expensive to procure and operate. Laser-induced breakdown spectroscopy (LIBS) is an alternative elemental analytical technique—one that is sensitive across the periodic table, easy to use on various sample types, and is cost-effective in both procurement and operation. LIBS has not been used on axenic filamentous fungal isolates grown in substrate media. In this work, as a proof of concept, we used LIBS on two genetically distinct fungal species grown on a nutrient-rich and nutrient-poor substrate media to determine whether robust elemental profiles can be detected and whether differences between the fungal isolates can be identified. This data set contains the raw LIBS spectral data for the summarized results described inRush, et. al. 2024

elemental profiling↗

The Genesis Mission Solar Wind Collection: Solar-Wind Statistics over the Period of Collection

The NASA Genesis spacecraft was launched August 8, 2001 on a mission to collect samples of solar wind for 2 years and return them to earth September 8, 2004. Detailed analyses of the solar wind ions implanted into high-purity collection substrates will be carried out using various mass spectrometry techniques. These analyses are expected to determine key isotopic ratios and elemental abundances in the solar wind, and by extension, in the solar photosphere. Further, the photospheric composition is thought to be representative of the solar nebula with a few exceptions, so that the Genesis mission will provide a baseline for the average solar nebula composition with which to compare present-day compositions of planets, meteorites, and asteroids. The collection of solar wind samples is almost complete. Collection began for most substrates in early December, 2001, and is scheduled to be complete on April 2 of this year. It is critical to understand the solar-wind conditions during the collection phase of the mission. For this reason, plasma ion and electron spectrometers are continuously monitoring the solar wind proton density, velocity, temperature, the alpha/proton ratio, and angular distribution of suprathermal electrons. Here we report on the solar-wind conditions as observed by these in-situ instruments during the first half of the collection phase of the mission, from December, 2001 to present.

Barraclough, B. L.↗

Space Station Freedom Solar Array design development

The Space Station Freedom Solar Array Program is required to provide a 75 kW power module that uses eight solar array (SA) wings over a four-year period in low Earth orbit (LEO). Each wing will be capable of providing 23.4 kW at the 4-year design point. Lockheed Missles and Space Company, Inc. (LMSC) is providing the flexible substrate SAs that must survive exposure to the space environment, including atomic oxygen, for an operating life of fifteen years. Trade studies and development testing, important for evolving any design to maturity, are presently underway at LMSC on the flexible solar array. The trade study and development areas being investigated include solar cell module size, solar cell weld pads, panel stiffener frames, materials inherently resistant to atomic oxygen, and weight reduction design alternatives.

Winslow, Cindy↗

Numerical Solution of Light Scattered from and Transmitted through a Rough Dielectric Surface with Applications to Periodic Roughness and Isolated Structures

Light scattering and transmission by rough surfaces are of considerable interest in a variety of applications including remote sensing and characterization of surfaces. In this work, the finite-difference time domain technique is applied to calculate the scattered and transmitted electromagnetic fields of an infinite periodic rough surface. The elements of Mueller matrix for scattered light are calculated by an integral of the near fields over a significant number of periods of the surface. The normalized Mueller matrix elements of the scattered light and the spatial distribution of the transmitted flux for a monolayer of micron-sized dielectric spheres on a silicon substrate are presented. The numerical results show that the nonzero Mueller matrix elements of the system of the monolayer of dielectric spheres on a silicon substrate have specific maxima at some scattering angles. These maxima may be used in characterization of the feature of the system. For light transmitted through the monolayer of spheres, our results show that the transmitted energy focuses around the ray passing through centers of the spheres. At other locations, the transmitted flux is very small. The technique also may be used to calculate the perturbance of the electromagnetic field due to the presence of an isolated structure on the substrate.

Sun, Wenbo↗

Ice nucleation measurements from DRUM impactors during TRACER campaign in the Houston TX region from July to September 2022

During TRACER, three Davis Rotating Uniform size-cut Monitors (DRUM; DRUMAir 4-DRUM) were used to collect aerosols for ice nucleation measurements in the Brooks laboratory at Texas A&M University. The three instruments were located at AMF1 in La Porte, Ancillary site in Guy (ANC), and onboard the Texas A&M Rapid Onsite Atmospheric Measurements Van (ROAM-V). ROAM-V was deployed to capture airmasses behind (maritime) and ahead (continental) of the passage of the sea-breeze front through Houston. On select sampling days, ROAM-V sampled in the morning/mid-day on the coast and then transited to a second inland site for the afternoon/evening. The suite of instruments deployed on ROAM-V included a Condensation Particle Counter (CPC; GRIMM Model 5.403 CPC), Scanning Mobility Particle Sizer (SMPS; TSI 3750 detector, TSI 3082 classifier, TSI 3088 neutralizer, TSI 3081A Differential Mobility Analyzer), Cloud Condensation Nuclei counter (Droplet Measurement Technologies CCN Counter), micro pulse lidar (Droplet Measurement Technologies Micro Pulse LiDAR (miniMPL)), and one of the Davis Rotating Uniform size-cut Monitors (DRUM; DRUMAir 4-DRUM). Before sampling at each location, the latitude and longitude were recorded using the GPS on the phone application “My Altitude”. Each DRUM sampler was operated at a flow rate of 23 LPM. Each DRUM has four stages where the aerodynamic diameter size cuts are as follows: stage 1 larger than 3 μm, stage 2 from 3 to 1.2 μm, stage 3 from 1.2 to 0.34 μm, and stage 4 from 0.34 to 0.15 μm. Pretreated aluminum foil was used as a substrate on all stages. At AMF1 and ANC sites, the DRUMs were operated on the shared aerosol inlet, with generous support of the DOE ARM site staff. These instruments rotated 24 mm per day and only contained aluminum foil substrates. Substrates were changed weekly and transported to Texas A&M for storage in -80C freezer until analysis. The DRUM onboard ROAM-V was operated at a faster rotation rate of 150 mm per day to clearly separate the multiple deployment locations for ROAM-V. For the ROAM-V DRUM, substrates were changed every deployment and transported to Texas A&M for storage in -80C freezer until analysis. At Texas A&M, ice nucleation experiments were conducted to measure the ice nucleation temperature of the ambient aerosol samples collected from the three DRUMs using our previously established procedures (Alsante et al., 2023; Fornea et al., 2009; Matthews et al., 2023). For ice nucleation, only samples collected on stage 3 were analyzed, given that these are the most relevant size (1.2 to 0.34 μm diameter) for potential ice nucleating particles. For the AMF1 and ANC sites, we cut and analyzed 2 mm (2-hour) samples. We analyzed the time periods of the AMF1 site instrument when the ROAM-V was deployed. A 72-hour period from July 11th at 23:49 through July 15th at 1:49 was analyzed from the ANC site instrument. For the ROAM-V instrument, we separated the daily samples by site location. Between 1- and 6-hour independent samples were analyzed at each location. We also cut the ROAM-V samples in half to allow for compositional analysis of the aerosol on the other half of the substrate. All viable samples from the ROAM-V were analyzed. Analysis was done using a custom-built ice nucleation apparatus, recently updated to include an array of 16 individual samples (Matthews et al., 2023). On our experimental setup, we used 100 μL of Ultra-High-Performance Liquid Chromatography (UHPLC) water (Sigma Aldrich, >99.9% purity) to wash off the aerosol from the DRUM substrate. Then, we micropipetted 2 μL droplet samples into each of the 16 wells of the array, using hydrophobically coated microscope slides. Experiments would cycle 28 times from 10 C to -40C over a 20-hour period. During analysis of the TRACER samples, nine experiments were conducted with UHPLC water process blanks that followed an identical preparation procedure. The average freezing temperature and standard deviation for these process blanks is -27.7±2.4 C. This data was collected for ARM Field Campaign AFC07023 and supported by DOE ASR grant DE-SC0021047. For any further questions, please feel free to contact the instrument PI, Sarah D. Brooks, sbrooks@tamu.edu. Alsante, A. N., Thornton, D. C., & Brooks, S. D. (2023). Ice nucleation catalyzed by the photosynthesis enzyme RuBisCO and other abundant biomolecules. Communications Earth & Environment, 4(1), 51. Fornea, A. P., Brooks, S. D., Dooley, J. B., & Saha, A. (2009). Heterogeneous freezing of ice on atmospheric aerosols containing ash, soot, and soil. Journal of Geophysical Research: Atmospheres, 114(D13). DOI:10.1029/2009JD011958 Matthews, B. H., Alsante, A. N., & Brooks, S. D. (2023). Pollen Emissions of Subpollen Particles and Ice Nucleating Particles. ACS Earth and Space Chemistry.

54 ENVIRONMENTAL SCIENCES↗

Radiocarbon Analyses Quantify Peat Carbon Losses With Increasing Temperature in a Whole Ecosystem Warming Experiment

Abstract Climate warming is expected to accelerate peatland degradation and release rates of carbon dioxide (CO 2 ) and methane (CH 4 ). Spruce and Peatlands Responses Under Changing Environments is an ecosystem‐scale climate manipulation experiment, designed to examine peatland ecosystem response to climate forcings. We examined whether heating up to +9 °C to 3 m‐deep in a peat bog over a 7‐year period led to higher C turnover and CO 2 and CH 4 emissions, by measuring 14 C of solid peat, dissolved organic carbon (DOC), CH 4 , and dissolved CO 2 (DIC). DOC, a major substrate for heterotrophic respiration, increased significantly with warming. There was no 7‐year trend in the DI 14 C of the ambient plots which remained similar to their DO 14 C. At +6.75 °C and +9 °C, the 14 C of DIC, a product of microbial respiration, initially resembled ambient plots but became more depleted over 7 years of warming. We attributed the shifts in DI 14 C to the increasing importance of solid phase peat as a substrate for microbial respiration and quantified this shift via the radiocarbon mass balance. The mass‐balance model revealed increases in peat‐supported respiration of the catotelm depths in heated plots over time and relative to ambient enclosures, from a baseline of 20%–25% in ambient enclosures, to 35%–40% in the heated plots. We find that warming stimulates microorganisms to respire ancient peat C, deposited under prior climate (cooler) conditions. This apparent destabilization of the large peat C reservoir has implications for peatland‐climate feedbacks especially if the balance of the peatland is tipped from net C sink to C source.

54 ENVIRONMENTAL SCIENCES↗

Site Selection for Mars Exopaleontology in 2001

The microbial fossil record encompasses a wide range of information, including cellular remains, stromatolites, biofabrics, trace fossils, biominerals and chemofossils. The preservation of fossils is strongly influenced by the physical, chemical and biological factors of the environment which, acting together, ultimately determine the types of information that will be captured and retained in the rock record. The critical factor in assessing the suitability of a site for a microbial fossil record is the paleoenvironment. The reconstruction of ancient sedimentary environments usually requires the integration of a wide variety of geological information, including the shape, geometry and internal structure of sedimentary deposits, their mineralogy, and geochemistry. For Mars, much of our knowledge about past environments is based on orbital imaging of geomorphic features. This evidence provides an important context and starting point for site selection. However, our knowledge of the martian surface is quite limited, and a major goal of the upcoming exploration effort is to reconstruct the history of Martian volatiles, climate, and hydrology as a context for the exploration for past or present life. Mineralogical mapping from orbit will be an important key in this effort. In exploring for evidence of past life, terrestrial experience suggests that the long-term preservation of biological information as fossils occurs under a fairly narrow range of geological conditions that are well known to paleontologists (1). In detrital sedimentary systems, microbial fossilization is favored by rapid burial in fine-grained, clay-rich sediments. In chemical sedimentary systems, preservation is enhanced by rapid entombment in fine-grained chemical precipitates. For long term preservation, host rocks must be composed of stable minerals that resist chemical weathering, and which form an impermeable matrix and closed chemical system that can protect biosignatures from alteration during subsequent diagenetic change or metamorphism. In this context, host rocks composed of highly ordered, chemically-stable mineral phases, like silica (forming cherts) or phosphate (forming phosphorites), are especially favored. Such lithologies tend to have very long crustal residence times and (along with carbonates and shales), are the most common host rocks for the Precambrian microfossil record on Earth. If we assume that a subsurface hydrosphere has been present throughout martian history, then life could have originated there at any time, perhaps emerging at the surface periodically when climate changes, induced by external forcing or endogenous processes (e.g. volcanism), allowed liquid water to exist at the surface. The recent discovery of subsurface chemolithoautotrophic organisms which are capable of synthesizing organic substrates from C02 and H2 liberated from the aqueous weathering of basalt, is especially. relevant as a model for martian life. While a subsurface habitable zone may yet exist on Mars, access to such environments will likely require drilling to depths of several kilometers. Given the technological challenge of deep drilling, this is unlikely to occur prior to human missions. So, even if there is extant life on Mars today in subsurface habitats, it may be much easier to find its fossil counterparts in ancient deposits exposed at the surface. In exploring for a fossil record in subsurface environments on Mars there are several geological situations that may provide access to the appropriate materials. These include 1) ejecta from impact craters, 2) talus slopes, debris flows or alluvial fans developed below the walls of deep canyons, and 3) the deposits of outflood channels. Examples of aqueous mineral deposits of formed in subsurface environments that could harbor a microbial fossil record include such things as cements in detrital sedimentary rocks, low temperature diagenetic minerals deposited in veins, or filling vesicles in volcanic rocks, and hydrothermal deposits formed below the upper temperature limit for life (about 160 degrees C). There are many sites within the present latitudinal constraints for the 2001 mission (15 deg S to 30 deg N) that meet these requirements. But the practical problem with these kinds of deposits is that they tend to be disseminated, making up only a small percentage of a host rock. Even with mineralogical information provided by the Thermal Emission Spectrometer (TES) presently in orbit around Mars, predicting their occurrence ahead of time may be quite difficult. The deposits of surficial aqueous sedimentary systems are likely to provide the largest targets for site selection in 2001. Of these, the deposits of hydrothermal systems (subaerial and subaqueous thermal springs) have been discussed previously. It is likely that hydrothermal systems were widespread on Mars early in its history and a number of common geo-tectonic settings on Mars are likely to have hosted hydrothermal activity. Most of these are represented within the latitudinal constraints presently identified for 2001. However, the deposits of surface spring systems are likely to be difficult to find as well. On Earth, exposure areas for hydrothermal spring mounds are typically a few square kms, less than a single TES pixel. But such deposits may be quite abundant within some volcanic terrains, It is estimated, for example, that between 15-20% of the floor of Yellowstone caldera is covered by thermal spring deposits. In such abundances, subaerial sinters could well be detected by TES. Where exposed, the shallow subsurface portions of these systems may be quite a lot larger (perhaps tens of square kms), although (as noted above) mineralization may be finely disseminated in the basement rock, making remote detection more difficult. Paleolake Basins. There are a large number of potential paleolake basins on Mars (inclusive of impact craters and volcanic calderas) that have been previously identified using Viking images. Most of these lie in the southern highlands beyond the l5 deg S constraint for 2001. However, deposits of paleolakes may offer the largest and most easily identified exopaleontological targets from orbit. Based on a variety of arguments, some workers have suggested that there was once an ancient ocean on the northern plains, and some sites of interest (potential shoreline terraces) fall within the 30 deg N constraint. From a paleontological standpoint the most interesting places of this type are terminal paleolake basins which are likely to have been both saline and alkaline. Models by Schaefer suggest such environments could be widespread on Mars. The conditions in terminal lake basin settings favor widespread chemical sedimentation, an important condition for microbial fossilization. Important lithological targets for a microbial fossil record in terminal lake basins include spring-deposited carbonates, shoreline cements, a wide variety of evaporite minerals and fine-grained detrital sediments including shales, marls, and water-lain volcanic ash deposits. In developing a strategy to explore for ancient hydrothermal deposits on Mars, we can learn from the methods that have been developed by explorationists to explore for economic mineral deposits on Earth. Due to their simple mineralogy, hydrothermal deposits can often be detected using remote sensing methods. Common thermal spring mineral assemblages include silica, carbonate, and various metallic oxides and sulfides. But there are also a number of diagnostic silicate minerals, including clays, formed by the hydrothermal alteration of country rocks. These hydrothermal minerals have characteristic spectral signatures that could be detected from Mars orbit using high resolution infrared remote sensing methods. In playa lake settings, evaporite deposits often form a predictable "bull's eye" pattern with carbonates being deposited in marginal basin areas, and sulfates and halides occurring progressively more basinward. The floors of some impact craters on Mars, such as "White Rock" and Bequeral Crater (see Oxia Palus NE, Site 148), have floor deposits that could be evaporites, inclusive of carbonates. Evaporite minerals possess characteristic spectral signatures in the infrared and could similarly be identified from Mars orbit using high resolution remote sensing methods. Clearly, utilization of TES data will be important for optimizing site selection for Exopaleontology, and every effort should be made to benefit from that data before a final decision is made.

Farmer, Jack↗

Bladed Terrain on Pluto: Possible Origins and Evolutions

Pluto's Bladed Terrain (centered roughly 20 deg N, 225 deg E) covers the flanks and crests of the informally named Tartarus Dorsa with numerous roughly aligned blade-like ridges oriented approx. North-South; it may also stretch considerably farther east onto the non-close approach hemisphere but that inference is tentative. Individual ridges are typically several hundred meters high, and are spaced 5 to 10 km crest to crest, separated by V-shaped valleys. Many ridges merge at acute angles to form Y-shape junctions in plan view. The principle composition of the blades themselves we suspect is methane or a methane-rich mixture. (Methane is spectroscopically strongly observed on the optical surfaces of blades.) Nitrogen ice is very probably too soft to support their topography. Cemented mixtures of volatile and non-volatile ices may also provide a degradable but relief supporting "bedrock" for the blades, perhaps analogous to Callisto. Currently we are considering several hypotheses for the origins of the deposit from which Bladed Terrain has evolved, including aeolian disposition, atmospheric condensation, updoming and exhumation, volcanic intrusions or extrusions, crystal growth, among others. We are reviewing several processes as candidate creators or sculptors of the blades. Perhaps they are primary depositional patterns such as dunes, or differential condensation patterns (like on Callisto), or fissure extrusions. Or alternatively perhaps they are the consequence of differential erosion (such as sublimation erosion widening and deepening along cracks), variations in substrate properties, mass wasting into the subsurface, or sculpted by a combination of directional winds and solar isolation orientation. We will consider the roles of the long-term increasing solar flux and short periods of warm thick atmospheres. Hypotheses will be ordered based on observational constrains and modeling to be presented at the conference.

methane↗