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Launch Complex 34, SWMU CCO542022 DNAPL Source Zone Operations, Maintenance, and Monitoring, Site-Wide Long-Term Monitoring, and Hot Spot 6 Air Sparge System Annual Performance Monitoring 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 (HS) 6 Air Sparge (AS) System presents the results of Year 13 operation of the hydraulic containment (HC) Interim Measure (IM), the results of performance monitoring direct-push technology (DPT) sampling and monitoring well sampling conducted in the DSZ, results of the biennial site-wide LTM event, 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. This site has been designated Solid Waste Management Unit (SWMU) CC054 under the Kennedy Space Center (KSC) Resource Conservation and Recovery Act (RCRA) Corrective Action Program. For the site-wide biennial LTM event, a total of 55 monitoring wells were sampled for volatile organic compounds (VOCs) in February 2023 and one well was sampled for polychlorinated biphenyls (PCBs) in December 2022. One well planned for VOC sampling was found to be destroyed and could not be sampled (CW0002). The LTM wells are screened in two lithologic zones: Layer 1 (0 to 25 feet below land surface [bls]) and Layer 2 (25 to 30 ft bls), and are located in the outlying areas of LC34 to monitor groundwater conditions within the Low-Concentration Plume (LCP), defined as concentrations exceeding Groundwater Cleanup Target Levels (GCTLs), and the High-Concentration Plume (HCP), defined as concentrations exceeding Natural Attenuation Default Concentrations (NADCs). Results from the biennial sampling event indicated overall plume stability and delineation for the plume, which extends over 300 acres. The operational period for Year 13 of the HCS was from April 1, 2022 to March 31, 2023. Operational runtime for the system was 90 percent during Year 13, with downtime events attributed to planned maintenance, system repairs, and power outages. As of March 31, 2023, a total of 313,673,241 cumulative gallons of groundwater containing 88,337 pounds of VOCs have been removed by the HCS. Influent concentrations of trichloroethene (TCE) have decreased since startup from approximately 280,000 μg/L (January 2010) to 12,000 μg/L (March 2023). 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 December 2022 within the DSZ to evaluate TCE contamination. Groundwater samples were collected via DPT at nine locations, consistent with previous events between 2017 and 2021. Full vertical profile sampling was completed at each DPT from 8 to 98 feet 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 8 to 98 feet bls. In addition to DPT sampling, groundwater samples were collected from deep monitoring wells in the DSZ area (Layers 7 and 8) in December 2022 to verify vertical delineation. Layer 7/8 monitoring well results were non-detect in December 2022, with exception of three wells (IW0162, IW043D2, and IW044D2), where TCE, cis-1,2-dichloroethene (cDCE), and/or vinyl chloride (VC) were detected above GCTLs. These wells are screened 105 to 115 feet bls, which is below the existing recovery well capture zone. TCE was first detected in IW0162 in December 2021 and has since been sampled at least monthly to monitor TCE concentrations. The maximum TCE concentration during this operational period was 15,000 μg/L at IW0162 in March 2023. Because of the increased TCE concentrations in this well, a new recovery well (RW21D), screened 86 to 106 feet bls, was installed in January 2023 and incorporated into existing HCS operations. The HS 6 AS IM was initiated in 2018 with 160 AS wells, and expanded in 2019 with an additional 140 AS wells. Quarterly performance monitoring was reduced to semi-annual in 2020. The HS 6 AS system remained operational during the reporting period covered under this report. The results of the HS 6 system operation and semi-annual performance monitoring are summarized in this report. Semi-annual monitoring results collected in April and October 2022 show concentrations of contaminants of concern (cDCE, trans-1,2-dichloroethene, and vinyl chloride) are generally decreasing and not impacting the surface water drainage canal, indicating the HS 6 IM is meeting objectives. A Phase Two Expansion of the HS 6 AS IM was recently completed. As of the date of this report, the expansion became operational in August 2023 and the first quarter of monitoring was conducted in November 2023. Details of the construction, start-up, and performance monitoring will be included in a future Annual PMR. Overall, the tasks associated with Year 13 operation of the HC IM, operation of the HS 6 AS IM, and biennial site-wide sampling were performed in accordance with recommendations included in the previous 2021 LC34 (Year 12) annual report. Evaluation of results from the HC IM and HS 6 IM show that these systems are operating as designed and meeting performance objectives. Results from the site-wide biennial LTM program also show that the overall network of monitoring wells is adequate to continue monitoring plume-wide conditions.

Complex 34↗

Inexpensive, removable coating for plaster tooling

Procedure for thinning and spaying a vinyl material provides strippable film for plaster surfaces. Coating is low-cost, effective seal against moisture and other sources of damage. Coating consists of a mixture of hot-spray vinyl material and 30 to 50 percent by volume of methyl ethyl ketone.

Dimino, J. M.↗

Hydrocarbon polymeric binder for advanced solid propellant

The results of curing vinyl alcohol terpolymers of ethylene, propylene and vinyl acetate are reported for an average functionality of 1.24 when reacted with an equivalent amount of diisocynate, and saturated polyisoprene derivative is described having terminal methyl ester functionality. The development is reported of two hydroxy-telechelic polyisoprenes prepared by DEAB initiated free radical polymerization followed by LiAlH4 reduction of the end groups.

Potts, J. E.↗

Synthesis of improved polyester resins

Eighteen aromatic unsaturated polyester prepolymers prepared by a modified interfacial condensation technique were investigated for their solubility in vinyl monomers and ability to provide high char yield forming unsaturated polyester resins. The best resin system contained a polyester prepolymer of phthalic, fumaric and diphenic acids reacted with 2,7-naphthalene diol and 9,9-bis(4-hydroxyphenyl)fluorene. This prepolymer is very soluble in styrene, divinyl benzene, triallyl cyanurate, diallyl isophthalate and methylvinylpyridine. It provided anaerobic char yields as high as 41 percent at 800 C. The combination of good solubility and char yield represents a significant improvement over state-of-the-art unsaturated polyester resins. The majority of the other prepolymers had only low or no solubility in vinyl monomers. Graphite composites from this prepolymer with styrene were investigated. The cause for the observed low shear strengths of the composites was not determined, however 12-week aging of the composites at 82 C showed that essentially no changes in the composites had occurred.

Mcleod, A. H.↗

Silicon dendritic web material

The development of a low cost and reliable contact system for solar cells and the fabrication of several solar cell modules using ultrasonic bonding for the interconnection of cells and ethylene vinyl acetate as the potting material for module encapsulation are examined. The cells in the modules were made from dendritic web silicon. To reduce cost, the electroplated layer of silver was replaced with an electroplated layer of copper. The modules that were fabricated used the evaporated Ti, Pd, Ag and electroplated Cu (TiPdAg/Cu) system. Adherence of Ni to Si is improved if a nickel silicide can be formed by heat treatment. The effectiveness of Ni as a diffusion barrier to Cu and the ease with which nickel silicide is formed is discussed. The fabrication of three modules using dendritic web silicon and employing ultrasonic bonding for interconnecting calls and ethylene vinyl acetate as the potting material is examined.

Meier, D. L.↗

Dynamic-pressure measurements using an electronically scanned pressure module

Frequency response was measured for different lengths and diameters of tubing between a sinusoidal pressure source and a pressure sensing module from an electronically scanned pressure measuring system. Measurements were made for straight runs of both steel and vinyl tubing. For steel tubing, measured results are compared with results calculated by using equations developed by Tijdeman and Bergh. Measurements were also made with a bend in the vinyl tubing at the module. In addition, measurements were made with two coils placed in the tubing near the middle of the run.

Chapin, W. G.↗

Comparison of flexural properties of aramid-reinforced pultrusions having varied matrices, pretreatments and postcures

Aramid-reinforced composite materials of equal fiber volume and varied polymer thermoset matrices were pultruded and flexurally tested to failure. The objective was to improve the flexural properties of aramid-reinforced pultrusions. Pultrusions of both sized and unsized aramid fiber with four different resin systems were compared to determine the effects of sizing compounds and postcuring on flexural strength, fiber wettability, and fiber-to-resin interface bonding. Improvements in flexural strength resulting from pretreatments with the sizing solutions used were marginal. The most significant improvements in flexural properties resulted from postcuring. Flexural strengths ranged from a low of 39,647 psi (273MPa) to a high of 80,390 psi (554 MPa), an overall increase of 103 percent. The fact that postcuring improved the flexural properties of the pultrusions of the four resin systems indicates that a full cure did not occur in any of the resin systems during the pultrusion process. The increased flexural strengths of the polyester and vinyl ester pultrusions were the most surprising. The four resin systems examined were Interplastic Corporation VE 8300 vinyl ester, Ashland Chemical Company Aropol 7430 Polyester, and Shell Chemical Company Epon 9302 and Epon 9310 epoxides.

Wilson, Maywood L.↗

Review of thermal properties of graphite composite materials

Flammability, thermal, and selected mechanical properties of composites fabricated with epoxy and other thermally stable resin matrices are described. Properties which were measured included limiting-oxygen index, smoke evolution, thermal degradation products, total-heat release, heat-release rates, mass loss, flame spread, ignition resistance, thermogravimetric analysis, and selected mechanical properties. The properties of 8 different graphite composite panels fabricated using four different resin matrices and two types of graphite reinforcement are described. The resin matrices included: XU71775/H795, a blend of vinyl polystyryl pyridine and bismaleimide; H795, a bismaleimide; Cycom 6162, a phenolic; and PSP 6022M, a polystyryl pyridine. The graphite fiber used was AS-4 in the form of either tape or fabric. The properties of these composites were compared with epoxy composites. It was determined that the blend of vinyl polystyryl pyridine and bismaleimide (XU71775/H795) with the graphite tape was the optimum design giving the lowest heat release rate.

Kourtides, D. A.↗

Plasma-polymerized coating for polycarbonate: Single-layer, abrasion resistant, and antireflection

Plasma-polymerized vinyl trimethoxy silane films were deposited on transparent polycarbonate substrates. The adherent, clear films protected the substrates from abrasion and also served as antireflection coatings. Post-treatment of the vinyl trimethoxy silane films in an oxygen glow discharge further improved their abrasion resistance. The coatings were characterized by elemental analysis of the bulk, ESCA analysis of the surface, transmission, thickness, abrasion resistance, haze, and adhesion. This patented process is currently used by the world's largest manufacturers of non-prescription sunglasses to protect the plastic glasses from scratching and thereby to increase their useful lifetime.

Wydeven, Theodore↗

Upper limits for the ethyl-cyanide abundances in TMC-1 and L134N - Chemical implications

Interstellar ethyl-cyanide has been sought via its 2(02)-1(01) transition towards two cold, dark clouds, and upper limits of the total column densities of 3 x 10 to the 12th/sq cm and 2 x 10 to the 12th/sq cm for TMC-1 and L134N, respectively. The 2(02)-1(01) transition of vynil cyanide, previously identified in TMC-1 by Matthews and Sears (1983b), was also observed. The detection of vinyl cyanide and the nondetection of ethyl cyanide in TMC-1 are consistent with gas phase ion-molecule chemical models, and there is thus no necessity of invoking grain surface synthesis for vinyl cyanide in cold clouds.

Minh, Y. C.↗

Ion exchange polymers and method for making

An ion exchange polymer comprised of an alkali metal or alkaline earth metal salt of a poly(carboxylic acid) in a poly(vinyl acetal) matrix is described. The polymer is made by treating a mixture made of poly(vinyl alcohol) and poly(acrylic acid) with a suitable aldehyde and an acid catalyst to cause acetalization with some cross-linking. The material is then subjected to an alkaline aqueous solution of an alkali metal salt or an alkali earth metal salt. All of the film forming and cross-linking steps can be carried out simultaneously, if desired.

Philipp, Warren H.↗

Characterization of the Minimum Energy Paths and Energetics for the Reaction of Vinylidene with Acetylene

The reaction of vinylidene (CH2C) with acetylene may be an initiating reaction in soot formation. We report minimum energy paths and accurate energetics for a pathway leading to vinyl-acetylene and for a number of isomers of C4H4. The calculations use complete active space self-consistent field (CASSCF) derivative methods to characterize the stationary points and internally contacted configuration interaction (ICCI) and/or coupled cluster singles and doubles with a perturbational estimate of triple excitations (CCSD(T)) to determine the energetics. We find an entrance channel barrier of about 5 kcal/mol for the addition of vinylidene to acetylene, but no barriers above reactants for the reaction pathway leading to vinyl-acetylene.

Walch, Stephen P.↗

Contamination of Critical Surfaces from NVR Glove Residues Via Dry Handling and Solvent Cleaning

Gloves are often used to prevent the contamination of critical surfaces during handling. The type of glove chosen for use should be the glove that produces the least amount of non-volatile residue (NVR). This paper covers the analysis of polyethylene, nitrile, latex, vinyl, and polyurethane gloves using the contact transfer and gravimetric determination methods covered in the NASA GSFC work instruction Gravimetric Determination and Contact Transfer of Non-volatile Residue (NVR) in Cleanroom Glove Samples, 541-WI-5330.1.21 and in the ASTM Standard E-1731M-95, Standard Test Method for Gravimetric Determination of Non-Volatile Residue from Cleanroom Gloves. The tests performed focus on contamination of critical surfaces at the molecular level. The study found that for the most part, all of the gloves performed equally well in the contact transfer testing. However, the polyethylene gloves performed the best in the gravimetric determination testing, and therefore should be used whenever solvent contact is a possibility. The nitrile gloves may be used as a substitute for latex gloves when latex sensitivity is an issue. The use of vinyl gloves should be avoided, especially if solvent contact is a possibility. A glove database will be established by Goddard Space Flight Center (GSFC) Code 541 to compile the results from future testing of new gloves and different glove lots.

Sovinski, Marjorie F.↗

Sound Guard

Lubrication technology originally developed for a series of NASA satellites has produced a commercial product for protecting the sound fidelity of phonograph records. Called Sound Guard, the preservative is a spray-on fluid that deposits a microscopically thin protective coating which reduces friction and prevents the hard diamond stylus from wearing away the softer vinyl material of the disc. It is marketed by the Consumer Products Division of Ball Corporation, Muncie, Indiana. The lubricant technology on which Sound Guard is based originated with NASA's Orbiting Solar Observatory (OSO), an Earth-orbiting satellite designed and built by Ball Brothers Research Corporation, Boulder, Colorado, also a division of Ball Corporation. Ball Brothers engineers found a problem early in the OSO program: known lubricants were unsuitable for use on satellite moving parts that would be exposed to the vacuum of space for several months. So the company conducted research on the properties of materials needed for long life in space and developed new lubricants. They worked successfully on seven OSO flights and attracted considerable attention among other aerospace contractors. Ball Brothers now supplies its "Vac Kote" lubricants and coatings to both aerospace and non-aerospace industries and the company has produced several hundred variations of the original technology. Ball Corporation expanded its product line to include consumer products, of which Sound Guard is one of the most recent. In addition to protecting record grooves, Sound Guard's anti-static quality also retards particle accumulation on the stylus. During comparison study by a leading U.S. electronic laboratory, a record not treated by Sound Guard had to be cleaned after 50 plays and the stylus had collected a considerable number of small vinyl particles. The Sound Guard-treated disc was still clean after 100 plays, as was its stylus.

Source record↗

Hydrogen Migration and Vinylidene Pathway for Formation of Methane in the 193 nm Photodissociation of Propene: CH3CH=CH2 and CD3CD=CD2

Photodissociation channels and the final product yields from the 193 nm photolysis of propene-h6 (CH2=CHCH3) and propene-d6 (CD2=CDCD3) have been investigated, employing gas chromatography, mass spectroscopy, and flame ionization (GC/MS/FID) detection methods. The yields of methane as well as butadiene relative to ethane show considerable variations when propene-h6 or propene-d6 are photolyzed. This suggests significant variances in the relative importance of primary photolytic processes and/or secondary radical reactions, occurring subsequent to the photolysis. Theoretical calculations suggest the potential occurrence of an intramolecular dissociation through a mechanism involving vinylidene formation, accompanied by an ethylenic H-migration through the pi-orbitals. This process affects the final yields of methane-h4 versus methane-d4 with respect to other products. The product yields from previous studies of the 193 nm photolysis of methyl vinyl ketone-h6 and -d6 (CH2=CHCOCH3, CD2=CDCOCD3), alternative precursors for generating methyl and vinyl radicals, are compared with the current results for propene.

Zhao, Yi-Lei↗

Calculational and Experimental Investigations of the Pressure Effects on Radical - Radical Cross Combinations Reactions: C2H5 + C2H3

Pressure-dependent product yields have been experimentally determined for the cross-radical reaction C2H5 + C2H3. These results have been extended by calculations. It is shown that the chemically activated combination adduct, 1-C4H8*, is either stabilized by bimolecular collisions or subject to a variety of unimolecular reactions including cyclizations and decompositions. Therefore the "apparent" combination/disproportionation ratio exhibits a complex pressure dependence. The experimental studies were performed at 298 K and at selected pressures between about 4 Torr (0.5 kPa) and 760 Torr (101 kPa). Ethyl and vinyl radicals were simultaneously produced by 193 nm excimer laser photolysis of C2H5COC2H3 or photolysis of C2H3Br and C2H5COC2H5. Gas chromatograph/mass spectrometry/flame ionization detection (GC/MS/FID) were used to identify and quantify the final reaction products. The major combination reactions at pressures between 500 (66.5 kPa) and 760 Torr are (1c) C2H5 + C2H3 yields 1-butene, (2c) C2H5 + C2H5 yields n-butane, and (3c) C2H3 + C2H3 yields 1,3-butadiene. The major products of the disproportionation reactions are ethane, ethylene, and acetylene. At moderate and lower pressures, secondary products, including propene, propane, isobutene, 2-butene (cis and trans), 1-pentene, 1,4-pentadiene, and 1,5-hexadiene are also observed. Two isomers of C4H6, cyclobutene and/or 1,2-butadiene, were also among the likely products. The pressure-dependent yield of the cross-combination product, 1-butene, was compared to the yield of n-butane, the combination product of reaction (2c), which was found to be independent of pressure over the range of this study. The [ 1-C4H8]/[C4H10] ratio was reduced from approx.1.2 at 760 Torr (101 kPa) to approx.0.5 at 100 Torr (13.3 kPa) and approx.0.1 at pressures lower than about 5 Torr (approx.0.7 kPa). Electronic structure and RRKM calculations were used to simulate both unimolecular and bimolecular processes. The relative importance of C-C and C-H bond ruptures, cyclization, decyclization, and complex decompositions are discussed in terms of energetics and structural properties. The pressure dependence of the product yields were computed and dominant reaction paths in this chemically activated system were determined. Both modeling and experiment suggest that the observed pressure dependence of [1-C4H8]/[C4H10] is due to decomposition of the chemically activated combination adduct 1-C4H8* in which the weaker allylic C-C bond is broken: H2C=CHCH2CH3 yields C3H5 + CH3. This reaction occurs even at moderate pressures of approx.200 Torr (26 kPa) and becomes more significant at lower pressures. The additional products detected at lower pressures are formed from secondary radical-radical reactions involving allyl, methyl, ethyl, and vinyl radicals. The modeling studies have extended the predictions of product distributions to different temperatures (200-700 K) and a wider range of pressures (10(exp -3) - 10(exp 5) Torr). These calculations indicate that the high-pressure [1-C4H8]/[C4H10] yield ratio is 1.3 +/- 0.1.

Fahr, Askar↗

Multiscale Modeling of Thermal Conductivity of Polymer/Carbon Nanocomposites

Molecular dynamics simulation was used to estimate the interfacial thermal (Kapitza) resistance between nanoparticles and amorphous and crystalline polymer matrices. Bulk thermal conductivities of the nanocomposites were then estimated using an established effective medium approach. To study functionalization, oligomeric ethylene-vinyl alcohol copolymers were chemically bonded to a single wall carbon nanotube. The results, in a poly(ethylene-vinyl acetate) matrix, are similar to those obtained previously for grafted linear hydrocarbon chains. To study the effect of noncovalent functionalization, two types of polyethylene matrices. -- aligned (extended-chain crystalline) vs. amorphous (random coils) were modeled. Both matrices produced the same interfacial thermal resistance values. Finally, functionalization of edges and faces of plate-like graphite nanoparticles was found to be only modestly effective in reducing the interfacial thermal resistance and improving the composite thermal conductivity

Clancy, Thomas C.↗

Primary Volatile Abundances in Comets from Infrared Spectroscopy: Implications for Reactions on Grain Surfaces in the Interstellar/Nebular Environment

Comets retain relatively primitive icy material remaining from the epoch of Solar System formation, however the extent to which they are modified from their initial state remains a key question in cometary science. High-resolution lR spectroscopy has emerged as a powerful tool for measuring vibrational emissions from primary volatiles (i.e., those contained in the nuclei of comets). With modern instrumentation, most notably NIRSPEC at the Keck II 10-m telescope, we can quantify species of astrobiological importance (e.g., H20, C2H2, CH4, C2H6, CO, H2CO, CH30H, HCN, NH3). In space environments, compounds of keen interest to astrobiology could originate from HCN and NH3 (leading to amino acids), H2CO (leading to sugars), or C2H6 and CH4 (suggested precursors of ethyl- and methylamine). Measuring the abundances of these precursor molecules (and their variability among comets) is a feasible task that contributes to understanding their delivery to Earth's early biosphere and to the synthesis of more complex pre biotic compounds. Over 20 comets have now been measured with IR spectroscopy, and this sample reveals significant diversity in primary volatile compositions. From this, a taxonomic classification scheme is emerging, presumably reflecting the diverse conditions experienced by pre-cometary grains in interstellar and subsequent nebular environs. The importance of H-atom addition to C2H2 on the surfaces of interstellar grains to produce C2H6 was validated by the discovery of abundant ethane in comet C/1996 B2 (Hyakutake) with C2H6/CH4 well above that achievable by gas-phase chemistry , and then in irradiation experiments on laboratory ices at 10 - 50 K. The large abundance ratios C2H6/CH4 observed universally in comets establish H-atom addition as an important and likely ubiquitous process, and comparing C2H6/C2H2 among comets can provide information on its efficiency. The IR is uniquely capable since symmetric hydrocarbons (e.g., C2H2, CH4, C2H6) have no electric dipole moment and thus no allowed pure rotational transitions. CO should also be hydrogenated on grain surfaces. Irradiation experiments on interstellar ice analogs show this to require very low temperatures, the resulting yields of H2CO and CH30H being highly dependent on temperature in the range approx 10 - 25 K. The relative abundances of these chemically-related molecules in comets provide one measure of the efficiency of H-atom addition to CO Oxidation of CO is also important on grain mantles, as evidenced by the widespread presence of C02 ice towards interstellar sources observed with ISO and in a survey of 17 comets observed with AKARI. H-atom addition to C2H2 produces the vinyl radical, and through subsequent oxidation1reduction reactions can lead to vinyl alcohol, acetaldehyde, and ethanol This may have implications for interpreting observed abundance ratios CO/C2H2. We will discuss possible implications regarding formation conditions in the context of measured primary volatile compositions, emphasizing recently observed comets and published results. These are continually providing new insights regarding our taxonomic scheme and also delivery of pre-biological material to the young Earth.

DiSanti, M. A.↗