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NASA NTRS2017

Glyoxal Yield from Isoprene Oxidation and Relation to Formaldehyde: Chemical Mechanism, Constraints from SENEX Aircraft Observations, and Interpretation of OMI Satellite Data

Glyoxal (CHOCHO) is produced in the atmosphere by the oxidation of volatile organic compounds(VOCs). Like formaldehyde (HCHO), another VOC oxidation product, it is measurable from space by solar backscatter. Isoprene emitted by vegetation is the dominant source of CHOCHO and HCHO in most of the world. We use aircraft observations of CHOCHO and HCHO from the Southeast Nexus (SENEX) campaign over the southeast US in summer 2013 to better understand the CHOCHO time-dependent yield from isoprene oxidation, its dependence on nitrogen oxides (NO (sub x) triple bonded to NO plus NO2), the behavior of the CHOCHO-HCHO relationship, the quality of Ozone Monitoring Instrument (OMI) CHOCHO satellite observations, and the implications for using CHOCHO observations from space as constraints on isoprene emissions. We simulate the SENEX and OMI observations with the Goddard Earth Observing System chemical transport model (GEOSChem) featuring a new chemical mechanism for CHOCHO formation from isoprene. The mechanism includes prompt CHOCHO formation under low-NO (sub x) conditions following the isomerization of the isoprene peroxy radical (ISOPO2).The SENEX observations provide support for this prompt CHOCHO formation pathway, and are generally consistent with the GEOS-Chem mechanism. Boundary layer CHOCHO and HCHO are strongly correlated in the observations and the model, with some departure under low-NO (sub x) conditions due to prompt CHOCHO formation. SENEX vertical profiles indicate a free-tropospheric CHOCHO background that is absent from the model. The OMI CHOCHO data provide some support for this free-tropospheric background and show southeast US enhancements consistent with the isoprene source but a factor of 2 too low. Part of this OMI bias is due to excessive surface reflectivities assumed in the retrieval. The OMI CHOCHO and HCHO seasonal data over the southeast US are tightly correlated and provide redundant proxies of isoprene emissions. Higher temporal resolution in future geostationary satellite observations may enable detection of the prompt CHOCHO production under low-NO (sub x) conditions apparent in the SENEX data.

OMI↗
NASA NTRS2014

True Emission Factors for Forest Fires and the Role of Non-Fire NOx

True Emission Factors for Forest Fires and the Role of Non-Fire NOx Robert B. Chatfield and Meinrat Andreae The standard way to estimate biomass burning emissions factors from airborne, surface, or laboratory data is to relate the emitted pollutant concentration to the carbon burned, C(sub tot), and liberated to the air, mostly CO2. We approximate total emitted carbon C(sub tot) ~ (CO2 + CO). Emission ratios that are based on CO, describing burning effects, delta-parameter delta-CO, are often used to quantify fire emissions. These are not as useful as emission factors, for they often complicate analyses, since delta-CO delta-CO2 may vary by unto tenfold, and can have bias artifacts of similar magnitude. We present a methodology that estimates both emission factors and a reasonable description of background C(sub tot). High O3 values require a history of the balanced interaction of two pollutant types, nitrogen oxides (NOx) and a radical source, VOCs. However, high VOC NOx ratios seen in many plumes, especially from smoldering-dominated fires, make substantial O3 formation less likely. One particularly intense fire we analyzed, the notorious Rim Fire of 2013, near Yosemite, California. It produced notable quantities of free NOx and (both gas- and particle-phase) Cl species. Consequently, we also outline a quantitative way to assess the effects of anthropogenic or lightning NOx. We provide the example of California burning emissions using measurements of HCHO, NO, and the photolysis rate j(sub HCHO).

Chatfield, Robert B.↗
NASA NTRS2019

Mid-21st Century Ozone Air Quality and Health Burden in China Under Emissions Scenarios and Climate Change

Despite modest emissions reductions of air pollutants in recent years, China still suffers from poor air quality, and the outlook for future air quality in China is uncertain. We explore the impact of two disparate 2050 emissions scenarios relative to 2015 in the context of a changing climate with the Geophysical Fluid Dynamics Laboratory Atmospheric Model version 3 (GFDL-AM3) chemistry-climate model. We impose the same near-term climate change for both emission scenarios by setting global sea surface temperature (SST) and sea ice cover (SIC) to the average over 2010–2019 and 2046–2055, respectively, from a three-member ensemble of GFDL coupled climate model simulations under the RCP8.5 (Representative Concentration Pathway) scenario. By the 2050s, annual mean surface ozone increases throughout China by up to 8 ppbv from climate change alone (estimated by holding air pollutants at 2015 levels while setting SIC and SST to 2050 conditions in the model) and by 8–12 ppbv in a scenario in which emissions of ozone precursors nitrogen oxides (NO (sub x) ) and anthropogenic volatile organic compounds (VOCs) increase by ~10%. In a scenario in which NO (sub x) and anthropogenic VOC emissions decline by 60%, annual mean surface ozone over China decreases by 16–20 ppbv in the 2050s relative to the 2010s. The ozone increase from climate change alone results in an additional 62 000 premature deaths in China as compared to 330 000 fewer premature deaths by the 2050s under a strong emissions mitigation scenario. In springtime over Southwestern China in the 2050s, the model projects 9–12 ppbv enhancements to surface ozone from the stratosphere (diagnosed with a model tracer) and from international anthropogenic emissions (diagnosed by differencing AM3 simulations with the same emissions within China but higher versus lower emissions in the rest of the world). Our findings highlight the effectiveness of emissions controls in reducing the health burden in China due to air pollution, and also the potential for climate change and rising global emissions to offset, at least partially, some of the ozone decreases attained with regional emission reductions in China.

Westervelt, D. M.↗
NASA NTRS2019

Anthropogenic Control over Wintertime Oxidation of Atmospheric Pollutants

Anthropogenic air pollutants such as nitrogen oxides (NO(x) = NO + NO(2)), sulfur dioxide (SO(2)), and volatile organic compounds (VOC), among others, are emitted to the atmosphere throughout the year from energy production and use, transportation, and agriculture. These primary pollutants lead to the formation of secondary pollutants such as fine particulate matter (PM(2.5)) and ozone (O(3)) and perturbations to the abundance and lifetimes of short-lived greenhouse gases. Free radical oxidation reactions driven by solar radiation govern the atmospheric lifetimes and transformations of most primary pollutants and thus their spatial distributions. During winter in the mid and high latitudes, where a large fraction of atmospheric pollutants are emitted globally, such photochemical oxidation is significantly slower. Using observations from a highly instrumented aircraft, we show that multi-phase reactions between gas-phase NO(x) reservoirs and aerosol particles, as well as VOC emissions from anthropogenic activities, lead to a suite of atypical radical precursors dominating the oxidizing capacity in polluted winter air, and thus, the distribution and fate of primary pollutants on a regional to global scale.

Haskins, J. D.↗
NASA NTRS2021

Evaluating Drought Responses of Surface Ozone Precursor Proxies: Variations With Land Cover Type, Precipitation, and Temperature

Prior work suggests drought exacerbates US air quality by increasing surface ozone concentrations. We analyze 2005–2015 tropospheric column concentrations of two trace gases that serve as proxies for surface ozone precursors retrieved from the OMI/Aura satellite: Nitrogen dioxide (ΩNO2; NOx proxy) and formaldehyde (ΩHCHO; VOC proxy). We find 3.5% and 7.7% summer drought enhancements (classified by SPEI) for ΩNO2 and ΩHCHO, respectively, corroborating signals previously extracted from ground‐level observations. When we subset by land cover type, the strongest ΩHCHO drought enhancement (10%) occurs in the woody savannas of the Southeast US. By isolating the influences of precipitation and temperature, we infer that enhanced biogenic VOC emissions in this region increase ΩHCHO independently with both high temperature and low precipitation during drought. The strongest ΩNO2 drought enhancement (6.0%) occurs over Midwest US croplands and grasslands, which we infer to reflect the sensitivity of soil NOx emissions to temperature.

drought↗
NASA NTRSDate not supplied

PFAS Treatment Pilot Study using Granular Activated Carbon at Kennedy Space Center, Florida

Per- and polyfluoroalkyl substances (PFAS) have been found in investigative derived waste (IDW) generated from groundwater sampling and remediation activities conducted at Kennedy Space Center (KSC), Florida. PFAS are exceptionally strong compounds because of carbon-fluorine bonds resulting in resistance to degradation, low chemical reactivity, compound stability, and persistence in the environment. The regulatory status of PFAS is very dynamic. PFAS is not considered a hazardous waste and has no federal or state (Florida) cleanup requirements at this time. Due to the current and unknown future of the regulatory and treatment landscape, non-hazardous IDW, based upon site volatile organic compounds (VOCs) regulated under Title 40 of Federal Regulations part 261, containing PFAS is not being processed for off-site waste disposal under KSC’s Resource Conservation and Recovery Act permit as a proactive precaution. Long-term storage of aqueous IDW in the meantime was determined to be inadequate due to the potential for spills and/or leaks. A very limited number treatment methods are available at this time. To date, granular activated carbon (GAC) and ion exchange technologies have been found to be some of the most consistent treatment options for removing PFAS from aqueous media. Therefore, a pilot study using GAC was developed at KSC to determine the feasibility of treating non-hazardous IDW containing PFAS to reduce the total volume of PFAS waste and minimize the risk of leaks or spills while storing the waste until complete PFAS-destructive treatment options are more readily available. NASA wanted the pilot test to be able to demonstrate the ability to completely remove 18 PFAS compounds and the site VOCs to below the state of Florida groundwater cleanup target levels (GCTLs).

Michael J Deliz↗
NASA NTRSDate not supplied

Cropland and Land-Clearing Emission Factors From Firex-AQ

The Fire Influence on Regional to Global Environments and Air Quality (FIREX-AQ) campaign is a NOAA/NASA interagency intensive study of North American fires that took place from July to September 2019. Agricultural fires were sampled on 7 flights from August 21st to September 3rd, 2019. We present emission factors for gas-phase and aerosol-phase species for the different fuel types identified during the campaign. We discuss the dependence of these emission factors on both fuel type and burning characteristics such as modified combustion efficiency (MCE). We analyze 73 fires encompassing four different agricultural fuels (corn, rice, soybean, wheat) and four different types of land-clearing fuels (grass, slash, pile, shrub). Approximately half of all sampled fires were burning corn agricultural residue. We report emission factors for 118 VOCs, where two thirds of emissions are made up of species with lifetimes against oxidation by OH of less than 12 hours (near-field impacts) and the remainder have longer-lifetimes (far-field impacts). We also include an additional 9 aerosol species, 12 halogenated species, 5 sulfur-containing species, and 22 nitrogen-containing species, including NH3 and NOx. There is a statistically significant difference in MCE between agricultural and land-clearing fires that accounts for some of the differences in emission factors across these fuels. VOCs generally have a strong negative correlation with MCE but with different slopes across fuel types. There is a significant positive relationship between MCE and three gas-phase (NO, NO2, SO2) and two aerosol-phase (pCl, pNH4) species. Many emission factors show additional dependence factors beyond MCE that could be related to fuel composition, fire temperature, soil moisture, or other possible differences in burning conditions. Therefore, important differences in emission factors may result when averaging together different types of agricultural and land-clearing fuels in compilations for use in modeling efforts.

biomass burning↗
NASA NTRS2022

Wilson Corners Solid Waste Management Unit (SWMU) 001: 2021 Annual Long-Term Monitoring Report, Kennedy Space Center, Florida

This report presents a summary of the long-term monitoring (LTM) activities that occurred in 2021 at Wilson Corners, Solid Waste Management Unit (SWMU) 001, at Kennedy Space Center (KSC), Florida. The site is monitored under KSC’s Resource Conservation and Recovery Act (RCRA) Corrective Action Program. Adaptive site management is being utilized through ongoing assessment, design, and interim measures (IM). Annual LTM of the groundwater is also being conducted at the site. This approach also meets the requirements of Chapter 62-780, Florida Administrative Code (F.A.C.). The goal of LTM at this site is threefold: to determine groundwater flow characteristics, monitor the downgradient concentration trends, and monitor select locations internal to the groundwater plume. Every 5 years, upgradient and side-gradient monitoring wells are sampled to verify delineation. The last time this was performed was in 2015. The sampling of these wells in 2020 was replaced with the direct push technology (DPT) investigations completed in October 2020 and April 2021. This DPT groundwater data was presented in an Advance Data Package (ADP) in September 2021 and discussed in the Implementation Work Plan (IWP) dated November 2021 for installation of an air sparge (AS) system. Based on results from groundwater sampling activities performed during the previous reporting period, including the 2020 and 2021 DPT groundwater sampling, it was determined that the LTM sampling plan was no longer meeting the goal of LTM because delineation was not verified. The 2021 LTM sampling plan was modified to include the sampling of monitoring wells located around the perimeter of the low concentration plume (LCP); the area with concentrations of contaminants of concern [COCs] greater than Groundwater Cleanup Target Levels [GCTLs]), and sampling of 10 monitoring wells proposed for installation (April 2021 KSC Remediation Team (KSCRT) Meeting, Decision 2104-D32). The modified LTM plan received team consensus at the September 2021 KSCRT Meeting (Decision Number 2109-D03), and sampling of the existing monitoring wells was completed in December 2021. The proposed monitoring wells are planned for installation in late 2022, concurrent with ongoing IM construction activities. December 2021 LTM data was presented at the May 2022 KSCRT Meeting, and activities are summarized in this report. The activities presented in this report include the December 2021 groundwater gauging of 42 monitoring wells and sampling of 44 monitoring wells. During the December 2021 event, the low flow sampling method was used, and samples were analyzed for a select list of volatile organic compounds (VOCs), including 1,1,2-trichloro-1,2,2-trifluoroethane (Freon 113). The following conclusions can be made based on the 2021 LTM results: - In December 2021, groundwater flow for the site was generally to the west at all intervals. This is generally consistent with historical observations at the site, with the exception of a southwest and southeast flow component observed at 34 to 48 feet below land surface (bls). - The vertical extent of VOCs was historically delineated by monitoring wells screened greater than 48 feet bls. The results from the two vertical extent monitoring wells, WILC-MW0078 (screened 65 to 70 feet bls) and WILC-MW0130 (screened 56 to 66 feet bls) that were sampled during the 2021 LTM indicate that groundwater vinyl chloride (VC) concentrations in both wells were greater than the GCTL. The Remediation Team has previously agreed to delay deeper DPT investigations in this area to prevent the creation of additional pathways for vertical migration. - The LCP continues to extend both horizontally, predominantly to the west, and vertically beyond the current monitoring well network, with some retraction observed to the southeast. Evaluation of this data combined with data from the 2020 and 2021 DPT sampling event indicate that the LCP encompasses an estimated 20.7 acres based on an expanded sampling area, as compared to the 2020 LCP footprint of 17.0 acres. - Freon 113 was not detected above GCTLs during the 2021 LTM event. Based on groundwater sampling activities performed in 2021, including April 2021 DPT groundwater sampling, the following recommendations are provided: - Perform the next LTM sampling event, targeted to occur in 2023, concurrently with the IM baseline sampling prior to AS system installation; - Include sampling from nine monitoring wells that are planned to be installed in late 2022, concurrent with upcoming IM construction activities. Installation of one deep vertical well, screened 70 to 80 feet bls, will be delayed to prevent the creation of an additional pathway for vertical migration; - Continue to sample under the modified annual LTM plan as presented in Table 4-1 concurrently with IM baseline sampling; and - Once the AS system install and start-up is complete, select monitoring wells from the LTM program will transition into the performance monitoring plan, and LTM will be temporarily discontinued. Performance monitoring will be performed quarterly, and the monitoring well network will be evaluated following the first performance monitoring sampling event.

long-term monitoring (LTM)↗
NASA NTRS2023

Two Air Quality Regimes in Total Column NO2 over the Gulf of Mexico in May 2019: Shipboard and Satellite Views

The Satellite Coastal and Oceanic Atmospheric Pollution Experiment (SCOAPE) cruise in the Gulf of Mexico was conducted in May 2019 by NASA and the Bureau of Ocean Energy Management to determine the feasibility of using satellite data to measure air quality in a region of concentrated oil and natural gas (ONG) operations. SCOAPE addressed both technological and scientific issues related to measuring NO2 columns over the Outer Continental Shelf. Featured were nitrogen dioxide (NO 2 ) instruments (Pandora, Teledyne API analyzer) at Cocodrie, LA (29.26°, -90.66°), and on the Research Vessel Point Sur operating off the Louisiana coast with measurements of ozone, carbon monoxide and volatile organic compounds (VOC). The findings: (1) All NO 2 observations revealed two atmospheric regimes over the Gulf, the first influenced by tropical air in 10-14 May, the second influenced by flow from urban areas on 15-17 May; (2) Comparisons of OMI v4 and TROPOMI v1.3 TC (total column) NO 2 data with shipboard Pandora NO 2 column observations averaged 13% agreement with the largest difference during 15-17 May (~20%). At Cocodrie, the satellite-Pandora agreement was ~5%. (3) Three new-model Pandora instruments displayed a TC NO 2 precision of 0.01 Dobson Units (~5%); (4) Regions of smaller, older natural gas operations showed high methane readings from leakage; elevated VOC were also detected. Neither satellite nor spectrometer captured the magnitude of ambient NO 2 variability near ONG platforms. Given an absence of regular air quality monitoring over the Gulf of Mexico, SCOAPE data constitute a baseline against which future observations can be compared.

Nitrogen dioxide↗
NASA NTRSDate not supplied

Differential Mobility Spectrometry on the ISS: Successes and Current Concerns

With the construction of the International Space Station (ISS), crew members moved from the relatively short flights of the Space Shuttle (~ 2 weeks) to missions lasting months to a year. As such, environmental monitoring needs also changed, transitioning from a reliance on archival sampling to a combination of archival sampling and in-flight data collection. In the case of trace volatile organic compound (VOC) monitoring, this in-flight monitoring was performed early on by the Volatile Organic Analyzer (VOA), a gas chromatograph-ion mobility spectrometer, which operated on the ISS for 7 years. This large, fixed-position analyzer was replaced by Air Quality Monitors (AQMs), a pair of small gas chromatograph-differential mobility spectrometers, in the spring of 2013. During their initial half decade of use, and covering multiple sets of units, the AQMs performed well, meeting all of their validation criteria and generally showing excellent accuracy when compared to the now-reduced archival samples. These instruments were also used to perform a survey of the US Operating Segment (US Lab Module, European Columbus Module, and Japanese Pressurized Module), confirming that the atmosphere in this segment is well-mixed. The AQMs were also able to provide important information in contingency situations, such as confirming that no ammonia was present on the ISS following alarms suggesting that the coolant loops had leaked in January 2015. As the fleet of AQMs has aged, though, issues of concern have arisen. These have ranged from pervasive electronics board problems to loss of sensitivity due to carbon dioxide to incorrect identification of compounds. Some of these issues are unavoidable due to the nature of the AQM’s use and preparation prior to flight. However, with the extension of the ISS to 2030 (well past its original 2024 lifetime), the fleet of AQMs will be asked to perform longer, requiring solutions to some of the inherent problems. In this presentation, we will discuss the history of the AQM on the ISS with a focus on more recent results. These results show both the continued usefulness of the AQM for atmospheric monitoring and also the current concerns, including: 1) the incorrect identification of benzene, 2) reporting of elevated isopropanol concentrations, and 3) the loss of the reactant ion peak (RIP) that must be resolved in order for the instrument to continue to serve as the primary trace VOC monitor on the ISS.

W T Wallace↗
NASA NTRSDate not supplied

Differential Mobility Spectrometry on the ISS: Successes and Current Concerns

With the construction of the International Space Station (ISS), crew members moved from the relatively short flights of the Space Shuttle (~ 2 weeks) to missions lasting months to a year. As such, environmental monitoring needs also changed, transitioning from a reliance on archival sampling to a combination of archival sampling and in-flight data collection. In the case of trace volatile organic compound (VOC) monitoring, this in-flight monitoring was performed early on by the Volatile Organic Analyzer (VOA), a gas chromatograph-ion mobility spectrometer, which operated on the ISS for 7 years. This large, fixed-position analyzer was replaced by Air Quality Monitors (AQMs), a pair of small gas chromatograph-differential mobility spectrometers, in the spring of 2013. During their initial half decade of use, and covering multiple sets of units, the AQMs performed well, meeting all of their validation criteria and generally showing excellent accuracy when compared to the now-reduced archival samples. These instruments were also used to perform a survey of the US Operating Segment (US Lab Module, European Columbus Module, and Japanese Pressurized Module), confirming that the atmosphere in this segment is well-mixed. The AQMs were also able to provide important information in contingency situations, such as confirming that no ammonia was present on the ISS following alarms suggesting that the coolant loops had leaked in January 2015. As the fleet of AQMs has aged, though, issues of concern have arisen. These have ranged from pervasive electronics board problems to loss of sensitivity due to carbon dioxide to incorrect identification of compounds. Some of these issues are unavoidable due to the nature of the AQM’s use and preparation prior to flight. However, with the extension of the ISS to 2030 (well past its original 2024 lifetime), the fleet of AQMs will be asked to perform longer, requiring solutions to some of the inherent problems. In this presentation, we will discuss the history of the AQM on the ISS with a focus on more recent results. These results show both the continued usefulness of the AQM for atmospheric monitoring and also the current concerns, including: 1) the incorrect identification of benzene, 2) reporting of elevated isopropanol concentrations, and 3) the loss of the reactant ion peak (RIP) that must be resolved in order for the instrument to continue to serve as the primary trace VOC monitor on the ISS.

William T. Wallace↗
NASA NTRS2024

Assessing Acetone for the GISS ModelE2.1 Earth System Model

Acetone is an abundant volatile organic compound (VOC) in the atmosphere, with important influences on ozone and oxidation capacity. Direct sources include chemical production from other VOCs and anthropogenic emissions, terrestrial vegetation, biomass-burning emissions, and ocean production. Sinks include chemical loss, deposition onto the land surface, and ocean uptake. Acetone also has a lifetime that is long enough to allow transport and reactions with other compounds remote from its sources. The NASA Goddard Institute for Space Studies (GISS) Earth system model ModelE2.1 simulates a variety of Earth system interactions. Previously, acetone had a very simplistic representation in the ModelE chemical scheme. This study assesses a more sophisticated acetone scheme in which acetone is a full 3-dimensional tracer with explicit sources, sinks, and atmospheric transport. We first evaluate the new global acetone budget in the context of past literature. Estimated source and sink fluxes fall within the range of previous models, although total atmospheric burden and lifetime are at the lower end of the published literature. Acetone's new representation in ModelE2.1 also results in more realistic spatial and vertical distributions, which we compare against previous models and field observations. The seasonality of acetone-related processes was also studied in conjunction with field measurements, and these comparisons show promising agreement but also shortcomings at high-emission urban locations, where the model's resolution is too coarse to capture the true behavior. Finally, we conduct a variety of sensitivity studies that explore the influence of key parameters on the acetone budget and its global distribution. An impactful finding is that the production of acetone from precursor hydrocarbon oxidation has strong leverage on the overall chemical source, indicating the importance of accurate molar yields. Overall, our implementation is one that corroborates with previous studies and marks a significant improvement in the development of the acetone tracer in GISS ModelE2.1.

Acetone↗
NASA NTRS2024

False Cape Data Collection Annex, Solid Waste Management Unit 113, Limited Resource Conservation and Recovery Act Facility Investigation Report, Kennedy Space Center, Florida

This Resource Conservation and Recovery Act (RCRA) Facility Investigation (RFI) Report summarizes groundwater investigation activities performed between July 2020 and October 2023 at the False Cape Data Collection Annex (FCDC) (Solid Waste Management Unit [SWMU] 113) located at Kennedy Space Center, Florida. The purpose of the RFI is to characterize the nature and extent of volatile organic compound (VOC)-contaminated groundwater at FCDC; evaluate the fate and transport of VOC contamination; collect sufficient data to evaluate potential future requirements for the site, such as corrective measures, long term monitoring, or No Further Action; and conduct a human health preliminary risk evaluation (PRE) based on the groundwater data.

False Cape Data Collection Annex↗
NASA NTRS2024

Converter/Compressor Building Solid Waste Management Unit (SWMU) #89 Monitoring Well 21 Area Interim Measure Work Plan

This Work Plan details the approach and design for the Interim Measure (IM) to remediate groundwater within the MW21 Area where VOC concentrations exceed Florida Department of Environmental Protection Natural Attenuation Default Concentrations. The IM includes in-situ bioremediation via injection of emulsified vegetable oil (EVO) and emulsified zero-valent iron (EZVI). The in-situ bioremediation technology consists of injecting an electron donor substrate into the subsurface to promote microbial breakdown of VOCs. The EVO injections for this IM are designed based on the use of Provectus ERD-CH4, which is a vegetable oil/carbon substrate mixture. The EZVI injections for this IM are designed based on the use of Provectus EZVI-CH4. The IM treatment layout consists of nine injection locations of EVO at approximately 10-foot radius of influence (ROI) and three injections locations of EZVI at approximately 6-foot ROI. The injection method will be direct push using a DPT rig. The overall injection depths range from 7 to 17 ft bls. The 7 ft bls top depth is designed to be 2 ft below the water table to prevent substrates from reaching the top of the water table. Injections are planned to be implemented using 2 ft intervals and will take place using a bottom-up approach to 2 ft below the water table. This work plan further describes the IM design, injection calculations, performance monitoring plan, and provides an injection layout. Revision 1 of this Work Plan includes quarterly performance sampling during Year 1 in accordance with F.A.C. 62-780. These changes are reflected in Section 7 and Table 2 of the Work Plan.

Mark J Jonnet↗
NASA NTRS2022

Launch Complex 34, SWMU Cc054 2021 DNAPL Source Zone Operations, Maintenance, and 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) and Hot Spot 6 (HS 6) Air Sparge (AS) System presents the results of Year 12 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, 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. Site-wide biennial LTM sampling was not conducted during this reporting period and is scheduled to be conducted in December 2022. The timeframe for activities documented in this PMR extends from April 1, 2021 to March 31, 2022. 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 DSZ and deep 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 re-characterize the DSZ, which included investigating TCE mass in Layer 7. This data was subsequently used to optimize the pumping rates of the HCS to more adequately capture residual contaminant mass. The operational period for Year 12 of the HCS was from April 1, 2021 to March 31, 2022. Operational runtime for the system was 94 percent during Year 12, with downtime events attributed to planned maintenance, system repairs, and power outages. As of March 31, 2022, a total of 285,712,801 gallons of groundwater containing 84,933 pounds of VOCs have been removed by the HCS. Influent concentrations of TCE have decreased since startup from approximately 280,000 µg/L (January 2010) to 12,000 µg/L (March 2022). 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 2021 within the DSZ to evaluate TCE contamination. Groundwater samples were collected via DPT at nine locations, consistent with previous events in 2017, 2018, 2019, and 2020. Full vertical profile sampling was completed at each DPT from 8 to 98 ft 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 at depths ranging from 8 to 98 ft bls. An overall increasing trend of TCE concentrations was observed in DPT samples during this reporting period, which may be due to several recovery wells that were turned off during the AS Pilot Study in the DSZ that operated from July 2021 to February 2022 (documented separately from this report). The maximum TCE concentration in 2021 was 15,400,000 µg/L in the 58 ft bls depth interval at DPT597 (previous maximum result in 2020 was 1,690,000 at 48 ft bls at DPT596). During the 2021 DPT event, the overall majority of TCE contamination was identified in the 58 ft bls interval (below Layer 4), where in the previous year the majority of mass was observed in Layer 4. This trend appears to indicate continued mass discharge from Layer 4 (fine-grained unit). In addition to DPT sampling, monitoring well samples were collected from deep wells in the DSZ area (Layers 7 and 8) to verify vertical delineation. All monitoring well results were non-detect or below cleanup levels, with exception of one well (IW0162, screened 105 to 115 ft bls, which is below the existing recovery well capture zone) where TCE was identified above cleanup target levels. The HS 6 AS system remained operational during the reporting period covered under this report. 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 prior to this operational period. 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 2021 show concentrations of contaminants of concern (cis-1,2-dichloroethene, 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. Overall, the tasks associated with Year 12 operation of the HC IM and operation of the HS 6 AS IM were performed in accordance with the recommendations of the 2020 LC34 (Year 11) Operations, Maintenance, and Monitoring Report for DNAPL Source Zone, Site Wide LongTerm Monitoring, and Hot Spot 6 Air Sparging System PMR (NASA, 2021c). Evaluation of results from the HC IM and HS 6 IM show that these systems are operating as designed and meeting performance objectives.

trichloroethene↗
NASA NTRS2024

Paint and Oil Locker SWMU 067 Southern Treatment Area Air Sparge System Year 2 Performance Monitoring and Paint and Oil Locker Northern Area (SWMU 067) and Supply Warehouse #3, SWMU 088 Long-Term Monitoring Kennedy Space Center, Florida

This Year 2 Air Sparge (AS) System Performance Monitoring (PM) Report for Paint and Oil Locker (POL) Solid Waste Management Unit (SWMU) 067 Southern Treatment Area and Long- Term Monitoring (LTM) Report for POL Northern Area (SWMU 067) and Supply Warehouse #3 (SW3) SWMU 088 documents ongoing remedial efforts at the POL and SW3 sites at Kennedy Space Center (KSC), Florida. The overall goal for these sites is to reduce concentrations of groundwater contaminants of concern (COCs), specifically trichloroethene (TCE), cis-1,2-dichloroethene (cDCE), trans-1,2-dichloroethene (tDCE) and vinyl chloride (VC), to below the State of Florida Groundwater Cleanup Target Levels (GCTLs). Remediation and reporting of POL and SW3 have been streamlined over the years due to the proximity of the two sites. The scope for these sites currently includes two main components: (1) LTM at SW3 and the POL Northern Area, where an AS system began operation in May 2009 (with expansion in December 2012) and June 2013, respectively, and subsequently turned off for both sites in March 2018 (NASA, 2019a); and (2) Active AS operations and PM in the POL Southern Treatment Area where an AS system was installed and began operation in 2021. The timeframe for activities covered under this report is from September 2022 to July 2023. Based on Year 2 system operation and PM results, the AS system at POL operated as designed and successfully met the performance objective of reducing VOCs to concentrations that support transition of the site from active remediation to long-term monitoring. The results from the samples collected from performance monitoring wells within the AS system ROI showed a significant decrease in COC concentrations since the baseline sampling event conducted in April 2020. Based on the Year 2 OM&M and monitoring results obtained from the POL Southern Treatment Area, the IM objective to reduce concentrations to below the LTM transition target concentrations for TCE, cDCE, tDCE, and VC has been achieved. LTM sampling events at SW3 were conducted in October 2022 and July 2023. LTM sampling was conducted at the POL Northern Area in October 2022, December 2022, March 2023, and July 2023. Analytical results from October 2022 and July 2023 generally indicate that concentrations of COCs have been stable or decreasing compared to the previous year. TCE remains greater than the NADC in one monitoring well (POL-MW0034S) and greater than the GCTL in one monitoring well (POL-MW0009S). Concentrations of cDCE were greater than the GCTL in one monitoring well (POL-MW0026S), and tDCE was non-detect or less than the GCTL in all monitoring wells sampled. VC was greater than the GCTL in four monitoring wells (MW0024, MW0025, MW0027, and MW0028) at SW3 and one monitoring well (MW0026S) at the POL Northern Area.

remediation↗
NASA NTRS1977

A first order theory of the p/+/-n-n/+/ edge-illuminated silicon solar cell at very high injection levels

A first order theory of the edge-illuminated p(+)-n-n(+) silicon solar cell under very high injection levels has been derived. The very high injection level illuminated J-V characteristic is derived for any general base width to diffusion length (W/L) ratio and it includes the minority carrier reflection by the n-n(+) high-low junction. The beneficial effects of the high-low junction are shown to be significant until extremely high injection levels are reached. The theoretical dependencies of Jsc and Voc on temperature, incident intensity, and base resistivity are derived and discussed in detail. Some experimental results are given and these are discussed in relation to the theory.

Goradia, C.↗
NASA NTRS1978

A simple theory of back surface field /BSF/ solar cells

A theory of an n-p-p/+/ junction is developed, entirely based on Shockley's depletion layer approximation. Under the further assumption of uniform doping the electrical characteristics of solar cells as a function of all relevant parameters (cell thickness, diffusion lengths, etc.) can quickly be ascertained with a minimum of computer time. Two effects contribute to the superior performance of a BSF cell (n-p-p/+/ junction) as compared to an ordinary solar cell (n-p junction). The sharing of the applied voltage among the two junctions (the n-p and the p-p/+/ junction) decreases the dark current and the reflection of minority carriers by the builtin electron field of the p-p/+/ junction increases the short-circuit current. The theory predicts an increase in the open-circuit voltage (Voc) with a decrease in cell thickness. Although the short-circuit current decreases at the same time, the efficiency of the cell is virtually unaltered in going from a thickness of 200 microns to a thickness of 50 microns. The importance of this fact for space missions where large power-to-weight ratios are required is obvious.

Von Roos, O.↗