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All sources NASA NTRS DOE OSTI

NASA NTRS1988

Heterogeneous physicochemistry of the winter polar stratosphere

Present chemical theories of the Antarctic ozone hole assume that heterogeneous reactions involving polar stratospheric clouds (PSCs) are the precursor of springtime ozone depletions. However, none of the theories quantify the rates of proposed heterogeneous processed, and none utilize the extensive data base on PSC's. Thus, all of the theories must be considered incomplete until the heterogeneous mechanisms are properly defined. A unified treatment developed of the cloud related processes, both physical and chemical, and the importance of these processes using observation data is calibrated. The rates are compared competitive heterogeneous processes to place reasonable limits on critical mechanisms such as the denitrification and dechlorination of the polar winter stratosphere. Among the subjects addressed here are the physical/chemical properties of PSC's including their relevant microphysical, optical and compositional characteristics, mass transfer rates of gaseous constituents to cloud particles, adsorption, accommodation and sticking coefficients on cloud particles, time constants for condensation, absorption and other microphysical processes, effects of solubility and vapor pressure on cloud composition, the statistics of cloud processing of chemically active condensible species, rate limiting steps in heterogeneous chemical reactions, and the nonlinear dependence of ozone loss on physical and chemical parameters.

Turco, R. P.↗

NASA NTRS1992

Measurements and model calculations of HCl column amounts and related parameters over McMurdo during the austral spring in 1989

Solar spectra obtained from a ground-based Fourier transform infrared instrument at McMurdo (Antarctica) in the spring of 1989 have been analyzed to determine total HCl column amounts. A one-dimensional photochemical model was used to simulate the rate of recovery of HCl in the springtime. Low column amounts (about 1 x 10 exp 15 molecules/sq cm) were observed in early September and may be attributed to the heterogeneous conversion of HCl to active chlorine species during the polar night. The rate of recovery of HCl is consistent with its production by chlorine atoms reacting with methane and is dependent on concentrations of active chlorine species and NO molecules in the altitude region from 12 to 22 km. High HCl column amounts (about 7 x 10 exp 15 molecules/sq cm) were observed following recovery in late October, suggesting that the lower stratosphere in the polar region had descended relative to mid-latitudes and that the degree of dechlorination of the transported air was very small.

Liu, X.↗

NASA NTRS2005

Valiant 'Zero-Valent' Effort Restores Contaminated Grounds

Dense non-aqueous phase liquids (DNAPLs) are chemical compounds that can contaminate soil and groundwater to the point of irreparability. These substances are only slightly soluble in water, and are much denser than water. Because of their solubility, DNAPLs form separate liquid phases in groundwater, and because of their density, DNAPLs sink in aquifers instead of floating at the water table, making it extremely difficult to detect their presence. If left untreated in the ground, they can taint fresh water sources. Common DNAPLs include chlorinated hydrocarbon compounds such as carbon tetrachloride, chloroform, tetrachloroethylene, and trichloroethylene. Trichloroethylene was used during the early days of the Space Program, as a solvent for flushing rocket engines, and for metal cleaning and degreasing of equipment, electronics, and heavy machinery. As a result, areas of Cape Canaveral s Launch Complex 34, the site of several historic Saturn rocket launches occurring from 1959 to 1968, were polluted with chlorinated DNAPLs. Through the direction and guidance of Dr. Jacqueline Quinn, an environmental engineer in the Spaceport Engineering and Technology Directorate at NASA s Kennedy Space Center, a biodegradable environmental cleanup technology was developed to reductively dechlorinate DNAPL sources in polluted water at Launch Complex 34. It was important for Kennedy to nip this problem in the bud, in light of the fact that the Space Center is also a National Wildlife Refuge, home to thousands of shorebirds, endangered sea turtles and eagles, manatees, alligators, and diverse habitats that include brackish marshes and salt water estuaries. The success in remediating this historic launch site has led to numerous commercial applications that are restoring the health of our environmental surroundings.

Source record↗

NASA NTRS2023

In Situ Chemical Reduction Interim Measures Work Plan Hot Spot 3 Mobile Launcher Platform Rehabilitation Sites / Vehicle Assembly Building Area (SWMU 056) Kennedy Space Center, Florida

This document presents the design details of an In Situ Chemical Reduction (ISCR) Interim Measures Work Plan for Hot Spot 3 within Mobile Launcher Platform Rehabilitation Sites/Vehicle Assembly Building Area, Solid Waste Management Unit (SWMU) 056 (SWMU 056), located at the John F. Kennedy Space Center, Florida. The interim measures (IM) treatment zone encompasses an area identified as the High Concentration Plume (HCP), which is defined as the area with chlorinated volatile organic compound (CVOC) groundwater concentrations greater than their respective Natural Attenuation Default Concentration (NADC). The objective of the IM is to remove CVOC mass within the treatment area to levels that facilitate a transition to natural attenuation monitoring. The IM design consists of the selected ISCR amendment, Provect-IR, which is a mixture of solid reagents in a single product that promotes enhanced reductive dechlorination and ISCR. ProvectIR includes natural antimethanogenic compounds; multiple hydrophilic, nutrient-rich organic carbon sources; zero valent iron; chemical oxygen scavengers; and vitamin and mineral sources. The proposed treatment area for this IM encompasses less than 1 acre and includes three vertical treatment intervals to reach the NADC plumes that vary per CVOC and depth: 4 to 10 feet below land surface (bls), 10 to 18 feet bls, and 42 to 52 feet bls. The amendment will be distributed through 16 injection points (IP01 through IP16) using dosing rates ranging from 0.4% to 0.6% of soil mass within the treatment interval and a 15% or 20% slurry strength. Dosage rates and slurry strength are based on groundwater geochemistry, soil characteristics, and contaminant concentrations. To aid in the evaluation of the ISCR IM performance, six performance monitoring wells will be installed following injections and sampled semiannually. CVOC parameters will be sampled until concentrations reduce to below their NADC. Underground Injection Control parameters will be sampled until concentrations decrease to background levels or to levels that meet respective groundwater standards. Sampling frequency will be evaluated annually and modified as needed. The path forward for the ISCR IM implementation includes preparing the IM Implementation Work Plan, ISCR injections, monitoring well installation, performance monitoring, and reporting.

Randall K. Sillan↗

DOE OSTI2021

Elucidating the Role of Single-Atom Pd for Electrocatalytic Hydrodechlorination

In this study, we loaded Pd catalysts onto a reduced graphene oxide (rGO) support in an atomically dispersed fashion [i.e., Pd single-atom catalysts (SACs) on rGO or Pd 1 /rGO] via a facile and scalable synthesis based on anchor-site and photoreduction techniques. The as-synthesized Pd 1 /rGO significantly outperformed the Pd nanoparticle (Pdnano) counterparts in the electrocatalytic hydrodechlorination of chlorinated phenols. Downsizing Pd nano to Pd 1 leads to a substantially higher Pd atomic efficiency (14 times that of Pdnano), remarkably reducing the cost for practical applications. The unique single-atom architecture of Pd 1 additionally affects the desorption energy of the intermediate, suppressing the catalyst poisoning by Cl – , which is a prevalent challenge with Pdnano. Characterization and experimental results demonstrate that the superior performance of Pd 1 /rGO originates from (1) enhanced interfacial electron transfer through Pd–O bonds due to the electronic metal–support interaction and (2) increased atomic H (H*) utilization efficiency by inhibiting H 2 evolution on Pd 1 . Furthermore, this work presents an important example of how the unique geometric and electronic structure of SACs can tune their catalytic performance toward beneficial use in environmental remediation applications.

36 MATERIALS SCIENCE↗