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NASA NTRS1985

Measurements of concentrations of chlorofluoromethanes (CFMs) carbon dioxide and carbon isotope ratio in stratospheric and tropospheric air by grab-sampling systems

Measurements of concentrations of chlorofluoromethanes (CFMs), carbon dioxide and carbon isotope ratio in stratospheric and tropospheric air by grab-sampling systems are reported. The balloon-borne grab-sampling system has been launched from Sanriku Balloon Center three times since 1981. It consists of: (1) six sampling cylinders, (2) eight motor driven values, (3) control and monitor circuits, and (4) pressurized housing. Particular consideration is paid to the problem of contamination. Strict requirements are placed on the choice of materials and components, construction methods, cleaning techniques, vacuum integrity, and sampling procedures. An aluminum pressurized housing and a 4-m long inlet line are employed to prevent the sampling air from contamination by outgassing of sampling and control devices. The sampling is performed during the descent of the system. Vertical profiles of mixing ratios of CF2Cl2, CFCl3 and CH4 are given. Mixing ratios of CF2Cl2 and CFCl3 in the stratosphere do not show the discernible effect of the increase of those in the ground level background, and decrease with altitude. Decreasing rate of CFCl3 is larger than that of CF2Cl2. CH4 mixing ratio, on the other hand, shows diffusive equilibrium, as the photodissociation cross section of CH4 is small and concentrations of OH radical and 0(sup I D) are low.

Itoh, T.↗

DOE OSTI2022

Demonstration of VOC Fenceline Sensors and Canister Grab Sampling near Chemical Facilities in Louisville, Kentucky

Experimental fenceline sensor pods (SPods) fitted with 30 s duration canister grab sampling (CGS) systems were deployed at a site near chemical facilities in Louisville, KY, from 4 June 2018 to 5 January 2020. The objective of the study was to better understand lower cost 10.6 eV photoionization detector (PID)-based volatile organic compound (VOC) sensors and investigate their utility for near-source emissions detection applications. Prototype SPods containing PID sensor elements from two different manufacturers yielded between 78% and 86% valid data over the study, producing a dataset of over 120,000 collocated pair fenceline measurements averaged into 5-min datapoints. Ten-second time-resolved SPod data from an elevated fenceline sensor signal day are presented, illustrating source emission detections from the direction of a facility 500 m west of the monitoring site. An SPod-triggered CGS acquired in the emission plume on this day contained elevated concentrations of 1,3-butadiene and cyclohexane (36 parts per billion by volume (ppbv) and 637 ppbv, respectively), compounds known to be emitted by this facility. Elevated concentrations of these compounds were observed in a subset of the 61 manual and triggered CGS grab samples acquired during the study, with winds from the west. Using novel wind-resolved visualization and normalization approaches described herein, the collocated pair SPod datasets exhibited similarity in emission source signature. With winds from the west, approximately 50% of SPod readings were above our defined theoretical detection limit indicating persistent measurable VOC signal at this site. Overall, this 19-month study demonstrated reasonable prototype SPod operational performance indicating that improved commercial forms of lower cost PID sensors could be useful for select VOC fenceline monitoring applications.

1,3-butadiene↗

NASA NTRS2010

Evaluation of the Air Quality Monitor's Performance on the International Space Station

The Air Quality Monitor (AQM) was flown to the International Space Station (ISS) as an experiment to evaluate its potential to replace the aging Volatile Organic Analyzer (VOA), which ceased operations in August 2009. The AQM (Figure 1) is a small gas chromatography/differential mobility spectrometer (GC/DMS) manufactured by Sionex. Data was presented at last year s ISIMS conference that detailed the preparation of the AQM for flight, including instrument calibration. Furthermore, initial AQM data was compared to VOA results from simultaneous runs of the two instruments. Although comparison with VOA data provided a measure of confidence in the AQM performance, it is the comparison with results from simultaneously acquired air samples (grab sample containers-GSCs) that will define the success (or failure) of the AQM performance. This paper will update the progress in the AQM investigation by comparing AQM data to results from the analyses of GSC samples, returned from ISS. Additionally, a couple of example will illustrate the AQM s ability to detect disruptions in the spacecraft s air quality. Discussion will also focus upon a few unexpected issues that have arisen and how these will be a addressed in the final operational unit now being built.

Limero, Thomas↗

DOE OSTI2020

Applications of Hyporheic Zone Sampling for Assessing VOC Plume Engineered Remediation and Natural Attenuation Effectiveness - 20414

Determining the efficacy of engineered remedial actions and/or natural attenuation as an acceptable EPA Record of Decision (ROD) must address long-term temporal and spatial variability. Since final plume downslope destinations are aquifers and related surface streams and rivers, hyporheic zone sampling is essential. Comprehensive hyporheic sampling documents plume groundwater remediation prior to upwelling into stream benthic strata and natural attenuation within this dynamic zone itself. Our intensive sampling of the Savannah River Site (SRS) Chemical, Metals, and Pesticides (CMP) Pits VOC plume-fringe from 2005 to 2018 documented PCE natural attenuation and effectiveness of In Situ Thermal Treatment (ISTT). Most plume hyporheic upwelling was delimited to a 20 m inflow reach along Pen Branch. Our study utilized corroborative sampling methodologies: ambient hole-water grab samples: passive diffusion bags (PDB); and hole-core sediment samples to confirm station to station spatial and temporal trends. VOC hot spot detections were confirmed from both groundwater and soil core samples. VOC pathways through the Pen Branch hyporheic zone were assessed at hole-installation using sequential soil samples from augered cores and grab-samples of hole-bottom water. Longer term, composite water samples were collected from PDBs deployed for a minimum two-week equilibration period. Soil samples were collected from the 15 and 65 cm core levels in December 2017 and June 2018 at six stations. Additional core depths of 40 and 85 cm were sampled in June 2018 at the highest VOC station (5DB80). All samples were analyzed in an EPA certified lab by purge and trap GC-MS. Effectiveness of previous ISTT and soil vapor extraction (SVE) for this CMP Pits PCE plume, was clearly documented by significant downward trends in VOC at hyporheic zone stations prior to December 2015. Achieving final stage conversions of PCE daughter products to ethene and CO{sub 2} may be limited depending upon suitable interactions between hyporheic zone sediment morphology, hydrology, and redox conditions. Because declines in VOC daughter products at our hyporheic stations may also be caused by physical actions of dilution and dispersion rather than true biochemical dechlorination, full quantification of natural attenuation requires the use of compound-specific isotope ratio analysis (CSIA) and microbial 16S rRNA with qPCR. To assist these next-phase efforts, a natural attenuation index (NAI) was used to help produce quicker, more cost-effective decision making for locating CSIA and microbial sampling efforts. The NAI used natural logarithm transformed GC-MS results for station VOC degradation compounds versus VOC parent compounds. Wide differences were observed between stations. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

DOE OSTI2026

Post-fire time series of sensor and geochemistry sample data from surface water, groundwater, precipitation, soil, and vegetation across Oak Creek watershed, Washington

This dataset supports a broader study examining wildfire impacts on hydrologic connectivity across 5 sites within the Oak Creek watershed and the resulting biogeochemical impacts. Stream sites were selected using the Advanced Terrestrial Simulator (ATS) hydrologic model to identify locations with varying groundwater contributions and hydrologic responses across different burn severity scenarios. The Retreat Fire burned from July 23 to August 2 in 2024, affecting the five study sites at varying burn severities. Each site is equipped with YSI EXO2 sondes logging sub-hourly throughout the year, and grab samples are collected approximately every six weeks. YSI sondes are used to measure temporally resolved proxies for groundwater inputs (specific conductivity) and organic matter (fluorescent dissolved organic matter; fDOM) along with basic water quality and depth. Grab samples of surface water, groundwater, and precipitation are analyzed for water stable isotopes and conductivity to understand endmembers for hydrologic mixing Grab samples of surface water, groundwater, soil water, and litter/vegetation/soil leachates are analyzed for organic matter composition measured by Fourier-Transform Ion Cyclotron Resonance Mass Spectrometry (FTICR-MS) to understand organic matter dynamics. Game camera photos are provided in a separate data package available at https://data.ess-dive.lbl.gov/datasets/doi:10.15485/3018598. Future versions of this dataset will include time series data from YSI EXO2 sondes (fDOM, dissolved oxygen, temperature, depth, specific conductance, turbidity, pH), BaroTROLL sensors (air temperature and barometric pressure), rain gauges (precipitation), and data from the soil and vegetation samples. Because this study is ongoing, this data package will be updated regularly to include newly collected data and the additional data types. For details on how to navigate data packages generated by this project, see https://data.ess-dive.lbl.gov/portals/PNNLRiverCorridorSFA/About. In addition to a readme, this data package also includes a file-level metadata (FLMD) file that describes each file and a data dictionary (DD) that describes all column/row headers and variable definitions. This dataset is comprised of (1) a folder of field photos; (2) a folder of surface water sample data; (3) a folder of raw Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS) data; (4) a data checks report; (5) file-level metadata; (6) data dictionary; (7) field metadata; (8) readme; (9) international generic sample number (IGSN) mapping file; and (10) field protocols. The sample data subfolder contains (1) dissolved organic carbon (DOC, measured as non-purgeable organic carbon, NPOC) data and averages; (2) total dissolved nitrogen data and averages; (3) stable water isotopes and averages; (4) methods codes; (5) FTICR-MS methods; and (15) a subfolder of 9.4 Tesla (9.4T) FTICR-MS data. This folder contains the processed data and three subfolders, one containing the .xml files, one containing the water CoreMS output files, and the other containing instructions and scripts for processing the files in CoreMS (https://github.com/EMSL-Computing/CoreMS). All files are .csv, .pdf, .R, .xml, .d, .html, .Rmd, .py, .cal, .json, .jpg, .jpeg, .png, .mov, or .mp4.

Biogeochemistry↗

NASA NTRS1974

Apollo Saturn 511 effluent measurements from the Apollo 16 launch operations: An experiment

An experiment was performed in conjunction with the Apollo 16 launch to define operational and instrumentational problems associated with launch-vehicle exhaust effluent monitoring. Ground and airborne sampling were performed for CO, CO2, hydrocarbons, and particulates. Sampling systems included filter pads and photometers for particulates and whole-air grab samples for gases. Launch debris was identified in the particulate samples at ground level(taken immediately after launch) and in the airborne measurements (taken 40 to 50 minutes after launch approximately 40 km downwind of the pad). Operational problems were identified and included the need for higher instrumentation mobility and the need for real-time sampling instrumentation as opposed to collection-type samples such as the whole-air grab sample.

Gregory, G. L.↗

NASA NTRS2012

Space X1 First Entry Sample

One mini-grab sample container (m-GSC) was returned aboard Space X1 because of the importance of quickly knowing first-entry conditions in this new commercial module. This sample was analyzed alongside samples of the portable clean room (PCR) used in the Space X complex at KSC. The recoveries of C-13-acetone, fluorobenzene, and chlorobenzene from the GSCs averaged 130, 129, and 132 %, respectively.

James, John T.↗

NASA NTRS2013

Toxicological Assessment of ISS Air Quality: Contingency Sampling - February 2013

Two grab sample containers (GSCs) were collected by crew members onboard ISS in response to a vinegar-like odor in the US Lab. On February 5, the first sample was collected approximately 1 hour after the odor was noted by the crew in the forward portion of the Lab. The second sample was collected on February 22 when a similar odor was noted and localized to the end ports of the microgravity science glovebox (MSG). The crewmember removed a glove from the MSG and collected the GSC inside the glovebox volume. Both samples were returned on SpaceX-2 for ground analysis.

Meyers, Valerie↗

DOE OSTI2021

Greenhouse production contributes to pesticide occurrences in Swedish streams

Greenhouse and other covered cultivation systems have increased globally over the past several decades, leading to considerably improved product quality and productivity per land area unit. However, there is a paucity in information regarding the environmental impacts of covered production systems, especially regarding pesticides entering the surrounding environment. Aiming to address this knowledge gap, we collected grab samples downstream of greenhouses from seven Swedish streams every 14 days during a 12 month period. In three of the streams, samples were also taken upstream of the greenhouses and in four of the streams time-integrated samples were collected by TIMFIE samplers in the period between grab sampling occasions. The samples were analyzed for 28 substances (27 that were permitted for use in greenhouse production systems in Sweden and one degradation product to a permitted substance). Pesticide use journals were collected from the greenhouse producers for the 12 month period. The results were examined for indications of greenhouse contributions to detection frequencies, maximum and average concentrations, and potential ecotoxicicity in several ways: (1) comparing locations downstream of greenhouses with registered use of a substance with those without registered use, (2) comparing results from this study with those from the Swedish environmental monitoring program of pesticides in surface water from catchments with no greenhouses from the same period and region, (3) comparing concentration trends with registered pesticide application times in the greenhouses, and (4) comparing up- and downstream concentrations. The results strongly suggest that greenhouse applications do contribute to pesticide occurrences, maximum and median concentrations for most of the pesticides included in this study, and to potential toxicity to aquatic organisms for several of them, most notably imidacloprid, acetamiprid, carbendazim, and pirimicarb.

54 ENVIRONMENTAL SCIENCES↗

NASA NTRS1986

Day and night profiles of tropospheric nitrous oxide

Daytime and nighttime vertical profiles of the tropospheric trace gas N2O were determined from grab sample collections off the Atlantic and Gulf coasts of Florida. The grab samples were collected during the week of October 7-13, 1984, from a Lear jet during descent spirals over an altitude range of 12.5-0.3 km in approximately 1.2-km intervals. During this period there were two distinct airflow regimes sampled: (1) the surface boundary layer (less than 2 km), in which the wind direction was typically easterly; and (2) the regime above the boundary layer, which was predominantly characterized by westerly flow. N2O mixing ratios, normalized to dry air, were determined from 148 daytime and nighttime samplings. N2O was found to be uniformly mixed at all altitudes at 301.9 + or - 2.4 parts per billion by volume.

Cofer, Wesley R., III↗

NASA NTRS2007

Volatile Organic Analyzer (VOA) in 2006: Repair, Revalidation, and Restart of Elektron Event

The Volatile Organic Analyzer (VOA) was launched to the International Space Station (ISS) in August 2001 and was the first instrument to provide near real-time measurement of volatile organic compounds in a spacecraft atmosphere. The VOA performed an analysis of the ISS air approximately twice a month for most of its operation through May 2003. This intermittent operation, caused by a software interface issue with the ISS communication bus, slowed the validation of the VOA. However, operational validation was completed in 2003 when analysis of air samples collected in grab sample containers (GSCs) compared favorably with simultaneous VOA runs (1). The VOA has two channels that provide redundant function, albeit at slightly reduced performance, when only one channel is operating (2). Most target compounds can be detected on both channels. In January 2003, the VOA identified a malfunction in the channel 2 preconcentrator and it shut down that channel. The anomaly profile suggested that a fuse might have failed, but the root cause could not be determined. In May 2003, channel 1 was shut down when the detector s elevated temperature could not longer be maintained. Since both VOA channels were now deactivated, VOA operations ended until an in-flight repair could be planned and executed. This paper describes the process to repair the VOA and to revalidate it for operations, and then an account is given of the VOA s contribution following a contingency event on ISS.

Limero, Thomas↗

DOE OSTI2020

Monthly Sewer Monitoring Report for LLNL Livermore Site, April 2020

Lawrence Livermore National Laboratory (LLNL) collects effluent samples from its sewer outfall at the B196 Sewer Monitoring Station (SMS). Effluent flow-proportional composite samples are collected at the SMS on a daily (midnight-to-midnight), weekly (Thursday through Wednesday), and “monthly” (composited from daily) basis; effluent grab samples are also collected each month at that same location. Certified contract laboratories analyzes these compliance samples, and results (Tables 1–3) are used to establish LLNL compliance with the 2019–2020 Wastewater Discharge Permit (Permit 1250) granted by the City of Livermore Water Resources Division (WRD). Supplemental analyses for biochemical oxygen demand (BOD) and total suspended solids (TSS) are performed onsite and reported (Table 4) for the calculation and assessment of sewer service charges. Quarterly, effluent is sampled for metals (24-hour composite) and cyanide (grab sample) concentrations (mg/L). The results are presented in Table 5. In addition to the sampling noted above, the SMS continuously monitors LLNL sewage effluent in real-time for flow rate, pH, metals, and radioactivity. Standard measurement methods are used to monitor flow and pH to determine permit compliance. Unique nonstandard analytical methods monitor for the presence of metals and radioactivity using x-ray fluorescence (XRF) and gamma spectroscopy, respectively. If an anomalous condition is detected by the monitoring system, an alarm activates LLNL’s Sewer Diversion Facility (SDF) and Livermore Water Reclamation Plant (LWRP) operators are notified that a potential release has occurred.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2020

Monthly Sewer Monitoring Report for LLNL Livermore Site (Jun 2020)

54 ENVIRONMENTAL SCIENCES↗

NASA NTRS1982

Measurements of the global distribution of carbon monoxide in the troposphere

Carbon monoxide and methane grab samples were obtained simultaneously with ozone, aerosol, nitric oxide and DACOM CO measurements. Eighty grab samples were collected at various altitudes up to 19,000 ft. along a north-south flight path from Wallops Flight Center, VA to 11 N. CO and CH were analyzed by flame ionization gas chromatography with cryogenic preconcentration. The relationship between CO and O3 concentrated is examined. A comparative analysis between trends in aerosol and CO concentration is performed.

Hinton, R. R.↗

NASA NTRS1978

Luna 24: 90-150 micrometer fraction - Implications for remote sampling of regolith

An analysis of the mineral grains and glasses found in the 90 to 150 micron fraction of the Luna 24 core sample is presented and implications for the automatic collection of planetary and asteroidal regoliths are discussed. Electron microprobe analysis for pyroxene, olivine, plagioclase, opaque minerals and glass in samples at various depths indicate that polymineralic grains have compositions similar to those of gabbroic and basaltic fragments from coarser samples, while monomineralic grains contain an additional population of Mg-rich olivines and pyroxene. Most of the glasses are found to be related to mare basalts or local regolith, with nonmare material represented by glasses of highland basalt and low K Fra Mauro composition. It is concluded that as regards mineralogy and petrology, a single grab sample would have been as useful and a series of grab samples on a long traverse would have been more useful than the Luna 24 core sample, with the fine sample being more informative than the coarse.

Papp, H. A.↗

NASA NTRS1982

Stratospheric CCN sampling program

Two one liter grab samples of stratospheric aerosol were returned from each of six U-2 sampling missions. Cloud condensation nuclei (CCN) spectra from each sample were obtained. Interest was centered on the effects of volcanic activity. Spurious particle generation was found to be a serious problem in container 9 LFT and a much smaller problem in container 9 RT. Initial studies of an option for improved sample containers and values were completed. A CCN spectrometer, able to operate at an internal pressure of 300 mb, was designed.

Rogers, C. F.↗

DOE OSTI2021

Evaluating Manual Sampling Locations for Regulatory and Emergency Response

Drinking water systems commonly use manual or grab sampling to monitor water quality, identify or confirm issues, and verify that corrective or emergency response actions have been effective. In this paper, the effectiveness of regulatory sampling locations for emergency response is explored. An optimization formulation based on the literature was used to identify manual sampling locations to maximize overall nodal coverage of the system. Results showed that sampling locations could be effective in confirming incidents for which they were not designed. When evaluating sampling locations optimized for emergency response against regulatory scenarios, the average performance was reduced by 3%–4%, while using optimized regulatory sampling locations for emergency response reduced performance by 7%–10%. Secondary constraints were also included in the formulation to ensure geographical and water age diversity with minimal impact on the performance. This work highlighted that regulatory sampling locations provide value in responding to an emergency for these networks.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2024

High Frequency Monitoring and Nitrate Sourcing Reveals Baseflow and Stormflow Controls on Total Dissolved Nitrogen and Carbon Export Along a Rural‐Urban Gradient

Abstract Efforts to reduce nitrogen and carbon loading from developed watersheds typically target specific flows or sources, but across gradients in development intensity there is no consensus on the contribution of different flows to total loading or sources of nitrogen export. This information is vital to optimize management strategies leveraging source reductions, stormwater controls, and restorations. We investigate how solute loading and sources vary across flows and land‐use using high frequency monitoring and stable nitrate isotope analysis from five catchments with different sanitary infrastructure, along a gradient in development intensity. High frequency monitoring allowed estimation of annual loading and attribution to storm versus baseflows. Nitrate loads were 16 kg/km 2 /yr. from the forested catchment and ranged from 68 to 119 kg/km 2 /yr., across developed catchments, highest for the septic served site. Across developed catchments, baseflow contributions ranged from 40% of N loading to 75% from the septic served catchment, and the contribution from high stormflows increased with development intensity. Stormflows mobilized and mixed many surface and subsurface nitrate sources while baseflow nitrate was dominated by fewer sources which varied by catchment (soil, wastewater, or fertilizer). To help inform future sampling designs, we demonstrate that grab sampling and targeted storm sampling would likely fail to accurately predict annual loadings within the study period. The dominant baseflow loads and subsurface stormflows are not treated by surface water management practices primarily targeted to surface stormflows. Using a balance of green and gray infrastructure and stream/riparian restoration may target specific flow paths and improve management.

Delesantro, Joseph M.↗