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At least 307 records · Page 17
All sourcesNASA NTRSDOE OSTI
NASA NTRS2016

The Investigation of Chlorate and Perchlorate/Saponite Mixtures as a Possible Source of Oxygen and Chlorine Detected by the Sample Analysis at Mars (SAM) Instrument in Gale Crater

The Sample Analysis at Mars (SAM) instrument on board the Curiosity Rover has detected O2 and HCl gas releases from all analyzed Gale Crater sediments, which are attributed to the presence of perchlorates and/or chlorates in martian sediment. Previous SAM analog laboratory analyses found that most pure perchlorates and chlorates release O2 and HCl at different temperatures than those observed in the SAM data. Subsequent studies examined the effects of perchlorate and chlorate mixtures with Gale Crater analog iron phases, which are known to catalyze oxychlorine decomposition. Several mixtures produced O2 releases at similar temperatures as Gale Crater materials, but most of these mixtures did not produce significant HCl releases comparable to those detected by the SAM instrument. In order to better explain the Gale Crater HCl releases, perchlorates and chlorates were mixed with Gale Crater analog saponite, which is found at abundances from 8 to 20 wt % in the John Klein and Cumberland drill samples. Mixtures of chlorates or perchlorates with calcium-saponite or ferrian-saponite were heated to 1000 deg C in a Labsys EVO differential scanning calorimeter/mass spectrometer configured to operate similarly to the SAM oven/quadrupole mass spectrometer system. Our results demonstrate that all chlorate and perchlorate mixtures produce significant HCl releases below 1000 deg C as well as depressed oxygen peak release temperatures when mixed with saponite. The type of saponite (calcium or ferrian saponite) did not affect the evolved gas results significantly. Saponite/Mg-perchlorate mixtures produced two HCl releases similar to the Cumberland drilled sample. Mg-chlorate mixed with saponite produced HCl releases similar to the Big Sky drilled sample in an eolian sandstone. A mixture of Ca-perchlorate and saponite produced HCl and oxygen releases similar to the Buckskin mudstone drilled sample and the Gobabeb 2 eolian dune material. Ca-chlorate mixed with saponite produced both HCl and oxygen releases within the same range as the Rock-nest windblown deposit, the Greenhorn eolian sandstone, and the John Klein drilled mudstone. Overall, mixtures of perchlorates or chlorates with saponite provide the first explanation for the high temperature HCl releases in addition to the oxygen releases observed in Gale Crater materials.

Clark, J.↗
NASA NTRS2017

Experimental Study into the Partitioning Behavior of Fluorine, Chlorine, Hydroxyl, and Sulfur (S2-) Between Apatite and a Synthetic Kreep Basalt Melt

The mineral apatite (Ca5 (PO4)3(F, Cl, OH)) is known for its ability to constrain the petrogenesis of the rock in which it is hosted and for its ubiquity throughout the Solar System, as it is found in lunar, martian, and terrestrial rocks alike (McCubbin et. al, 2015). The abundance of volatile elements, and for this particular study, the elevated abundance of sulfur (S2-) in high-Al basalt samples bearing apatite, could provide more insight for inquiries posed about the behavior of volatiles in lunar and martian magmatic systems (Boyce et. al, 2010). Oxygen fugacity will be an important parameter for these experiments, as the Moon, Mars, and Earth have different redox states (Herd, 2008). The objective of this experimental endeavor is to determine apatite-melt partition coefficients for the volatile elements (F-, Cl-, OH-, S2-) that make up the X-site (i.e., the typically monovalent anion site) in the mineral apatite in a lunar melt composition under lunar oxygen fugacity conditions approx.1-2 log units below the iron-wüstite buffer). All experiments will be conducted at NASA, Johnson Space Center in the High Pressure Experimental Petrology Laboratory. In order to conduct apatite-melt partition experiments with oxygen fugacity as an additional parameter, we will create a synthetic mix of the lunar KREEP basalt 15386, a sample retrieved during Apollo 15 that is believed to represent an indigenous volcanic melt derived from the lunar interior (Rhodes, J.M et. al, 2006). Other geochemically significant elements including C, Co, Ni, Mo, and rare earth elements will be included in the mix at trace abundances in order to assess their partitioning behavior without effecting the overall behavior of the system. The synthetic mix will then be loaded into a piston cylinder, an apparatus used to simulate high-pressure/high-temperature conditions of planetary interiors, and exposed to 0.5 GPa of pressure, the pressure observed in the upper mantle of the Moon, and heated to the melting temperature of the materials. To make sure crystals grow large enough for the necessary analyses, the sample will be kept at the crystallization temperature for 8 hours. This extended run time should also allow the sample to achieve a steady state which is necessary to accurately assess the partitioning of these elements between apatite and melt. The results from this experimental study will allow us to determine the fate of F-, Cl-, OH-, and S2- during the magmatic evolution of the Moon.

Turner, Amber↗
NASA NTRS2020

High-temperature Hydrogen Chloride Releases from Mixtures of Sodium Chloride with Sulfates: Implications for the Chlorine-Mineralogy as Determined by the Sample Analysis at Mars Instrument on the Curiosity Rover in Gale Crater, Mars

Hydrogen chloride releases above 500 °C occurred in several samples analyzed by the Sample Analysis at Mars (SAM) evolved gas analyzer on the Curiosity rover in Gale crater. These have been attributed to reactions between chlorides (original or from oxychlorine decomposition) and water. Some of these HCl releases that peaked below the melting temperature of common chlorides did not co-evolve with oxygen or water, and were not explained by laboratory analog work (Figure 1). Therefore, these HCl releases were not caused by MgCl2 or soley due to reactions between water and melting chlorides. The goal of this work was to explain the HCl releases that did not co-evolve with oxygen or water and occurred below the melting point of common chlorides, which have not been explained by previous laboratory analog work. This work specifically evaluates the role of evolved SO2 in the production of HCl.

Clark, J.V.↗
NASA NTRS2020

The Chlorine-Isotopic Composition of Lunar KREEP From Magnesian-Suite Troctolite 76535

We conducted in-situ Cl isotopic measurements of apatite within intercumulus regions and within a holocrystalline olivine-hosted melt inclusion in magnesian-suite troctolite 76535 from Apollo 17. These data were collected to place constraints on the Cl-isotopic composition of the last liquid to crystallize from the lunar magma ocean (i.e., urKREEP, named after its enrichments in incompatible lithophile trace elements like potassium, rare earth elements, and phosphorus). The apatite in the olivine-hosted melt inclusion and within the intercumulus regions of the sample yielded Cl-isotopic compositions of 28.3 ± 0.9 ‰ (2σ) and 30.3 ± 1.1 ‰ (2σ), respectively. The concordance of these values from both textural regimes we analyzed indicates that the Cl-isotopic composition of apatites in 76535 likely represents the Cl-isotopic composition of the KREEP-rich magnesian-suite magmas. Based on the age of 76535, these results imply that the KREEP reservoir attained a Cl-isotopic composition of 28–30 ‰ by at least 4.31 Ga, consistent with the onset of Cl-isotopic fractionation at the time of lunar magma ocean crystallization or shortly thereafter. Moreover, lunar samples that yield Cl-isotopic compositions higher than the value for KREEP are likely affected by secondary processes such as impacts and/or magmatic degassing. The presence of KREEP-rich olivine-hosted melt inclusions within one of the most pristine and ancient KREEP-rich rocks from the Moon provides a new opportunity to characterize the geochemistry of KREEP. In particular, a broader analysis of stable isotopic compositions of highly and moderately volatile elements could provide an unprecedented advancement in our characterization of the geochemical composition of the KREEP reservoir and of volatile-depletion processes during magma ocean crystallization, more broadly.

Francis M. McCubbin↗
NASA NTRS2020

Strong Sensitivity of the Isotopic Composition of Methane to the Plausible Range of Tropospheric Chlorine

The C-13 isotopic ratio of methane, δC-13 of CH4, provides additional constraints on the CH4 budget to complement the constraints from CH4 observations. The interpretation of δC-13 observations is complicated, however, by uncertainties in the methane sink. The reaction of CH4 with Cl is highly fractionating, increasing the relative abundance of 13CH4, but there is currently no consensus on the strength of the tropospheric Cl sink. Global model simulations of halogen chemistry differ strongly from one another in terms of both the magnitude of tropospheric Cl and its geographic distribution. This study explores the impact of the inter-model diversity in Cl fields on the simulated δC-13 of CH4. We use a set of GEOS global model simulations with different predicted Cl fields to test the sensitivity of the δC-13 of CH4 to the diversity of Cl output from chemical transport models. We find that δC-13 is highly sensitive to both the amount and geographic distribution of Cl. Simulations with Cl providing 0.28% or 0.66% of the total CH4 loss bracket the δC-13 observations for a fixed set of emissions. Thus, even when Cl provides only a small fraction of the total CH4 loss and has a small impact on total CH4, it provides a strong lever on δC-13. Consequently, it is possible to achieve a good representation of total CH4 using widely different Cl concentrations, but the partitioning of CH4 loss between the OH and Cl reactions leads to strong differences in isotopic composition depending on which model’s Cl field is used. Comparing multiple simulations, we find that altering the tropospheric Cl field leads to approximately a 0.5‰ increase in δ(13)CH4for each percent increase in how much CH4 is oxidized by Cl. The geographic distribution and seasonal cycle of Cl also impacts the hemispheric gradient and seasonal cycle of δC-13. The large effect of Cl on δC-13 compared to total CH4 broadens the range of CH4 source mixtures that can be reconciled with δC-13 observations. Stronger constraints on tropospheric Cl are necessary to improve estimates of CH4 sources from δC-13 observations.

Global model simulations of halogen chemistry↗
NASA NTRS2016

Potential Precursor Compounds for Chlorohydrocarbons Detected in Gale Crater, Mars, by the SAM Instrument Suite on the Curiosity Rover

The detection of chlorinated organic compounds in near-surface sedimentary rocks by the Sample Analysis at Mars (SAM) instrument suite aboard the Mars Science Laboratory Curiosity rover represents an important step toward characterizing habitable environments on Mars. However, this discovery also raises questions about the identity and source of their precursor compounds and the processes by which they become chlorinated. Here we present the results of analog experiments, conducted under conditions similar to SAM gas chromatography-mass spectrometry analyses, in which we pyrolyzed potential precursor compounds in the presence of various Cl salts and Fe oxides that have been identified in Martian sediments. While chloromethanes could not be unambiguously identified, 1,2-dichloropropane (1,2-DCP), which is one of the chlorinated compounds identified in SAM data, is formed from the chlorination of aliphatic precursors. Additionally, propanol produced more 1,2-DCP than nonfunctionalized aliphatics such as propane or hexanes. Chlorinated benzenes ranging from chlorobenzene to hexachlorobenzene were identified in experiments with benzene carboxylic acids but not with benzene or toluene. Lastly, the distribution of chlorinated benzenes depended on both the substrate species and the nature and concentration of the Cl salt. Ca and Mg perchlorate, both of which release O2 in addition to Cl2 and HCl upon pyrolysis, formed less chlorobenzene relative to the sum of all chlorinated benzenes than in experiments with ferric chloride. FeCl3, a Lewis acid, catalyzes chlorination but does not aid combustion. Accordingly, both the precursor chemistry and sample mineralogy exert important controls on the distribution of chlorinated organics.

Miller, Kristen E.↗
NASA NTRS2014

Understanding Differences in Chemistry Climate Model Projections of Stratospheric Ozone

Chemistry climate models (CCMs) are used to project future evolution of stratospheric ozone as concentrations of ozone-depleting substances (ODSs) decrease and greenhouse gases increase, cooling the stratosphere. CCM projections exhibit not only many common features but also a broad range of values for quantities such as year of ozone return to 1980 and global ozone level at the end of the 21st century. Multiple linear regression is applied to each of 14 CCMs to separate ozone response to ODS concentration change from that due to climate change. We show that the sensitivity of lower stratospheric ozone to chlorine change Delta Ozone/Delta inorganic chlorine is a near-linear function of partitioning of total inorganic chlorine into its reservoirs; both inorganic chlorine and its partitioning are largely controlled by lower stratospheric transport. CCMs with best performance on transport diagnostics agree with observations for chlorine reservoirs and produce similar ozone responses to chlorine change. After 2035, differences in Delta Ozone/Delta inorganic chlorine contribute little to the spread in CCM projections as the anthropogenic contribution to inorganic chlorine becomes unimportant. Differences among upper stratospheric ozone increases due to temperature decreases are explained by differences in ozone sensitivity to temperature change Delta Ozone/Delta T due to different contributions from various ozone loss processes, each with its own temperature dependence. Ozone decrease in the tropical lower stratosphere caused by a projected speedup in the Brewer-Dobson circulation may or may not be balanced by ozone increases in the middle- and high-latitude lower stratosphere and upper troposphere. This balance, or lack thereof, contributes most to the spread in late 21st century projections.

Stratospheric Transport↗
NASA NTRS1988

Heterogeneous chemistry related to Antarctic ozone depletion: Reaction of ClONO2 and N2O5 on ice surfaces

Laboratory studies of heterogeneous reactions of possible importance for Antarctic ozone depletion were performed. In particular, the reactions of chlorine nitrate (ClONO2) and dinitrogen pentoxide (N2O5) were investigated on ice and HCl/ice surfaces. These reactions occur on the surfaces of polar stratospheric clouds (PSCs) over Antarctica. One reaction transforms the stable chlorine reservoir species (ClONO2 and HCl) into photochemically active chlorine in the form of HOCl and Cl2. Condensation of HNO3 in the reactions removes odd nitrogen from the stratosphere, a requirement in nearly all models of Antarctic ozone depletion. Other reactions may also be important for Antarctic ozone depletion. Like the reactions of chlorine nitrate, these reactions deplete odd nitrogen through HNO3 condensation. In addition, one reaction converts a stable chlorine reservior species (HCl) into photochemically active chlorine (ClNO2). These reactions were studied with a modified version of a Knudsen cell flow reactor.

Tolbert, Margaret A.↗
NASA NTRS1991

NASA Li/CF(x) cell problem analysis: Scanning electron microscopy with energy dispersive x ray spectrometry

An analysis was made of Lithium/carbon fluoride cell parts for possible chloride contamination induced by exposure to thionyl chloride (SOCl2); various samples were submitted for analysis. Only a portion of the analysis which has been conducted is covered, herein, namely analysis by scanning electron microscopy with energy dispersive x ray spectrometry (SEM/EDS). A strip of nickel was exposed to SOCl2 vapors to observe variations in surface concentrations of sulfur and chlorine with time. By detecting chlorine one can not infer contamination by SOCl2 only that contamination is present. Six samples of stainless steel foil were analyzed for chlorine using EDS. Chlorine was not detected on background samples but was detected on the samples which had been handled including those which had been cleaned. Cell covers suspected of being contaminated while in storage and covers which were not exposed to the same storage conditions were analyzed for chlorine. Although no chlorine was found on the covers from cells, it was found on all stored covers. Results are presented with techniques shown for analysis and identification. Relevant photomicrographs are presented.

Baker, John↗
NASA NTRS1994

Aqueous alternatives for metal and composite cleaning

For many years the metalworking industry has cleaned metal and composite substrates with chlorinated solvents. Recently, however, health and disposal related environmental concerns have increased regarding chlorinated solvents, including 1,1,1-trichloroethane, trichloroethylene, methylene chloride, or Freon'. World leaders have instituted a production ban of certain ozone depleting chlorofluorocarbons (CFC's) by 1996. The Occupational Safety and Health Administration (OSHA) has instituted worker vapor exposure limitations for virtually all of the solvents used in solvent-based cleaners. In addition, the United States Environmental Protection Agency (EPA) has defined nearly all solvent-based cleaners as 'hazardous'. Cradle to grave waste responsibility is another reason manufacturers are trying to replace chlorinated solvents in their cleaning processes. Because of these factors, there now is a world wide effort to reduce and/or eliminate the use of chlorinated solvents for industrial cleaning. Waterbased cleaners are among the alternatives being offered to the industry. New technology alkaline cleaners are now available that can be used instead of chlorinated solvents in many cleaning processes. These waterbased cleaners reduce the release of volatile organic compounds (VOC's) by as much as 99 percent. (The definition and method of calculation of VOC's now varies from region to region.) Hazardous waste generation can also be significantly reduced or eliminated with new aqueous technology. This in turn can ease worker exposure restrictions and positively impact the environment. This paper compares the chemical and physical properties of this aqueous cleaners versus chlorinated solvents.

Quitmeyer, Joann↗
NASA NTRS2014

Reducing Uncertainty in Chemistry Climate Model Predictions of Stratospheric Ozone

Chemistry climate models (CCMs) are used to predict the future evolution of stratospheric ozone as ozone-depleting substances decrease and greenhouse gases increase, cooling the stratosphere. CCM predictions exhibit many common features, but also a broad range of values for quantities such as year of ozone-return-to-1980 and global ozone level at the end of the 21st century. Multiple linear regression is applied to each of 14 CCMs to separate ozone response to chlorine change from that due to climate change. We show that the sensitivity of lower atmosphere ozone to chlorine change deltaO3/deltaCly is a near linear function of partitioning of total inorganic chlorine (Cly) into its reservoirs; both Cly and its partitioning are controlled by lower atmospheric transport. CCMs with realistic transport agree with observations for chlorine reservoirs and produce similar ozone responses to chlorine change. After 2035 differences in response to chlorine contribute little to the spread in CCM results as the anthropogenic contribution to Cly becomes unimportant. Differences among upper stratospheric ozone increases due to temperature decreases are explained by differences in ozone sensitivity to temperature change deltaO3/deltaT due to different contributions from various ozone loss processes, each with their own temperature dependence. In the lower atmosphere, tropical ozone decreases caused by a predicted speed-up in the Brewer-Dobson circulation may or may not be balanced by middle and high latitude increases, contributing most to the spread in late 21st century predictions.

chemistry climate models↗
NASA NTRS2022

Contractors Road Heavy Equipment Area (SWMU 055) 2021 Annual Groundwater Monitoring Report

This document presents a summary of activities completed at the Contractors Road Heavy Equipment (CRHE) Area, located at Kennedy Space Center (KSC), Florida, from January through December 2021. The activities conducted at the CRHE Area include: - Annual groundwater sampling activities associated with site-wide plume monitoring and Underground Injection Control (UIC) monitoring in the former bioremediation Interim Measures (IM) Hot Spot 1 (HS1) area; - Direct push technology (DPT) groundwater investigation; and - Semi-annual vapor intrusion (VI) evaluation activities. This facility is designated Solid Waste Management Unit (SWMU) Number 055 (SWMU 055) under KSC’s Resource Conservation and Recovery Act Corrective Action program. This report was prepared by HydroGeoLogic, Inc. (HGL) for the National Aeronautics and Space Administration (NASA) under contract number 80KSC019F0096. The annual groundwater sampling results demonstrated that the footprint where chlorinated volatile organic compounds (VOC) are present above their State of Florida groundwater cleanup target levels (GCTLs) is not expanding overall. One non-chlorinated VOC (1,4-dioxane) is found above its GCTL at isolated points within the chlorinated VOC plume. The DPT groundwater investigation is being used to delineate the horizontal and vertical boundaries where chlorinated VOCs are present at levels above natural attenuation default concentrations. That data supports an evaluation of potential additional remedial actions. The potential for VI into the CRHE Area Office (K6-1996H) is evaluated by collected sub-slab vapor samples from four locations twice a year (once in the wet season and once in the dry season). The results for 2021 were all below the Environmental Protection Agency's vapor intrusion screening levels (VISLs) for both commercial and residential settings. The path forward for the site is to continue annual monitoring for chlorinated VOCs and 1,4-dioxane until additional remedies are implemented or the site is transitioned to long-term monitoring.

Contractors Road Heavy Equipment↗
NASA NTRS1973

Batteries for storage of wind-generated energy

Cost effectiveness characteristics of conventional-, metal gas-, and high energy alkali metal-batteries for wind generated energy storage are considered. A lead-acid battery with a power density of 20 to 30 watt/hours per pound is good for about 1500 charge-discharge cycles at a cost of about $80 per kilowatt hour. A zinc-chlorine battery that stores chlorine as solid chlorine hydrate at temperatures below 10 C eliminates the need to handle gaseous chlorine; its raw material cost are low and inexpensive carbon can be used for the chlorine electrode. This system has the best chance to replace lead-acid. Exotic alkali metal batteries are deemed too costly at the present stage of development.

Schwartz, H. J.↗
NASA NTRS1990

Photodissociation of Cl2O2 in the spring Antarctic lower stratosphere

The likely photodissociation pathways of chlorine peroxide are examined. Reasoning by analogy between hydrogen peroxide and chlorine peroxide, it is shown that photodissociation of chlorine peroxide at wavelengths longer than 250 nm is not likely to give chlorine atoms as a primary product. Reasoning by analogy with molecules whose visible spectra are known, it is concluded that chlorine peroxide is also likely to photodissociate in the visible to give ClO radicals as primary products.

Eberstein, Igor J.↗