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All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Observations of ozone, acyl peroxy nitrates, and their precursors during summer 2019 at Carlsbad Caverns National Park, New Mexico

Carlsbad Caverns National Park (CAVE) is located in southeastern New Mexico and is adjacent to the Permian Basin, one of the most productive oil and natural gas (O&G) production regions in the United States. Since 2018, ozone (O 3 ) at CAVE has frequently exceeded the 70 ppbv 8-hour National Ambient Air Quality Standard. We examine the influence of regional emissions on O 3 formation using observations of O 3 , nitrogen oxides (NO x = NO + NO 2 ), a suite of volatile organic compounds (VOCs), peroxyacetyl nitrate (PAN), and peroxypropionyl nitrate (PPN). Elevated O 3 and its precursors are observed when the wind is from the southeast, the direction of the Permian Basin. We identify 13 days during the July 25 to September 5, 2019 study period when the maximum daily 8-hour average (MDA8) O 3 exceeded 65 ppbv; MDA8 O 3 exceeded 70 ppbv on 5 of these days. The results of a positive matrix factorization (PMF) analysis are used to identify and attribute source contributions of VOCs and NO x . On days when the winds are from the southeast, there are larger contributions from factors associated with primary O&G emissions; and, on high O 3 days, there is more contribution from factors associated with secondary photochemical processing of O&G emissions. The observed ratio of VOCs to NO x is consistently high throughout the study period, consistent with NO x -limited O 3 production. Finally, all high O 3 days coincide with elevated acyl peroxy nitrate abundances with PPN to PAN ratios > 0.15 ppbv ppbv -1 indicating that anthropogenic VOC precursors, and often alkanes specifically, dominate the photochemistry. Implications: The results above strongly indicate NO x -sensitive photochemistry at Carlsbad Caverns National Park indicating that reductions in NO x emissions should drive reductions in O 3 . However, the NO x -sensitivity is largely driven by emissions of NO x into a VOC-rich environment, and a high PPN:PAN ratio and its relationship to O 3 indicate substantial influence from alkanes in the regional photochemistry. Thus, simultaneous reductions in emissions of NO x and non-methane VOCs from the oil and gas sector should be considered for reducing O 3 at Carlsbad Caverns National Park. Reductions in non-methane VOCs will have the added benefit of reducing formation of other secondary pollutants and air toxics.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2023

Source characterization of volatile organic compounds at Carlsbad Caverns National Park

Carlsbad Caverns National Park (CAVE), located in southeastern New Mexico, experiences elevated ground-level ozone (O 3 ) exceeding the National Ambient Air Quality Standard (NAAQS) of 70 ppbv. It is situated adjacent to the Permian Basin, one of the largest oil and gas (O&G) producing regions in the US. In 2019, the Carlsbad Caverns Air Quality Study (CarCavAQS) was conducted to examine impacts of different sources on ozone precursors, including nitrogen oxides (NO x ) and volatile organic compounds (VOCs). Here, we use positive matrix factorization (PMF) analysis of speciated VOCs to characterize VOC sources at CAVE during the study. Seven factors were identified. Three factors composed largely of alkanes and aromatics with different lifetimes were attributed to O&G development and production activities. VOCs in these factors were typical of those emitted by O&G operations. Associated residence time analyses (RTA) indicated their contributions increased in the park during periods of transport from the Permian Basin. These O&G factors were the largest contributor to VOC reactivity with hydroxyl radicals (62%). Two PMF factors were rich in photochemically generated secondary VOCs; one factor contained species with shorter atmospheric lifetimes and one with species with longer lifetimes. RTA of the secondary factors suggested impacts of O&G emissions from regions farther upwind, such as Eagle Ford Shale and Barnett Shale formations. The last two factors were attributed to alkenes likely emitted from vehicles or other combustion sources in the Permian Basin and regional background VOCs, respectively. Implications: Carlsbad Caverns National Park experiences ground-level ozone exceeding the National Ambient Air Quality Standard. Volatile organic compounds are critical precursors to ozone formation. Measurements in the Park identify oil and gas production and development activities as the major contributors to volatile organic compounds. Emissions from the adjacent Permian Basin contributed to increases in primary species that enhanced local ozone formation. Observations of photochemically generated compounds indicate that ozone was also transported from shale formations and basins farther upwind. Therefore, emission reductions of volatile organic compounds from oil and gas activities are important for mitigating elevated O 3 in the region.

54 ENVIRONMENTAL SCIENCES↗
NASA NTRS2016

Wilson Corners SWMU 001 2015 Annual Long Term Monitoring Report Kennedy Space Center, Florida

This document presents the findings of the 2015 Long Term Monitoring (LTM) that was completed at the Wilson Corners site, located at the National Aeronautics and Space Administration John F. Kennedy Space Center, Florida. The objectives of the 2015 LTM event were to evaluate the groundwater flow direction and gradient, to monitor the vertical and horizontal extent of the volatile organic compounds (VOCs; including the upgradient and sidegradient extents, which are monitored every five years), and to monitor select locations internal to the dissolved groundwater plume. The 2015 LTM event included several upgradient and sidegradient monitoring wells that are not sampled annually to verify the extent of VOCs in this portion of the site. The December 2015 LTM groundwater sampling event included, depth to groundwater measurements, 40 VOC samples collected using passive diffusion bags, and one VOC sample collected using low-flow techniques. Additionally, monitoring well MW0052DD was overdrilled and abandoned using rotasonic drilling techniques. The following conclusions can be made based on the 2015 LTM results: groundwater flow is generally to the west with northwest and southwest flow components from the water table to approximately 55 feet below land surface (ft BLS); peripheral monitoring wells generally delineate VOCs to groundwater cleanup target levels (GCTLs) except for monitoring wells MW0088, MW0090, MW0095, and NPSHMW0039, which had vinyl chloride (VC) concentrations near the GCTL and MW0062, which had trichloroethene (TCE), cis-1,2-dichloroethenen (cDCE), and VC concentrations above natural attenuation default concentrations (NADCs); VOCs in interior downgradient wells generally fluctuate within historic ranges except for monitoring wells in the north-northwest portion of the site, which have increasing VC concentrations indicating potential plume migration and expansion; Historically, the vertical extents of the VOCs were delineated by monitoring wells screened greater than 60 ft BLS (MW0083 through MW0086, and MW0078). The 2015 LTM results indicate that concentrations of daughter product cDCE is greater than the NADC in MW0078 and that cDCE and VC are greater than NADCs in MW0130. TCE was greater than the GCTL in monitoring well MW130 and not detected above method detection limits (9 micrograms per Liter) in monitoring well MW0078. No GCTL exceedances were identified in monitoring wells MW0083 or MW0086; the dissolved plume footprint appears generally stable, though not fully delineated by monitoring well data in the northeast portion of the site; and 2015 LTM results generally support the existing Conceptual Site Model. Geosyntec recommends modifying the LTM program, collecting a verification sample from monitoring well MW0062, and performing a direct push technology instigation in the northnortheastern portion of the site. A cluster of monitoring wells (MW0132 [2 to 12 ft BLS], MW0133 [15 to 25 ft BLS], and MW0134 [29 to 34 ft BLS]) is proposed to delineate impacts in the northnortheast portion of the site. Geosyntec recommends installation of a vertical extent well in the center of the site (Hot Spot 2 area) post-remediation implementation.

groundwater↗
NASA NTRSDate not supplied

Plasma Abatement of Volatile Organic Compounds

One difficulty with crewed space operations is the potential for the contamination of the spacecraft habitable volume from volatile organic compounds (VOCs) that may be present. One possible VOC abatement process is to apply a plasma to the contaminated gases. Plasmas provide high energy electrons and ions that are capable of breaking down gaseous organic species generally into smaller compounds. To explore plasma VOC abatement, the authors constructed a plasma gas system that recirculates a particular VOC-laden gas mixture through a plasma torch. This allows for the periodic collection of aliquots of gaseous samples for subsequent analyses via gas chromatography mass spectrometry, designed to quantify the remaining VOC materials. The VOCs evaluated included 100 ppm of acetone, benzene, ethanol, and pentane in a background of carbon dioxide. The plasma conversion of all analytes followed first-order rate kinetics, and VOC elimination was observed after 10 min or less of treatment for all analytes measured. Additionally, it was observed that the plasma caused the conversion of CO 2 into oxygen and CO.

Joel A. Olson↗
DOE OSTI2022

Capturing the microbial volatilome: an oft overlooked 'ome'

Among the diverse metabolites produced by microbial communities, some are volatile. Volatile organic compounds (VOCs) are vigorously cycled by microbes as metabolic substrates and products and as signaling molecules. Yet, current microbial metabolomic studies predominantly focus on nonvolatile metabolites and overlook VOCs, which therefore represent a missing component of the metabolome. Advances in VOC detection now allow simultaneous observation of the numerous VOCs constituting the ‘volatilome’ of microbial systems. Here, we present a roadmap for integrating and advancing VOC and other ‘omics approaches and highlight the potential for realtime VOC measurements to help overcome limitations in discrete ‘omics sampling. Including volatile metabolites in metabolomics, both conceptually and in practice, will build a more comprehensive understanding of microbial processes across ecological communities.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2020

Functional metal–organic frameworks as effective sensors of gases and volatile compounds

Developing efficient sensor materials with superior performance for selective, fast and sensitive detection of gases and volatile organic compounds (VOCs) is essential for human health and environmental protection, through monitoring indoor and outdoor air pollutions, managing industrial processes, controlling food quality and assisting early diagnosis of diseases. Metal–organic frameworks (MOFs) are a unique type of crystalline and porous solid material constructed from metal nodes (metal ions or clusters) and functional organic ligands. They have been investigated extensively for possible use as high performance sensors for the detection of many different gases and VOCs in recent years, due to their large surface area, tunable pore size, functionalizable sites and intriguing properties, such as electrical conductivity, magnetism, ferroelectricity, luminescence and chromism. The high porosity of MOFs allows them to interact strongly with various analytes, including gases and VOCs, thus resulting in easily measurable responses to different physicochemical parameters. Although much of the recent work on MOF-based luminescent sensors have been summarized in several excellent reviews (up to 2018), a comprehensive overview of these materials for sensing gases and VOCs based on chemiresistive, magnetic, ferroelectric, and colorimertic mechanisms is missing. In this review, we highlight the most recent progress in developing MOF sensing and switching materials with an emphasis on sensing mechanisms based on electricity, magnetism, ferroelectricity and chromism. We provide a comprehensive analysis on the MOF–analyte interactions in these processes, which play a key role in the sensing performance of the MOF-based sensors and switches. We discuss in detail possible applications of MOF-based sensing and switching materials in detecting oxygen, water vapor, toxic industrial gases (such as hydrogen sulfide, ammonia, sulfur dioxide, nitrous oxide, carbon oxides and carbon disulfide) and VOCs (such as aromatic and aliphatic hydrocarbons, ketones, alcohols, aldehydes, chlorinated hydrocarbons and N,N'-dimethylformamide). Altogether, this review serves as a timely source of information and provides insight for the future development of advanced MOF materials as next-generation gas and VOC sensors.

36 MATERIALS SCIENCE↗
NASA NTRS2014

Native Fluorescence Detection Methods and Detectors for Naphthalene and/or Other Volatile Organic Compound Vapors

Naphthalene, benzene, toluene, xylene, and other volatile organic compounds have been identified as serious health hazards. This is especially true for personnel working with JP8 jet fuel and other fuels containing naphthalene as well as other hazardous volatile organic compounds (VOCs). Embodiments of the invention are directed to methods and apparatus for near-real-time in-situ detection and accumulated dose measurement of exposure to naphthalene vapor and other hazardous gaseous VOCs. The methods and apparatus employ excitation of fluorophors native or endogenous to compounds of interest using light sources emitting in the ultraviolet below 300 nm and measurement of native fluorescence emissions in distinct wavebands above the excitation wavelength. The apparatus of some embodiments are cell-phone-sized sensor/dosimeter "badges" to be worn by personnel potentially exposed to naphthalene or other hazardous VOCs. The badge sensor of some embodiments provides both real time detection and data logging of exposure to naphthalene or other VOCs of interest from which both instantaneous and accumulated dose can be determined. The badges employ a new native fluorescence based detection method to identify and differentiate VOCs. The particular focus of some embodiments are the detection and identification of naphthalene while other embodiments are directed to detection and identification of other VOCs like aromatic hydrocarbons such as benzene, toluene, and xylene.

Hug, William F.↗
NASA NTRSDate not supplied

Plasma Abatement of Volatile Organic Compounds for Treatment of Spacecraft Trash Combustion Gaseous Effluents.

One approach that has been investigated for trash management aboard long-duration crewed exploration space missions is the so-called Trash-to-Gas approach. This technology uses a thermal process (i.e., combustion, pyrolysis, etc.) to convert crew trash into relatively non-reactive gases (i.e., CO2, CO, etc.) that can be easily vented overboard. One difficulty with this approach is the potential for the contamination of the spacecraft habitable volume from the myriad volatile organic compounds (VOCs) that are concurrently produced from these thermal processes. One possible VOC abatement process is to apply a plasma to the effluent gases. Plasmas provide high energy electrons and ions that are capable of breaking down gaseous organic species generally into smaller compounds. To explore Plasma VOC abatement, the authors constructed a plasma gas system that recirculates a particular VOCladen gas mixture through a plasma torch. This allows the periodic collection of aliquots of gaseous samples for subsequent analyses via gas chromatography mass spectrometry, designed to quantify the remaining VOC materials. The VOCs evaluated included 100 ppm of acetone, benzene, ethanol, and pentane in a background of carbon dioxide. The plasma conversion of all analytes followed first order rate kinetics, and complete VOC elimination was observed after 10 min or less of treatment, for all analytes measured. Additionally, it was observed that the plasma caused the conversion of CO2 into oxygen and CO.

Joel A. Olson↗
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 NTRS2023

General Services Administration Reclamation Yard Solid Waste Management Unit 010: 2022 Groundwater Monitoring Report Kennedy Space Center, Florida

This report presents a summary of the groundwater monitoring activities that occurred in September and October 2022 at General Services Administration Reclamation Yard, Solid Waste Management Unit 010, located at the John F. Kennedy Space Center (KSC), Florida. The site is monitored under KSC’s Resource Conservation and Recovery Act Corrective Action Program. This approach also meets the requirements of Chapter 62-780, Florida Administrative Code. For the purposes of this report, two separate plumes, known as the Polychlorinated Biphenyl (PCB)/Volatile Organic Aromatic (VOA) Plume and the Chlorinated Volatile Organic Compound (VOC) Plume, were identified for this site. The contaminants of concern (COCs) for the PCB/VOA Plume consist of PCBs, 1,2,4-trichlorobenzene, and breakdown products of 1,2,4-trichlorobenzene. The COCs for the Chlorinated VOC Plume were tetrachloroethene, trichloroethene, cis-1,2-dichloroethene, and vinyl chloride. Groundwater monitoring for VOCs in the Chlorinated VOC Plume area was discontinued following the December 2021 annual monitoring event. Annual groundwater monitoring for underground injection control (UIC) parameters continues for both the PCB/VOA Plume and the Chlorinated VOC Plume areas. The activities presented in this report include one field event: September and October 2022, which includes sitewide semi-annual water level measurements of 55 monitoring wells, redevelopment of all monitoring wells listed in the sampling plan, and groundwater sampling of 28 monitoring wells. The sampling and analysis demonstrated that the PCB/VOA plume is not expanding and is significantly reduced compared to before a 2018 source removal interim measure. Recommendations are made for the 2023 groundwater monitoring program.

groundwater↗
NASA NTRS2023

Sources of Formaldehyde in U.S. Oil and Gas Production Regions

We analyzed observational and model data to study the sources of formaldehyde over oil and gas production regions and to investigate how these observations may be used to constrain oil and gas VOC emissions. The analysis of aircraft and satellite data consistently found that formaldehyde over oil and gas production regions during spring and summer is mostly formed by the photooxidation of precursor VOCs. Formaldehyde columns over the Permian basin, one of the largest oil and gas producing regions in the United States, are correlated with production locations. Formaldehyde simulations by the atmospheric chemistry and transport model WRF-Chem, which included oil and gas NOx and VOC emissions from the fuel-based oil and gas inventory, were in very good agreement with TROPOMI satellite measurements. Sensitivity studies illustrated that VOCs released from oil and gas activities are important precursors to formaldehyde, but other sources of VOCs contribute as well, and that the formation of secondary formaldehyde is highly sensitive to NOx. We also investigated the ability of the chemical mechanism used in WRF-Chem to represent formaldehyde formation from oil and gas hydrocarbons by comparing against the Master Chemical Mechanism. Further, our work provides estimates of primary formaldehyde emissions from oil and gas production activities, with per basin averages ranging from 0.07 kg h -1 to 2.2 kg h -1 in 2018. A separate estimate for natural gas flaring found that flaring emissions could contribute 5% to 12% to the total primary formaldehyde emissions for the Permian basin in 2018.

SAF↗
DOE OSTI2023

Chemical Characterization of Natural Gas Leaking from Abandoned Oil and Gas Wells in Western Pennsylvania

The U.S. Environmental Protection Agency estimates that there are over 3.2 million abandoned wells in the United States. Studies conducted on gas emissions from abandoned wells have been limited to methane, a powerful greenhouse gas, due to concerns regarding climate change. However, volatile organic compounds (VOCs), including benzene, a known human carcinogen, are known to be associated with upstream oil and gas development and hence could also be released when methane is emitted to the atmosphere. In this investigation, we analyze gas from 48 abandoned wells in western Pennsylvania for fixed gases, light hydrocarbons, and VOCs and estimate associated emission rates. We demonstrate that (1) gas from abandoned wells contains VOCs, including benzene; (2) VOCs are emitted from abandoned wells, the magnitude of which depends on the flow rate and concentration of VOCs in the gas stream; and (3) nearly one-quarter of abandoned wells are located within 100 m of buildings, including residences, in Pennsylvania. Together, these observations indicate that further investigation is necessary to determine whether emissions from abandoned wells pose an inhalation risk to people living, working, or congregating near abandoned wells.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Henry’s Solubility and Diffusion Coefficients for 29 Volatile Organic Compounds in Polydimethylsiloxane Sylgard 184 at 293 K

Two-dimensional (2D) inverse gas chromatography (IGC) enables simultaneous determination of Henry’s solubility and Fickian diffusion coefficients for volatile organic compounds (VOCs) in polymer films. This technique offers a significant advantage over traditional cylindrical column IGC by providing precise control and measurement of the film thickness (here, 0.064 ± 0.002 mm), which is the critical length scale for accurate diffusivity determination. We apply this methodology to characterize VOC transport in Sylgard 184, a widely used polydimethylsiloxane (PDMS)-based polymer containing substantial silica filler content. At room temperature (20 °C), we measured solubility and diffusion coefficients for 29 common VOCs spanning diverse chemical functionalities, including alkanes, aromatics, chlorinated solvents, ketones, esters, and alcohols. Comparison with literature data for pure PDMS reveals that VOC solubility in Sylgard 184 is generally higher; for most non-hydrogen-bonding compounds it remains within a factor of 2 of pure PDMS, whereas alcohols are enhanced by roughly 1.8 to 3.7 times, which we attribute to favorable interactions with residual silanol groups on the silanized silica filler. Diffusion coefficients range from 1.0 × 10 –6 cm 2 /s (n-undecane) to 8.9 × 10–5 cm 2 /s (acetonitrile) and align well with extrapolated literature values for PDMS. This study provides essential thermodynamic and transport data for predicting VOC permeation in Sylgard 184 while demonstrating the utility of 2D IGC as a robust technique for characterizing rubbery polymer membranes across diverse industrial applications.

organic↗
DOE OSTI2023

Site specific N- and O-glycosylation mapping of the spike proteins of SARS-CoV-2 variants of concern

Abstract The glycosylation on the spike (S) protein of the severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2), the virus that causes COVID-19, modulates the viral infection by altering conformational dynamics, receptor interaction and host immune responses. Several variants of concern (VOCs) of SARS-CoV-2 have evolved during the pandemic, and crucial mutations on the S protein of the virus have led to increased transmissibility and immune escape. In this study, we compare the site-specific glycosylation and overall glycomic profiles of the wild type Wuhan-Hu-1 strain (WT) S protein and five VOCs of SARS-CoV-2: Alpha, Beta, Gamma, Delta and Omicron. Interestingly, both N- and O-glycosylation sites on the S protein are highly conserved among the spike mutant variants, particularly at the sites on the receptor-binding domain (RBD). The conservation of glycosylation sites is noteworthy, as over 2 million SARS-CoV-2 S protein sequences have been reported with various amino acid mutations. Our detailed profiling of the glycosylation at each of the individual sites of the S protein across the variants revealed intriguing possible association of glycosylation pattern on the variants and their previously reported infectivity. While the sites are conserved, we observed changes in the N- and O-glycosylation profile across the variants. The newly emerged variants, which showed higher resistance to neutralizing antibodies and vaccines, displayed a decrease in the overall abundance of complex-type glycans with both fucosylation and sialylation and an increase in the oligomannose-type glycans across the sites. Among the variants, the glycosylation sites with significant changes in glycan profile were observed at both the N -terminal domain and RBD of S protein, with Omicron showing the highest deviation. The increase in oligomannose-type happens sequentially from Alpha through Delta. Interestingly, Omicron does not contain more oligomannose-type glycans compared to Delta but does contain more compared to the WT and other VOCs. O-glycosylation at the RBD showed lower occupancy in the VOCs in comparison to the WT. Our study on the sites and pattern of glycosylation on the SARS-CoV-2 S proteins across the VOCs may help to understand how the virus evolved to trick the host immune system. Our study also highlights how the SARS-CoV-2 virus has conserved both N - and O - glycosylation sites on the S protein of the most successful variants even after undergoing extensive mutations, suggesting a correlation between infectivity/ transmissibility and glycosylation.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2020

Rapid Patterning and Advanced Device Structures for Low Cost Manufacturable Crystalline Si IBC Cells

Recent record efficiency Si cells have had an interdigitated back contact (IBC) design where both positive and negative contacts are fabricated on the back side of the Si wafer. Many industry groups have investigated IBC cells but used photolithography to pattern the rear contacts although it is considered impractical for low cost, high volume manufacturing. Alternative patterning methods using lasers and mechanical masking have been utilized in fabrication of patterned regions in IBC Si solar cells to replace photolithography. Another exciting advance in Si solar cell technology has been replacing the high temperature diffusion of doped regions inside the crystalline Si wafer with low temperature deposition of very thin layers of doped amorphous hydrogenated Si (a-Si:H) on the Si wafer. This is called a Si heterojunction (HJ) device. The a-Si:H provides excellent passivation of surface defects and has produced the highest open circuit voltages (VOC) of any Si solar cell device structure. The Institute of Energy Conversion (IEC) demonstrated the first IBC-HJ solar cell combining these two strategies in 2007 and has fabricated IBC-HJ cells with 20% efficiency using three photolithography steps. Despite the demonstrated efficiency potential of this device by industry groups (>26%) there is no commercial production because of the challenges of patterning and processing the structure in an industrial environment. Our work sought to address that challenge. The objective of this 3 year project was to develop the processing for the IBC-HJ Si solar cell using lasers for patterning and contact formation instead of photolithography. Laser patterning enables rapid, contactless manufacturing of patterned regions. We intensively studied laser fired contacts, laser patterning of the a-Si multi-layer stacks and metal layers and the use of plasma shadow masks. After an exhaustive focus in the first year on the laser fired emitter (LFE) and contact (LFC), we were unable to achieve VOC greater than 660 mV, compared to the 720 mV required to meet our milestones. We discovered that an additional issue with our original IBC structure was the presence of an inversion layer at the back surface connecting the p and n regions which reduced the VOC and fill factor (FF). We developed innovative methods for characterizing the inversion layer. These two limitations in the original design lead to development of a new IBC-HJ process sequence and device structure which we called Plasma Masked Laser Processed (PMLP). It retained the original high efficiency features including manufacturability. The LFC was replaced with a standard n-type a-Si HJ contact. The inversion layer was eliminated by replacing the previous p-type stack in the gap with an n-type or SiN stack. The PMLP used laser ablation of a multi-layer a-Si stack followed by chemical etching to open the n-contact. It required deposition of a patterned stack through a mask in the plasma deposition chamber. This turned out to be a source of significant problems due to inevitable unwanted deposition ‘leakage’ under the mask. This formed a blocking contact on the emitter which significantly reduced Voc and FF. Several iterations in PMLP device structure and chemical etching steps resulted in a large improvements, e.g. the efficiency increasing from 3 to 15% and Voc from 450 to 660 mV but they were unable to completely eliminate it. The best IBC-HJ device we fabricated had only 15% efficiency. For perspective, our standard FHJ devices had 20% efficiency.

14 SOLAR ENERGY↗
NASA NTRS1995

Evaluations of an Enhanced Total Hydrocarbon Analyzer With Complex Mixtures of Volatile Organic Compounds

From the earliest manned missions, the volatile organic compound (VOC) content of spacecraft air has been a concern because of a much greater potential for contamination than air in most terrestrial settings. First, the volume of air is small compared to the mass of man- made materials comprising the interior furnishings of the spacecraft. These man-made materials offgas VOCs trapped during manufacture. Second, the nitrogen fraction of the air is recycled. Any VOCs not scrubbed out with charcoal filters or aqueous condensate (mainly water expired by the crew) will accumulate in the air. Third, the crew emits metabolic VOCs. Fourth, experimental payloads can also offgas or accidentally release a VOC; in fact a major organic constituent of the atmosphere is the disinfectant isopropanol released from swabs used in medical experiments.

Cross, John H.↗
NASA NTRS2015

Wilson Corners SWMU 001 2014 Annual Long Term Monitoring Report Kennedy Space Center, Florida

This document presents the findings of the 2014 Long Term Monitoring (LTM) that was completed at the Wilson Corners site, located at the National Aeronautics and Space Administration (NASA) John F. Kennedy Space Center (KSC), Florida. The goals of the 2014 annual LTM event were to evaluate the groundwater flow direction and gradient and to monitor the vertical and downgradient horizontal extent of the volatile organic compounds (VOCs) in groundwater at the site. The LTM activities consisted of an annual groundwater sampling event in December 2014, which included the collection of water levels from the LTM wells. During the annual groundwater sampling event, depth to groundwater was measured and VOC samples were collected using passive diffusion bags (PDBs) from 30 monitoring wells. In addition to the LTM sampling, additional assessment sampling was performed at the site using low-flow techniques based on previous LTM results and assessment activities. Assessment of monitoring well MW0052DD was performed by collecting VOC samples using low-flow techniques before and after purging 100 gallons from the well. Monitoring well MW0064 was sampled to supplement shallow VOC data north of Hot Spot 2 and east of Hot Spot 4. Monitoring well MW0089 was sampled due to its proximity to MW0090. MW0090 is screened in a deeper interval and had an unexpected detection of trichloroethene (TCE) during the 2013 LTM, which was corroborated during the March 2014 verification sampling. Monitoring well MW0130 was sampled to provide additional VOC data beneath the semi-confining clay layer in the Hot Spot 2 area.

Monitoring↗
NASA NTRS2020

Constraining Remote Oxidation Capacity with ATom Observations

The global oxidation capacity, defined as the tropospheric mean concentration of the hydroxyl radical (OH), controls the lifetime of reactive trace gases in the atmosphere such as methane and carbon monoxide (CO). Models tend to underestimate the methane lifetime and CO concentrations throughout the troposphere, which is consistent with excessive OH. Approximately half the oxidation of methane and non-methane volatile organic compounds (VOCs) is thought to occur over the oceans where oxidant chemistry has received little validation due to a lack of observational constraints. We use observations from the first two deployments of the NASA ATom aircraft campaign during July–August 2016 and January–February 2017 to evaluate the oxidation capacity over the remote oceans and its representation in the GEOS-Chem chemical transport model. The model successfully simulates the magnitude and vertical profile of remote OH within the measurement uncertainties. Comparisons against the drivers of OH production (water vapor, ozone, and NOy concentrations, ozone photolysis frequencies) also show minimal bias with the exception of wintertime NOy, for which a model overestimate may indicate insufficient wet scavenging and/or missing loss on seasalt aerosol but large uncertainties remain that require further studies of NOy partitioning and removal in the troposphere. During the ATom-1 deployment, OH reactivity (OHR) below 3 km is significantly enhanced, and this is not captured by the sum of its measured components (cOHRobs) or by the model (cOHRmod). This enhancement could suggest missing reactive VOCs but cannot be explained by new estimates of ocean VOC sources and additional modeled reactivity in this region would be difficult to reconcile with the full suite of ATom measurement constraints. The model generally reproduces the magnitude and seasonality of cOHRobs but underestimates the contribution of oxygenated VOC, mainly acetaldehyde, which is severely underestimated throughout the troposphere despite its calculated lifetime of less than a day. Missing model acetaldehyde in previous studies was attributed to measurement uncertainties that have been largely resolved. Observations of peroxyacetic acid (PAA) provide new support for remote levels of acetaldehyde. The underestimate in modeled acetaldehyde and PAA is present throughout the year in both hemispheres and peaks during Northern Hemisphere summer. The addition of ocean VOC sources in the model increases annual surface cOHRmod by 10 % and improves model-measurement agreement for acetaldehyde particularly in winter but cannot resolve the model summertime bias. Doing so would require a 100 Tg yr−1 source of a long-lived unknown precursor throughout the year with significant additional emissions in the Northern Hemisphere summer. Improving the model bias for remote acetaldehyde and PAA is unlikely to fully resolve previously reported model global biases in OH and methane lifetime, suggesting that future work should examine the sources and sinks of OH over land.

Travis, Katherine R.↗