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Armstrong, Anthony

Publications and source records attributed to Armstrong, Anthony.

Critical Literature Review of Low Global Warming Potential (GWP) Refrigerants and their Environmental Impact

Refrigeration and air conditioning currently account for ~20% of the total electricity consumption in buildings around the world. Over the next three decades as global temperatures are projected to increase, urbanization and economic growth will lead to an increased demand for refrigeration and cooling. Most commonly used refrigerants belong to the five following classes: (i) chlorofluorocarbons, (ii) hydrochlorofluorocarbons, (iii) hydrofluorocarbons (HFCs), (iv) hydrofluoroolefins (HFOs), and (v) natural refrigerants. Over the past century, there have been shifts in which compounds were used for refrigeration to improve safety and durability, allow for ozone protection, and, most recently, to reduce global warming potential (GWP). Although technological advances have led to increased cooling capacity and safer refrigerants, emissions from refrigeration systems can affect the environment by contributing to greenhouse gas emissions or by depleting the ozone layer, depending on the gas emitted. The focus is increasingly on adopting compounds that are both efficient at cooling and effective for reducing emissions and other adverse environmental impacts. Because of policy and regulatory changes to avert ozone depletion and global climate change, much discussion has centered on the environmental impacts of next-generation refrigerants. Of particular interest are the fluorinated refrigerants, HFCs and HFOs, most of which are defined as per- and polyfluoroalkyl substances (PFAS) and their breakdown products (especially trifluoroacetic acid). The US Environmental Protection Agency in 2021 drafted a Strategic Roadmap for PFAS, which has already resulted in an increase in investment in research on these compounds and has restricted the release of PFAS into the environment through the implementation of monitoring and reporting requirements. A critical evaluation of fluorinated refrigerants and their breakdown products with respect to persistence, biodegradation and toxicity, and global warming potential is needed to guide environmental regulations. This document aims to perform a critical review of the relevant scientific data on the most common refrigerants currently used, their degradation products, and their alternatives. Where available, estimates of precursor production quantities and existing environmental regulatory information are reviewed. Key data of interest for the evaluation include physicochemical properties, environmental fate parameters, ecological or human health toxicity/risk information, and GWP for compounds of interest.

54 ENVIRONMENTAL SCIENCES↗

Critical Literature Review of Low Global Warming Potential (GWP) Refrigerants and their Environmental Impact

Refrigeration and air conditioning currently account for ~20% of the total electricity consumption in buildings around the world. Over the next three decades as global temperatures are projected to increase, urbanization and economic growth will lead to an increased demand for refrigeration and cooling. Most commonly used refrigerants belong to the five following classes: (i) chlorofluorocarbons, (ii) hydrochlorofluorocarbons, (iii) hydrofluorocarbons (HFCs), (iv) hydrofluoroolefins (HFOs), and (v) natural refrigerants. Over the past century, there have been shifts in which compounds were used for refrigeration to improve safety and durability, allow for ozone protection, and, most recently, to reduce global warming potential (GWP). Although technological advances have led to increased cooling capacity and safer refrigerants, emissions from refrigeration systems can affect the environment by contributing to greenhouse gas emissions or by depleting the ozone layer, depending on the gas emitted. The focus is increasingly on adopting compounds that are both efficient at cooling and effective for reducing emissions and other adverse environmental impacts. Because of policy and regulatory changes to avert ozone depletion and global climate change, much discussion has centered on the environmental impacts of next-generation refrigerants. Of particular interest are the fluorinated refrigerants, HFCs and HFOs, most of which are defined as per- and polyfluoroalkyl substances (PFAS) and their breakdown products (especially trifluoroacetic acid). The US Environmental Protection Agency in 2021 drafted a Strategic Roadmap for PFAS, which has already resulted in an increase in investment in research on these compounds and has restricted the release of PFAS into the environment through the implementation of monitoring and reporting requirements. A critical evaluation of fluorinated refrigerants and their breakdown products with respect to persistence, biodegradation and toxicity, and global warming potential is needed to guide environmental regulations. This document aims to perform a critical review of the relevant scientific data on the most common refrigerants currently used, their degradation products, and their alternatives. Where available, estimates of precursor production quantities and existing environmental regulatory information are reviewed. Key data of interest for the evaluation include physicochemical properties, environmental fate parameters, ecological or human health toxicity/risk information, and GWP for compounds of interest.

54 ENVIRONMENTAL SCIENCES↗

Atmospheric Transformation of Refrigerants: Current Research Developments and Knowledge Gaps

Refrigerants have evolved through the years to reduce their global warming potential while providing sufficient cooling in refrigeration systems. Replacements for hydrofluorocarbons (HFCs) and chlorofluorocarbons (CFCs) are the hydrofluoroolefins (HFOs), which contain reactive double bonds that decrease the atmospheric lifetime of fluorinated compounds. However, the transformation of unsaturated fluorinated compounds in the atmosphere could generate persistent pollutants, particularly trifluoroacetic acid (TFA) which is the simplest Perfluoroalkyl carboxylic acids (PFCAs). Understanding the transformation of refrigerants is critical in assessing their contribution to atmospheric levels of TFA and their impact on watersheds and human health. This article will present the reactivity of the refrigerants, atmospheric oxidation source, and sink processes of fluorinated refrigerants under daytime conditions, particularly the variability of TFA from refrigerants. Moreover, the discussion will suggest experimental procedures that can quantify the low concentration (~parts per trillion) of TFA generated from the transformation of HFOs. New state-of-the-art techniques such as chemical ionization mass spectrometers (HR-CIMS) will be assessed in providing high temporal resolution (minutes to hourly) to fully capture the atmospheric sources and variability of TFA. Likewise, local, regional, and global concentrations of TFA accounted from the oxidation of refrigerants will be examined. This will include data from both experimental procedures and simulation models. Participation of TFA in critical atmospheric processes such as new particle formation will also be included in this study. Lastly, overall knowledge gaps related to the oxidation products and their dispersion in the environment will be summarized to guide future research needs.

Salvador, Christian↗

An Overview of the Risk Assessment Information System

This technical memorandum (TM) presents an overview of the Risk Assessment Information System (RAIS), a collection of web-based tools designed to assist with the environmental risk assessment process. The objective of the RAIS is to be a single resource for the risk assessment process, providing guidance when planning and performing the steps: data assessment, exposure assessment, toxicity assessment, and risk characterization. The RAIS evolved as a result of the initial remediation efforts at various United States (U.S.) Department of Energy (DOE) facilities. The goal was to increase the efficiency and transparency of the human health and ecological assessments being performed by DOE’s Office of Environmental Management, Oak Ridge Operations (ORO) office by providing a repository for toxicity information, physicochemical data, risk assessment procedures, standardized risk calculation methods, and web-based tools. Since the initial launch in 1996, the RAIS has expanded its user base outside of the federal government and now has users from over 100 countries, universities, states, and local governments. What sets the RAIS apart from other risk assessment sites are the publicly available, searchable toxicity and physicochemical databases and the wide range of chemical and radionuclide risk calculation tools. The purpose of this TM is to present the RAIS tools in order of the website menus and explain how they fit in the risk assessment process. In addition, this TM describes differences between the chemical and radionuclide tools of the RAIS. Screening level equations, chronic daily intake equations, and default exposure factors used in the chemical and radionuclide calculators are included in the appendices of this TM. This TM is not intended to be a detailed guide to risk assessment or the RAIS tools. The tools on the RAIS can be used to comply with procedures from multiple agencies, including but not limited to DOE, U.S. Environmental Protection Agency (EPA), U.S. Department of Defense (DoD), and many state governments. Further information on the RAIS tools can be found in the user guides and tutorials available on the webpage.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

Quantifying the Impact of Excluding the Submersion Exposure Route for Existing Superfund Radionuclide Screening Level Calculator Soil and Tap Water Models

The U.S. Environmental Protection Agency (EPA) provides initial data screening guidelines for radionuclide-contaminated Superfund sites using preliminary remediation goals (PRGs) and dose compliance concentrations (DCCs). PRGs and DCCs are target concentration values based on acceptable excess lifetime cancer risk and annual dose limits, respectively. They are calculated for various environmental media that may be encountered by residential and worker land uses. PRGs and DCCs typically consist of multiple exposure routes. One of these routes is submersion, which is exposure to a gaseous or particulate radionuclide that is suspended in air. Currently, submersion is only included in air calculations. This study focused on determining whether factoring submersion into total PRG/DCC calculations for soil and tap water created a significant difference in the target concentrations. New equations for individual submersion PRGs/DCCs for each land use of interest for soil and tap water were developed. A wind-driven particulate emission factor and Andelman’s constant were used to model the amount of soil and vapor in the air from soil and household use of tap water, respectively. The submersion PRG/DCC was then included in the total PRG/DCC for each radionuclide, followed by a percent difference comparison of the old and new totals to quantify the impact of the change. For total soil PRGs/DCCs, with and without submersion, the difference was less than 1 percent; however, many of the tap water radionuclides analyzed – including multiple radon and polonium isotopes – showed as high as a 200 percent difference.This technical memorandum (TM) presents recommendations for updates to current EPA guidelines for initial data screens of radionuclide contaminated tap water.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Characterization of the indoor far-field aerosol transmission in a model commercial office building

As businesses gradually reopen and employees return to work, the potential spread of SARS-CoV-2 and its variants through airborne transmission via the heating, ventilation, and air-conditioning (HVAC) systems of commercial building raises concerns. Since the general practice in commercial buildings is to use low-efficiency air filters and given that indoor air is generally recycled, the degree to which cross-zone aerosol transmission occurs is of interest. To quantify the cross-zone aerosol transmission, experiments were conducted using a synthetic test aerosol in the five zones on the first floor of a model commercial office building at the Oak Ridge National Laboratory. Because the synthetic aerosol was tagged with fluorescent salt, the aerosol generated from the source zone can be distinguished from the background aerosols due to its unique fluorescent signal. Data from cross-zone campaigns showed that submicron-aerosol transmission was higher than the micron aerosols. In campaigns with doors closed, the submicron aerosol transmission was less than 16% and less than 11% for micron aerosol transmission. Finally, opening the interior doors that connecting different zones can significantly enhance the aerosol transmission for zones at the close proximity to the source, but has less impact on those farther away.

60 APPLIED LIFE SCIENCES↗

Characterization of the indoor near-field aerosol transmission in a model commercial office building

To evaluate the exposure potential of infectious aerosols containing SARS-CoV-2 in an office building setting, synthetic test aerosols were used to experimental study airborne particle transmission in a multizone small office test building at the Oak Ridge National Laboratory. Nine measurement points in a single zone using active aerosol impactors report that the coefficient of variation of the time-averaged concentration is <10% in two campaigns and < 15% in one campaign, so a nearly well-mixed condition was noted. To understand the effect of HVAC system operation on the dynamic concentration of aerosols in office spaces, an aerosol transport model that includes factors such as outside air (OA) ratio, filtration, return air fraction, transport loss in air ducts, and particle deposition has been developed. The results of model fitting demonstrate strong agreement with experimental data. Overall, our investigation finds the return air fraction effects outweigh other mechanisms for the aerosol recirculation in this study, and the impact of air change rate (ACR) is more important than the small particle deposition for aerosol removal. Because ACR dominates the aerosol transport, the full model can be simplified to just one factor, the ACR, while maintaining an acceptable representation of the experimental data.

60 APPLIED LIFE SCIENCES↗

Biota Modeling in EPA’s Preliminary Remediation Goal and Dose Compliance Concentration Calculators for Use in EPA Superfund Risk Assessment: Explanation of Intake Rate Derivation, Transfer Factor Compilation, and Mass Loading Factor Sources

The Preliminary Remediation Goal (PRG) and Dose Compliance Concentration (DCC) calculators are screening level risk assessment tools that set forth the Environmental Protection Agency’s (EPA) recommended approaches and currently available risk assessment guidance for response actions at Comprehensive Environmental Response, Compensation, and Liability Act (CERCLA) sites, commonly known as Superfund. The environmental screening levels derived by the PRG and DCC calculators are used to identify isotopes contributing the highest risk and dose as well as establish preliminary remediation goals. Each calculator has residential gardening and subsistence farmer exposure scenarios that model transfer of contaminants from soil and water into various types of biota (crops and animal products). New publications of human intake rates of biota; farm animal intakes of water, soil, and fodder; and soil to plant interactions require updates be implemented into the PRG and DCC calculators. Recent improvements in the biota modeling for these calculators include newly derived biota intake rates, enhanced soil mass loading factors (MLFs), and more comprehensive soil to plant transfer factors (BV’s) and soil to tissue transfer factors (TFs) for animals. New biota have been added in both the produce and animal products categories that greatly improve the accuracy and utility of the PRG and DCC calculators and encompass greater geographic diversity on a national and international scale.

54 ENVIRONMENTAL SCIENCES↗

Installation Assignment Durations and Patterns of Army Personnel

The purpose of this document is to report on the development of personnel assignment duration statistical metrics and statistical descriptions for groups of Army personnel aggregated by rank, career management field, and other descriptors for 32 Continental United States (CONUS) Army installations. This information can be used for generating evidence-based measures of personnel exposure times associated with environmental health considerations at the installation and career management field levels. Assignment duration statistical descriptions were developed to provide temporal metrics for groups of personnel at Army installations as foundational data to support a variety of assessments. Statistical results of personnel assignment durations at the installation level are provided in several formats. The 50th percentile assignment duration represents the median number of days personnel in groups aggregated by rank and career management field spend at the 32 CONUS Army installations in this study. Likewise, other duration percentiles (90th) and quartiles of assignment durations for groups aggregated by rank and career management field spend at each installation were developed. Assignment path analysis provide statistical descriptions of assignment durations at Army installations throughout increments of time (e.g., 5 years, 10 years). Key groupings of assignment paths were achieved by analyzing the duration of assignments at installations in chronological order from entry throughout specified increments of military service to generate the most common assignment paths across the 32 CONUS Army installations in this study. The developed assignment duration analytics and duration statistical descriptions provide foundational temporal metrics for groups of personnel at 32 CONUS Army installations to support a variety of assessments including those by human resource planners and environmental health specialists.

96 KNOWLEDGE MANAGEMENT AND PRESERVATION↗