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SERDP PFAS 2.0 - An infrared spectral database for gas-phase quantitation of volatile per- and polyfluoroalkyl substances (PFAS)

We report the construction of a database of vetted infrared spectra specifically targeting volatile fluorocarbon gases that may be emitted during thermal treatment of per- and polyfluoroalkyl substances (PFAS) to assist understanding of treatment processes and improve quantification. To populate this database, protocols derived from the Pacific Northwest National Laboratory (PNNL) infrared spectral database are used, curtailing the species selection for this data set. Each spectrum in the database is a weighted average derived from 10 or more individual measurements at different partial pressures (static method) or flow rates (dissemination method) to yield good fidelity of both strong and weak infrared signatures, with each composite spectrum ranging from = 6500 cm-1 to = 600 cm-1 with an apodized resolution of 0.112 cm-1. This resolution was chosen to fully resolve all spectral features, recognizing that atmospheric pressure broadening results in nearly all ro-vibrational lines having linewidths = 0.1 cm-1. As an example case, application of the database is demonstrated via identification and quantification of dominant 1H-perfluoroheptane and perfluorohept-1-ene fluorocarbon products resulting from thermal decomposition of perfluorooctanoate (PFOA) below 450 °C.

Infrared, Gas-phase spectra, FTIR, Spectral databa↗

SERDP PFAS Database

The PNNL-PFAS database was constructed to provide quantitative infrared spectra of per- and polyfluoroalkyl substances (PFAS) in the gas phase. These fluorine-rich, organic compounds have been used as non-flammable solvents, cleaning agents, and in the manufacture of a diverse variety of consumer products. Due to their widespread use and relative inertness, PFAS have accumulated in the natural environment, and exposure to these chemicals may be linked to harmful health effects. Development of methods for detecting and remediating PFAS contamination are thus active areas of research. This database supports PFAS investigations where gas-phase infrared signatures may be measured (e.g., during treatment by thermal decomposition). The database currently contains infrared spectra for 15 compounds; these were selected based on the potential of these compounds being thermal degradation products of the manufactured chemicals mentioned above. • Additional compounds will be added to the database in the future. • Additional information about the database may be obtained from [link to future paper about the PFAS database].

PFAS, infrared(IR)spectroscopy, DATABASE, FTIR, sp↗

Marine Corps Base Camp Lejeune Climate Forecasts

Critical military training and testing on lands along the nation’s coastal and estuarine shorelines are increasingly placed at risk because of encroachment pressures in surrounding areas, impairments due to other anthropogenic disturbances, and changes in climate and sea level. The U.S. Department of Defense (DoD) intends to enhance and sustain its training and testing assets and also optimize its stewardship of natural resources through the development and application of an ecosystem-based management approach on DoD installations. To accomplish this goal, particularly for installations in estuarine/coastal environments, the Strategic Environmental Research and Development Program (SERDP) launched the Defense Coastal/Estuarine Research Program (DCERP) as a 10-year effort at Marine Corps Base Camp Lejeune (MCBCL) in North Carolina. The results of the second 5 years of the program (DCERP2) are presented in the DCERP2 Final Report.There were four overarching objectives of DCERP2. The first objective was to understand the effects of climate change impacts, including warming temperatures, variability in the hydrological cycle, storm events, and sea level rise on the coastal ecosystems at MCBCL from observations and measurements made over the 10-year program. The second objective was to understand the carbon cycle of the coastal and terrestrial ecosystems at MCBCL through a highly integrated sampling program. The third objective was to develop models, tools, and indicators to evaluate current and projected future ecosystem state changes and translate scientific findings into actionable information for installation managers. The last objective was to recommend adaptive management strategies to sustain ecosystem natural resources within the context of an active military installation.There are 252 mean change files represented in this dataset (12 months * 3 future time periods * 7 variables ). The mean change is calculated by taking the mean of the differences between the future projected average (e.g., 2046-2065) and the climate model baseline (e.g., 1979-1999). The differences were calculated for each downscaled GCM and then averaged across all models to obtain the mean change. This mean of the differences was calculated for each month, each future time period, and each variable.

54 ENVIRONMENTAL SCIENCES↗

Onslow Beach Washover Fan Morphology from 2012 to 2015

Critical military training and testing on lands along the nation’s coastal and estuarine shorelines are increasingly placed at risk because of encroachment pressures in surrounding areas, impairments due to other anthropogenic disturbances, and changes in climate and sea level. The U.S. Department of Defense (DoD) intends to enhance and sustain its training and testing assets and also optimize its stewardship of natural resources through the development and application of an ecosystem-based management approach on DoD installations. To accomplish this goal, particularly for installations in estuarine/coastal environments, the Strategic Environmental Research and Development Program (SERDP) launched the Defense Coastal/Estuarine Research Program (DCERP) as a 10-year effort at Marine Corps Base Camp Lejeune (MCBCL) in North Carolina. The results of the second 5 years of the program (DCERP2) are presented in the DCERP2 Final Report.There were four overarching objectives of DCERP2. The first objective was to understand the effects of climate change impacts, including warming temperatures, variability in the hydrological cycle, storm events, and sea level rise on the coastal ecosystems at MCBCL from observations and measurements made over the 10-year program. The second objective was to understand the carbon cycle of the coastal and terrestrial ecosystems at MCBCL through a highly integrated sampling program. The third objective was to develop models, tools, and indicators to evaluate current and projected future ecosystem state changes and translate scientific findings into actionable information for installation managers. The last objective was to recommend adaptive management strategies to sustain ecosystem natural resources within the context of an active military installation.These grid files were created from data collected using a Riegl 3-D laser scanner. Millions of x, y, and z points from the F2 Washover Fan on Onslow Beach were processed using the MARS software package to define a bare-earth model. Grid files were imported into Golden Software Surfer version 19 for editing and exported from that application as .grd files. Files can be opened in Surfer or ArcMap, but the coordinate system information will be lost if opened in ArcMap. These data were collected to quantify the morphological changes that occur on a washover fan through time.

54 ENVIRONMENTAL SCIENCES↗

Sequim Bay Underwater UXO (SBU2) Prototype Demonstration Site: Field Operations Summary, 2019

The U.S. Department of Defense (DoD) has identified more than 400 underwater sites that are potentially contaminated with munitions. Many of these sites are in shallow water (0–35 m deep) where the munitions pose a threat to human health and the environmental. To address this challenge, the Strategic Environmental Research and Development Program (SERDP) and Environmental Security Technology Certification Program (ESTCP) held a workshop in 2018 to establish the requirements and framework for developing a series of underwater unexploded ordnance (UXO) Standardized Demonstration sites (“test beds”) to support the evaluation of sensors, equipment, and technologies to detect UXO. Sequim Bay in Washington State was evaluated as a potential test bed and was determined to meet initial qualifying criteria with respect to environmental setting, and operational, logistical, and facilities support provided by the Pacific Northwest National Laboratory (PNNL).

45 MILITARY TECHNOLOGY, WEAPONRY, AND NATIONAL DEF↗

Sequim Bay Underwater UXO Prototype Demonstration Site: Field Operations Summary, 2020

This report provides a summary of Pacific Northwest National Laboratory’s (PNNL’s) activities to initiate Phase II development of the Sequim Bay Underwater UXO Prototype demonstration site (MR-2735) in 2020. Testbed development and field operations were conducted by PNNL’s Coastal and Marine Research Laboratory (MCRL) in support of the Strategic Environmental Research and Development Program (SERDP) and Environmental Security Technology Certification Program (ESTCP) underwater Munitions Response (MR) program. A series of standardized underwater unexploded ordnance (UXO) demonstration sites (“testbeds”) are being developed by SERDP/ESTCP to test, evaluate, and demonstrate technologies that can detect, geolocate, and classify proud and buried munitions in 0–35 m water depths. As a prototype demonstration site, Sequim Bay is a semi-enclosed marine waterbody containing sand and mud sediments with minimal clutter in 5–30 m water depths. MCRL is located at the entrance to Sequim Bay, where it provides operational, logistical, and facilities support for testbed activities.

45 MILITARY TECHNOLOGY, WEAPONRY, AND NATIONAL DEF↗

Evaluating the Long-Term Ecological Responses to Riparian Ecosystem Restoration at the Fort Benning, Georgia Military Installation

Riparian and instream restorations are commonly implemented to improve ecosystem condition. However, very few restoration activities are monitored for multiple years to assess long-term effectiveness. At the Department of Defense’s Fort Benning Military Installation (FBMI) in west-central Georgia, two experimental restoration projects (ephemeral drainage revitalization and instream habitat augmentation [i.e., coarse woody debris (CWD) additions]) were implemented ~14 years ago with the goal of reducing environmental impacts of military training activities. A SERDP project found that instream restoration improved some aspects of ecosystem function and community structure but not others. The objective of the current study was to re-evaluate the effect of these restoration practices on stream ecosystem processes ~14 years after implementation.

54 ENVIRONMENTAL SCIENCES↗

Air pollution control system research: An iterative approach to developing affordable systems

This paper describes a Strategic Environmental Research and Development Program (SERDP) funded project led jointly by the Marine Corps Multi-Commodity Maintenance Centers, and the Air and Energy Engineering Research Laboratory (AEERL) of the USEPA. The research focuses on paint booth exhaust minimization using recirculation, and on volatile organic compound (VOC) oxidation by the modules of a hybrid air pollution control system. The research team is applying bench, pilot and full scale systems to accomplish the goals of reduced cost and improved effectiveness of air treatment systems for paint booth exhaust.

Watt, Lewis C.↗