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NASA NTRS2015

Fluorine and Lithium at the Kimberley Outcrop, Gale Crater

ChemCam is an active remote sensing instrument which has operated successfully on MSL since landing in August, 2012. Its laser pulses remove dust and to profile through weathering coatings of rocks up to 7 m away. Laser-induced breakdown spectroscopy (LIBS) produces emission spectra of materials ablated from the samples in electronically excited states. As the plasma cools, elements can recombine and molecular emission lines are observed. Recent experiments have shown that some of these molecular emissions can be much brighter than the associated atomic lines, especially when halo-gens and rare earth elements are present. We observed these molecular emissions in some of the ChemCam spectra and report the first detection of chlorine and fluorine with ChemCam. It is also the first time ever that fluorine has been detected on the surface of Mars. Among all the F-bearing observations, one third are observed in the Kimberley outcrop. We will dis-cuss the potential mineralogies related to these observations as well as the related elemental correlations and propose interpretations.

Forni, O.↗
NASA NTRS1978

Calculated rate constants for the reaction ClO + O yields Cl + O2 between 220 and 1000 deg K

Classical trajectory calculations are presented for the reaction ClO + O yields Cl + O2, a reaction which is an important step in the chlorine-catalyzed destruction of ozone which is thought to occur in the 220 and 1000 K. The calculated rate constant is 4.36 x 10 to the minus 11th power exp (-191/T)cu cm molecule (-1)s(-1) and its value at 300 K is 2.3 plus or minus 10 to the 11th power cu cm molecule (-1)s(-1), about a factor of 2 lower than recent experimental data. The empirical potential energy surface used in the calculations was constructed to fit experimental data for ClO, O2 and ClOO molecules. Other important features of this potential surface, such as the barrier to reaction, were varied systematically and calculations were performed for a range of conditions to determine the best theoretical rate constants. Results demonstrate the utility of classical trajectory methods for determining activation energies and other kinetic data for important atmospheric reactions.

Jaffee, R. L.↗
NASA NTRS2025

Components Refurbishment and Chemical Analysis Facility, SWMU #041 - Per- and Polyfluoroalkyl Substances Site Assessment Report Kennedy Space Center, Florida

This PFAS Site Assessment (SA) Report presents the activities and results associated with PFAS investigations at the Components Refurbishment and Chemical Analysis (CRCA) facility located at Kennedy Space Center (KSC), Florida. In 2022, CRCA was identified as an Area of Potential Concern because the facility stores several potential PFAS-containing chemicals. A groundwater sample collected from an onsite monitoring well detected PFOA and PFOS at concentrations greater than State of Florida provisional Groundwater Cleanup Target Levels (pGCTLs). PFAS SA activities were conducted between March 2022 and February 2024. During this timeframe, a total of 16 direct-push technology (DPT) locations and 82 discrete samples were collected from these locations, along with 90 monitoring well samples. The analytical data screening process focused on State of Florida pGCTLs and United States Environmental Protection Agency (USEPA) Regional Screening Level (RSLs) from November 2023 to evaluate the data. Analytical results identified PFOS, PFOA, and PFBA at concentrations exceeding their respective RSLs at each depth interval (shallow, intermediate, and deep). PFOS and PFOA had the largest footprint of RSL exceedances in each depth interval, but pGCTL exceedances were only observed at limited locations in the shallow and intermediate intervals. PFBA had the highest detections of any PFAS compound, with concentrations exceeding 180,000 nanograms per liter (ng/L), which is 100-times the RSL of 1,800 ng/L in the shallow and intermediate intervals and 10-times the RSL in the deep interval. The maximum PFBA detection was 841,000 ng/L at shallow monitoring well, MW0006. The PFAS SA also included samples collected from the onsite hydraulic containment system (HCS) which was installed to control and treat the onsite chlorinated volatile organic compound (CVOC) plume. Influent and effluent aqueous samples were collected monthly from the system. PFAS concentrations were relatively the same for both influent and effluent samples, indicating that while the HCS has been effective for CVOC treatment, it does not provide any additional treatment for PFAS compounds. Since the HCS has achieved its objectives, the system was shut down in December 2024. PFAS data gaps still exist, to include surface water and soil, which were not sampled during this SA. Soil sampling near the Chemical Process Area is recommended. Surface water and soil sampling at select stormwater outfalls is also recommended. Additionally, further groundwater sampling is recommended (DPT and monitoring well) in all depth intervals to delineate the extent of PFAS impacts at CRCA.

K Alex Murphy↗
NASA NTRS2010

Effect of Fluorine on Near-Liquidus Phase Equilibria of Basalts

Volatile species such as H2O, CO2, F, and Cl have significant impact in generation and differentiation of basaltic melts. Thus far experimental work has primarily focused on the effect of water and carbon dioxide on basalt crystallization, liquid-line of descent, and mantle melting [e.g., 1, 2] and the effects of halogens have received far less attention [3-4]. However, melts in the planetary interiors can have non-negligible chlorine and fluorine concentrations. Here, we explore the effects of fluorine on near-liquidus phase equilibria of basalt. We have conducted nominally anhydrous piston cylinder experiments using graphite capsules at 0.6 - 1.5 GPa on an Fe-rich model basalt composition. 1.75 wt% fluorine was added to the starting mix in the form of AgF2. Fluorine in the experimental glass was measured by SIMS and major elements of glass and minerals were analyzed by EPMA. Nominally volatile free experiments yield a liquidus temperature from 1330 C at 0.8GPa to 1400 at 1.6GPa and an olivine(Fo72)-pyroxene(En68)-liquid multiple saturation point at 1.25 GPa and 1375 C. The F-bearing experiments yield a liquiudus temperature from 1260 C at 0.6GPa to 1305 at 1.5GPa and an ol(Fo66)-pyx(En64)-MSP at 1 GPa and 1260 C. This shows that F depresses the basalt liquidus, extends the pyroxene stability field to lower pressure, and forces the liquidus phases to be more Fe-rich. KD(Fe-Mg/mineral-melt) calculated for both pyroxenes and olivines show an increase with increasing F content of the melt. Therefore, we infer that F complexes with Mg in the melt and thus increases the melt s silica activity, depressing the liquidus and changing the composition of the crystallizing minerals. Our study demonstrates that on a weight percent basis, the effect of fluorine is similar to the effect of H2O [1] and Cl [3] on freezing point depression of basalts. But on an atomic fraction basis, the effect of F on liquidus depression of basalts is xxxx compared to the effect of H. Future studies on kimberlitic and subduction zone magmas, which could have significant amount of fluorine, will need to consider the combined effects of F, Cl, and H on their stability and chemical evolution.

Filiberto, Justin↗
NASA NTRS2008

The Long-term Middle Atmospheric Influence of Very Large Solar Proton Events

Long-term variations in ozone have been caused by both natural and humankind related processes. The humankind or anthropogenic influence on ozone originates from the chlorofluorocarbons and halons (chlorine and bromine) and has led to international regulations greatly limiting the release of these substances. Certain natural ozone influences are also important in polar regions and are caused by the impact of solar charged particles on the atmosphere. Such natural variations have been studied in order to better quantify the human influence on polar ozone. Large-scale explosions on the Sun near solar maximum lead to emissions of charged particles (mainly protons and electrons), some of which enter the Earth's magnetosphere and rain down on the polar regions. "Solar proton events" have been used to describe these phenomena since the protons associated with these solar events sometimes create a significant atmospheric disturbance. We have used the National Center for Atmospheric Research (NCAR) Whole Atmosphere Community Climate Model (WACCM) to study the long-term (> few months) influences of solar proton events from 1963 through 2004 on stratospheric ozone and temperature. There were extremely large solar proton events in 1972, 1989,2000,2001, and 2003. These events caused very distinctive polar changes in layers of the Earth's atmosphere known as the stratosphere (12-50 km; -7-30 miles) and mesosphere (50-90 km; 30-55 miles). The solar protons connected with these events created hydrogen- and nitrogen-containing compounds, which led to the polar ozone destruction. The nitrogen-containing compounds, called odd nitrogen, lasted much longer than the hydrogen-containing compounds and led to long-lived stratospheric impacts. An extremely active period for these events occurred in the five-year period, 2000- 2004, and caused increases in odd nitrogen which lasted for several months after individual events. Associated stratospheric ozone decreases of >lo% were calculated to last for up to five months past the largest events. However, the computed total column ozone and stratospheric temperature changes connected with the solar events were not found to be statistically significant. Thus, solar proton events do not likely contribute significantly to measured total column ozone fluctuations and stratospheric temperature changes.

Jackman, Charles H.↗
NASA NTRS2024

Launch Complex 34, SWMU CC054 2023 DNAPL Source Zone Operations, Maintenance, and Monitoring, Site-Wide Long-Term Monitoring, and Hot Spot 6 Air Sparge System Annual Performance Monitoring and Phase Two Expansion Construction Completion Report Cape Canaveral Space Force Station, Florida

This Annual Performance Monitoring Report (PMR) for the Dense Non-Aqueous Phase Liquid (DNAPL) Source Zone (DSZ), Site-Wide Long-Term Monitoring (LTM), and Hot Spot 6 (HS 6) Air Sparge (AS) System presents the results of Year 14 operations and performance monitoring of the hydraulic containment (HC) Interim Measure (IM), details associated with construction and implementation of the HS 6 AS system expansion (Phase Two), and the results of operations and performance sampling of the HS 6 AS IM at Launch Complex 34 (LC34), located at Cape Canaveral Space Force Station (CCSFS), Florida. The timeframe for activities documented in this PMR extends from April 1, 2023 to March 31, 2024. LC34 has been designated Solid Waste Management Unit CC054 under the Kennedy Space Center (KSC) Resource Conservation and Recovery Act Corrective Action Program. The objective of the HC IM at LC34 is to contain the shallow and deep DSZ and surrounding dissolved-phase trichloroethene (TCE) high concentration plume via operation of a hydraulic containment system (HCS). The pre-IM design 300 micrograms per liter (μg/L) TCE groundwater contour was used to establish the deep zone capture area for deep recovery wells, and the shallow zone capture area was defined by the DSZ. The system began operating in 2010, and in 2015, the system was expanded to provide HC for areas within the 300 μg/L TCE groundwater isocontours of HS 3 and 4. In 2018 and 2019, an investigation was conducted to recharacterize the DSZ, which included investigating TCE mass in Layer 7. This data was subsequently used to optimize the pumping rates of the HCS and install additional recovery wells in Layer 7 to more adequately capture residual contaminant mass. The operational period for Year 14 of the HCS was from April 1, 2023 to March 31, 2024. Operational runtime for the system was 94 percent during Year 14, with downtime events attributed to planned maintenance, system repairs, and power outages. As of March 31, 2024, a total of 344,849,634 cumulative gallons of groundwater containing 94,656 pounds of chlorinated volatile organic compounds (CVOCs) have been removed by the HCS. During the reporting period covered under this report, the HCS recovered 31,176,393 gallons and approximately 6,319 pounds of CVOC mass. Total combined influent concentrations of TCE have decreased since startup from approximately 280,000 µg/L (January 2010) to 25,000 µg/L (March 2024). During the reporting period, all effluent concentrations from the HCS (aqueous and vapor) were below regulatory reporting limits, indicating the system continues to operate as intended. Performance monitoring was conducted in January 2024 within the DSZ to evaluate TCE contamination. Groundwater samples were collected via DPT at nine locations, consistent with previous events between 2017 and 2022. Full vertical profile sampling was completed at each DPT from 8 to 98 feet below land surface (bls), at 5-foot intervals. The DPT performance monitoring results are summarized in this PMR. The results revealed TCE remains at concentrations greater than 11,000 µg/L in the DSZ (1-percent solubility, indicative of DNAPL) at eight of the nine DPT locations and at depths ranging from 28 to 98 feet bls. An overall decreasing trend of TCE concentrations was observed in DPT samples during this reporting period, which is a reduction from the previous event (December 2022) and the peak event in December 2021, where TCE percentages appeared to increase in all depth zones because several recovery wells were turned off during the AS pilot study in the DSZ. The maximum TCE concentration in January 2024 was 1,600,000 µg/L in the 53 feet bls depth interval at DPT594 (previous maximum result in 2022 was 1,800,000 µg/L in the 48 feet bls depth interval at DPT599). This maximum concentration in the 53 feet bls depth interval is in the deep capture zone. During the January 2024 DPT event, the largest portion of TCE mass was observed in the 48 feet bls interval above/within Layer 4. This trend remains consistent with previous years and appears to indicate continued mass discharge from Layer 4 (fine-grained unit). In addition to DPT sampling, annual groundwater samples were collected from 11 deep monitoring wells in the DSZ area (Layers 7 and 8) in December 2023 to verify vertical and horizontal delineation. Three of the wells were also sampled biweekly to evaluate operations of recovery well RW21D (screened 86 to 106 feet bls), which was installed in January 2023. Of the Layer 7/8 monitoring sampled only annually, results were non-detect or less than groundwater cleanup target levels GCTLs in December 2023, with the exception of one well, IW45D2, which had a cis-1,2-dichloroethene (cDCE), detection greater than the GCTL. Of the three wells sampled biweekly during the operational period, the well located closest to Layer 7 recovery well RW21D (IW44D2, screened 105 to 115 feet bls) had concentrations of TCE, cDCE and vinyl chloride (VC) greater than GCTLs throughout the operational period, but displayed a decreasing trend since the peak concentrations in September 2023. The maximum TCE concentration during this operational period was 190,000 µg/L at IW44D2 in September 2023, but reduced to 700 µg/L in March 2024, indicating the HCS is still effectively removing mass from the source area. Expansion of the HCS and addition of new recovery wells is ongoing and will continue to be evaluated as the groundwater recovery scheme is optimized. Details of the expansion and optimization will be provided in a future PMR. The HS 6 AS IM was initiated in 2018 with 160 AS wells and expanded in 2019 with another 140 AS wells. An additional expansion of the HS 6 AS IM was completed during the reporting period covered under this report and details of the construction implementation and startup of the expansion are detailed in Section III of this report. The new expansion, referred to as Phase Two, was implemented between August 17, 2022 and August 28, 2023, and included the installation of 190 air sparge wells to treat an additional 11.2 acres. The original configuration (referred to as Phase One) operated until Phase Two came online, then all but 52 AS wells were turned off so the components could be moved and utilized in the Phase Two area. The 52 AS wells that remain on are in a barrier configuration preventing contaminated groundwater from impacting the treated area. The HS 6 AS system (both Phase One and Two) operated normally during the reporting period covered under this report. Semi-annual performance monitoring of the Phase One configuration was conducted in April and November 2023, consistent with previous years. For the Phase Two configuration, 21 new monitoring wells were installed and sampled quarterly, with a baseline event in July 2023, and quarterly events in November 2023 and February 2024 summarized in this report. Semi-annual monitoring results collected in April and October 2023 show concentrations of contaminants of concern (cDCE, trans-1,2-dichloroethene, and VC) have decreased to less than GCTLs in nearly all wells and not impacting the surface water drainage canal, indicating the HS 6 IM continues to meet objectives. The baseline and quarterly sampling for the Phase Two configuration indicate generally decreasing concentrations in wells within and around the perimeter of the treatment area. At least two more quarters of monitoring will be conducted and once those results are evaluated a reduced the sampling frequency may be considered. Overall, the tasks associated with Year 14 operation of the HC IM and operation of the HS 6 AS IM were performed in accordance with recommendations included in the previous 2022 LC34 (Year 13) PMR. Evaluation of results from the HC IM and HS 6 IM show that these systems are operating as designed and meeting performance objectives.

groundwater remediation↗
NASA NTRS2001

Potential Evaporite Biomarkers from the Dead Sea

The Dead Sea is located on the northern branch of the African-Levant Rift systems. The rift system, according to one model, was formed by a series of strike slip faults, initially forming approximately two million years ago. The Dead Sea is an evaporite basin that receives freshwater from springs and from the Jordan River. The Dead Sea is different from other evaporite basins, such as the Great Salt Lake, in that it possesses high concentrations of magnesium and has an average pH of 6.1. The dominant cation in the Great Salt Lake is sodium, and the pH is 7.7. Calcium concentrations are also higher in the Dead Sea than in the Great Salt Lake. Both basins are similar in that the dominant anion is chlorine and the salinity levels are approximately 20 %. Other common cations that have been identified from the waters of the Dead Sea and the Great Salt Lake include sodium and potassium. A variety of Archea, Bacteria, and a single genus of a green algal, Dunaliella, has been described from the Dead Sea. Earlier studies concentrated on microbial identification and analysis of their unique physiology that allows them to survive in this type of extreme environment. Potential microbial fossilization processes, microbial fossils, and the metallic ions associated with fossilization have not been studied thoroughly. The present study is restricted to identifying probable microbial morphologies and associated metallic ions. XRD (X Ray Diffraction) analysis indicates the presence of halite, quartz, and orthoclase feldspar. In addition to these minerals, other workers have reported potassium chloride, magnesium bromide, magnesium chloride, calcium chloride, and calcium sulfate. Halite, calcium sulfate, and orthoclase were examined in this report for the presence of microbes, microbially induced deposits or microbial alteration. Neither the gypsum nor the orthoclase surfaces possesses any obvious indications of microbial life or fossilization. The sand-sized orthoclase particles are weathered with 122 extensive fan-shaped mineral deposits. The gypsum deposits are associated with halite minerals and also exhibit extensive weathering. Halite minerals represent the only substrates that have probable rod-shaped microbial structures with long, filamentous, apical extensions. EDS (energy dispersive x-ray) analysis of the putative microbes indicates elevated calcium levels that are enriched with magnesium. The rod-shaped structures exhibit possible fossilization stages. Rhombohedralshaped minerals of magnesium-enriched calcium carbonate are deposited on the microbial surfaces, and eventually coat the entire microbial surface. The sodium chloride continues to crystallize on nearby halite surface and even crystallizes on the fossilized microbial remains. The putative fossils are found exclusively on halite surfaces, and all contained elevated levels of calcium magnesium cations. Both of these metallic cations are associated with microbial activity and fossilization. Their morphological diversity is low in comparison with the reported living Dead Sea microbial population. If we examine the fossil record for multicellular organisms, fossilization rates are lower for soft-bodied organisms than for those possessing hard parts, i.e. shells, bones. For example, smaller, single celled organisms would have a smaller chance of fossilization; their fossilized shapes could be mistaken for abiotic products. Another consideration is that dead organisms in the water column are probably utilized as a food source by other microbes before fossilization processes are completed. This may be an important consideration as we attempt to model and interpret ancient microbial environments either on Earth or on Mars.

Morris, Penny A.↗