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DOE OSTI2024

Air quality impacts from the development of unconventional oil and gas well pads: Air toxics and other volatile organic compounds

Unconventional oil and natural gas development (UOGD) has expanded rapidly across the United States in recent decades and raised concerns about associated air quality impacts. While significant effort has been made to quantify methane emissions, relatively few observations have been made of Volatile Organic Compounds (VOCs), especially during drilling and completion of new wells. Extensive air monitoring during development of several large, multi-well pads in Broomfield, Colorado, in the Denver-Julesburg Basin, provides a novel opportunity to examine changes in local air toxics and other VOC concentrations during well drilling and completions and production. These operations offer an especially useful case to study as several management practices were implemented to reduce emissions (e.g., electrified, grid-powered drill rigs and closed loop fluid handling systems to reduce truck traffic and limit fluid handling on the pad). With simultaneous measurements of methane and 50 VOCs from October 2018 to December 2022 at as many as 19 sites near well pads, in adjacent neighborhoods, and at a more distant reference location, we identify impacts from each phase of well development and production. Use of weekly, time-integrated canisters, a Proton Transfer Reaction Mass Spectrometer (PTR-MS), continuous photoionization detectors (PID) to trigger canister collection upon detection of VOC-rich plumes, and an instrumented vehicle, provided a powerful suite of measurements to characterize both transient plumes and longer-term changes in air quality. Prior to the start of well development, VOC gradients were small across Broomfield. Once drilling commenced, concentrations of oil and gas (O&G) related VOCs, including alkanes and aromatics, increased around active well pads. Concentration increases were clearly apparent during certain operations, including drilling, coil tubing/millout operations, and production tubing installation. Emissions of C 8 –C 10 n-alkanes during drilling operations highlighted the importance of VOC emissions from synthetic drilling mud chosen to reduce odor impacts. More than 90 samples were collected of transient plumes. Using composition measurements, meteorological data, and information about well pad activities, these plumes were connected with specific UOGD operations including drilling, flowback, and production equipment maintenance. The chemical signatures of these plumes differed by operation type (e.g., C 8 –C 10 n-alkanes constituted a larger fraction of measured VOCs in drilling-related plumes). Concentrations of individual, oil and gas-related VOCs in these plumes were often several orders of magnitude higher than in background air, with maximum ethane and benzene concentrations of 79,600 and 819 ppbv, respectively. Because these plumes typically impact a monitoring site for just several minutes, they are easily missed by slower-responding instruments. Study measurements highlight future emission mitigation opportunities during UOGD operations, including better control of emissions from shakers that separate drill cuttings from drilling mud, production separator maintenance operations, and periodic emptying of sand cans during flowback operations.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2025

Measurement report: Extreme heat and wildfire emissions enhance volatile organic compounds in a temperate forest

Climate extremes are projected to cause unprecedented deviations in the emission and transformation of volatile organic compounds (VOCs), which trigger feedback mechanisms that will impact the atmospheric oxidation and formation of aerosols and clouds. However, the response of VOCs to future conditions such as extreme heat and wildfire events is still uncertain. This study explored the modification of the mixing ratio and distribution of several anthropogenic and biogenic VOCs in a temperate oak–hickory–juniper forest as a response to increased temperature and transported biomass burning plumes. A chemical ionization mass spectrometer was deployed on a tower at a height of 32 m in rural central Missouri, United States, for the continuous and in situ measurement of VOCs from June to August of 2023. The maximum observed temperature in the region was 38 °C, and during multiple episodes the temperature remained above 32 °C for several hours. Biogenic VOCs such as isoprene and monoterpene followed closely the temperature daily profile but at varying rates, whereas anthropogenic VOCs were insensitive to elevated temperature. During the measurement period, wildfire emissions were transported to the site and substantially increased the mixing ratios of acetonitrile and benzene, which are produced from burning of biomass. An in-depth analysis of the mass spectra revealed more than 250 minor compounds, such as formamide and methylglyoxal. Extreme heat and presence of wildfire plumes modified the overall volatility, reactivity, O : C, and H : C ratios of the extended list of VOCs. The calculated OH reactivities during extreme temperature condition and transport of biomass burning plumes were 106.37±4.27 and 106.22±5.15 s −1 , respectively, which are substantially higher than background level of 98.78±1.16 s −1 . Multivariate analysis also clustered the compounds into five factors, which highlighted the sources of the unaccounted-for VOCs. Ultimately, results here underscore the effect of extreme heat and wildfire emissions on the overall chemical properties VOC in a temperate forest.

Salvador, Christian Mark [Oak Ridge National Labor↗

DOE OSTI2026

Volatile Organic Compounds in Bankhead National Forest (AMF3). August to September, 2025

The formation of atmospheric aerosols through the transformation of volatile organic compounds (VOCs) is a fundamental process in aerosol-climate interactions, as these particles serve as cloud condensation nuclei and ultimately influence Earth’s radiative balance. However, there remains a critical need to quantify the effects of multiple coexisting VOC precursors on aerosol formation beyond the limitations of laboratory-scale studies. This research aims to advance the mechanistic understanding of secondary organic aerosol formation in the southeastern United States by investigating interactions among coexisting VOC precursors observed at the third ARM Mobile Facility located in the Bankhead National Forest. The dataset was generated from the deployment of Oak Ridge National Laboratory’s PTR-TOF 6000 X2 Proton Transfer Reaction Time-of-Flight Mass Spectrometer (PTR-ToF-MS) for the real-time, continuous monitoring of VOCs from August 21 to September 15, 2025. To minimize sampling artifacts and compound losses, the PTR-ToF-MS inlet was connected to the cabin flow line by replacing the existing Tygon tubing with 1/2-inch outer diameter perfluoroalkoxy (PFA) tubing. The instrument operated on an hourly measurement cycle consisting of 8 minutes of zero-air measurements followed by 52 minutes of ambient air sampling, with a temporal resolution of 10 seconds. The dataset includes concentrations, reported in ppb, of methanol, acetone, acetonitrile, isoprene, methyl vinyl ketone and methacrolein (MVK + MACR), monoterpenes, benzene, toluene, and catechol.

Atmospheric concentration of volatile organic comp↗

NASA NTRS2022

Photochemical Evolution of the 2013 California Rim Fire: Synergistic Impacts of Reactive Hydrocarbons and Enhanced Oxidants

Large wildfires markedly alter regional atmospheric composition, but chemical complexity challenges model predictions of downwind impacts. Here, we elucidate key facets of gas-phase photochemistry and assess novel chemical processes via a case study of the 2013 California Rim Fire plume. Airborne in situ observations, acquired during the NASA Studies of Emissions, Atmospheric Composition, Clouds and Climate Coupling by Regional Surveys (SEAC4RS) mission, illustrate the evolution of volatile organic compounds (VOC), oxidants, and reactive nitrogen over 12 hours of atmospheric aging. Measurements show rapid formation of ozone and peroxyacyl nitrates (PNs), sustained peroxide production, and prolonged enhancements in oxygenated VOC and nitrogen oxides (NOX). Measurements and Lagrangian trajectories constrain a 0-D puff model that approximates plume photochemical history and provides a framework for evaluating key processes. Simulations examine the effects of 1) previously-unmeasured reactive VOC identified in recent laboratory studies, and 2) emissions and secondary production of nitrous acid (HONO). Inclusion of estimated unmeasured VOC leads to a 250% increase in OH reactivity and a 70% increase in radical production via oxygenated VOC photolysis. HONO amplifies radical cycling and serves as a downwind NOX source, although two different HONO production mechanisms (particulate nitrate photolysis and heterogeneous NO2 conversion) exhibit markedly different effects on ozone, NOX, and PNs. Analysis of radical initiation rates suggests that oxygenated VOC photolysis is a major radical source, exceeding HONO photolysis when averaged over the first 2 hours of aging. Ozone production chemistry transitions from VOC-sensitive to NOX-sensitive within the first hour of plume aging, with both peroxide and organic nitrate formation contributing significantly to radical termination. To simulate smoke plume chemistry accurately, models should simultaneously account for the full reactive VOC pool and all relevant oxidant sources.

SEAC4RS↗

DOE OSTI2025

Application of Atmospheric Gases and Particulate Matter to the Assessment of Urban Heat Island

Background: Urban heat island (UHI), where built areas are warmer compared to non-urban regions, increases human related diseases and mortality. A key challenge in UHI analysis is the designation of sites as urban or suburban/rural; however, the growing complexity of green spaces in urban areas and the predominance of the transportation sector in nonurban areas creates a dilemma for distinct delineation. Objectives: This study aims to utilize the variability of atmospheric components such as particulate matter (PM), inorganic gases, and volatile organic compounds (VOCs) as direct tracers of the degree of urbanization for ground-based measurements to fully comprehend UHI in convoluted regions with indistinct delineation of urban and nonurban environments. Methods: Atmospheric gases and aerosols were used as direct tracers of urbanization for UHI analysis. Inorganic gases and particulate matter were monitored in two sites in a southeastern US city with varying degrees of urbanization. VOCs were analyzed using a proton transfer reaction time-of-flight mass spectrometer. Results: The more-urbanized site exhibited warmer night conditions and elevated total oxidant levels, leading to the formation of nanometer-sized particles. Machine learning analysis revealed similar atmospheric pollutant profiles for both sites, suggesting comparable sources and variability. Biogenic VOCs were enhanced at the less-urbanized site; however, levels of anthropogenic aromatic VOCs were comparable for both sites. A comprehensive mass spectra analysis revealed distinct molecular backbones per site that further affirmed the applicability of VOCs as indicators of urbanization. Conclusion: This study concludes that VOCs provide more direct and accurate information than typical inorganic gases and PM parameters for characterizing the degree of urbanization. Further exploration of VOCs can enhance our understanding of UHI dynamics and its interaction with vegetation in urban green spaces.

Air quality sensor↗

DOE OSTI2025

Demonstration of an Automated System for Vertical Profiles of Volatile Organic Compounds

Volatile organic compounds (VOCs) play important roles throughout the atmosphere, many of which are altitude dependent. This highlights the need for easily deployable devices to sample VOCs across different atmospheric layers. To address this, we present the design and initial application of a Time Resolved Automated Volatile organIc compounds Sampling system (TRAVIS). VOCs are collected on sorbent tubes, which are subsequently analyzed by a thermal desorption gas chromatography mass spectrometry pipeline. TRAVIS leverages a piezoelectric pump with an integrated pressure sensor for precise (0.1% flow rate relative standard deviation) and accurate (−3 ± 2% error in VOC quantitation) measurements. Via deployment on a tethered balloon system over an agricultural area, TRAVIS is used to show consistent vertically resolved VOC concentrations in a well-mixed (i.e., turbulent) atmosphere (e.g., 5% relative standard deviation for isoprene) and vertically dependent concentrations for a stratified atmosphere (e.g., prior to boundary layer development). Furthermore, we also show VOC information from an intermittent plume via both targeted and untargeted analysis, highlighting future applications for spurious events in agriculture, air quality monitoring, and environmental impact. Overall, the development of TRAVIS represents a lightweight, accurate, sensitive, and precise VOC sampling module for the scientific community.

Aerosols↗

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↗

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 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↗

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.↗

NASA NTRS2021

Wilson Corners SWMU 001 2019-2020 Annual Long-Term Monitoring Report Kennedy Space Center, Florida

This report presents a summary of the long-term monitoring (LTM) activities that occurred in 2019 and 2020 at Wilson Corners, Solid Waste Management Unit 001, at the John F. Kennedy Space Center (KSC), Florida. The site is monitored under KSC’s Resource Conservation and Recovery Act Corrective Action Program. Adaptive site management is being utilized through ongoing assessment, design, and interim measures. This approach also meets the requirements of Chapter 62-780, Florida Administrative Code. 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. Sampling of these wells in 2020 was replaced with the direct push technology investigations in October 2020 and April 2021. The activities presented in this report include three field events: (1) December 2019 -groundwater gauging of 38 monitoring wells and sampling of 36 monitoring wells; (2) May 2020 - groundwater sampling of 7 monitoring wells; and (3) December 2020 - groundwater gauging of 49 monitoring wells and sampling of 43 monitoring wells. During the December 2019 and May 2020 events, monitoring wells were sampled using passive diffusion bags and were analyzed for a “full list” of volatile organic compounds (VOCs), including Freon 113. During the December 2020 event, the low flow sampling method was used, and samples were analyzed for a “select list” of VOCs, including Freon 113. The following conclusions can be made based on the 2019 and 2020 LTM results: •In December 2019 and December 2020, groundwater flow for the site was generally to the west with the individual zones only varying by occasional northerly and southerly components. This is generally consistent with historical observations at the site. •The GCTL plume continues to extend both horizontally and vertically beyond our current monitoring well network. •The vertical extent of VOCs was historically generally delineated by monitoring wells screened greater than 48 feet bls. The results from the two vertical extent monitoring wells WILC-MW0078 and WILC-MW0130 that were sampled during the 2019 and 2020 LTM indicate that groundwater VOC concentrations in both wells were greater than the GCTL. •Freon 113 was not detected above GCTLs during the 2019 and 2020 LTM events. Based on groundwater sampling activities performed during this reporting period, including recent DPT groundwater sampling conducted for the implementation of an air sparge system, the following recommendations are provided: •Install 10 new monitoring wells, which will be sampled along with 49 existing monitoring wells, to assist with delineation of the low concentration plume. The wells are listed inTable 4-1, and the proposed locations are presented on Figures4 -1 through 4-5. (Figures 4-1, 4-2, 4-3, and 4-5 also show updated plumes and proposed performance monitoring well locations. This information will be discussed and presented under a separate cover.) •Modify the annual LTM sampling plan as presented inTable 4-1. •Sampling for future events at the site will be conducted using low flow pumping methods. The next annual LTM sampling event is currently planned for December 2021. Please note the 10 new monitoring wells will not be installed before this event but will be installed as part of the upcoming IM construction and will be sampled during baseline sampling, along with the 49 existing monitoring wells. Following this sampling event, it is recommended that the Annual LTM be combined with the performance monitoring under the IM implementation, and LTM be temporarily discontinued. Objectives of the 2021 LTM are to: (i) evaluate groundwater gradient and flow direction by collecting depth to water measurements from LTM wells; (ii) continue monitoring the peripheral VOC trends in the northern, southern, and western portions of the site by monitoring existing wells and installing and monitoring new wells as recommended; and (iii) monitor select internal plume wells.

Jennifer Lynn Joyal↗