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DOE OSTI2026

Transformative Impacts of Laser-Induced Breakdown Spectroscopy on Environmental and Biological Research at Oak Ridge National Laboratory

This manuscript will present an advancement of transformative research that has been conducted at Oak Ridge National Laboratory (ORNL) over a 25-year period (2000–2025) on a variety of environmental and biological matrices. These investigations derived a fundamental understanding of how elemental detection and analysis of these matrices led to the knowledge and discovery of natural processes in plants and the environment. Each project led to the initiation of a new research area which unearthed awesome and novel breakthroughs. Highlights are listed below: 1. The preliminary research at ORNL centered on the detection of aerosols utilizing Laser-induced Breakdown Spectroscopy (LIBS) technology. The Clean Air Act Amendment (CAAA) of 1990 highlighted the importance of identifying hazardous air pollutants (HAPs) due to their impact on environmental and human health, thereby underscoring the need to detect various toxic elements. Research in aerosol chemistry aimed to identify these harmful elements released by factories during periods of increased emissions in their manufacturing processes. LIBS emerged as the most effective method for real-time, in situ measurements of metal species in both gaseous and aerosol phases. 2. An understanding of the presence of total carbon in soils gives perspective on how to develop carbon sequestration strategies. The recognition that carbon sinks can evolve back to carbon sources to emit back to the atmosphere was an important consideration. Also, the concentration of carbon in soil indicates the health of land areas for growing crops successfully. 3. The direct detection of most of the elements in a wood sample in a single emission spectrum, without sample preparation, encouraged the research to use the LIBS technique for preservative treated wood coupled with use of multivariate statistical methodology. Additionally, it encouraged the researchers to try to differentiate natural woods from different parts of the country, and it was successfully demonstrated that LIBS coupled with MVA analysis could differentiate wood of different species from each other and of similar species grown in different environments based on their elemental spectra. This was a breakthrough since it revealed a systematic approach to connect elemental scarcity and abundance to either drought or typical rainfall conditions for the hardwood trees grown in specific areas. 4. Furthermore, the research progressed to reveal physiological and developmental processes contributing to biomass production such that the variation in leaf elemental composition increases our understanding of terrestrial nutrient cycles, as well as tracking the transfer of toxic elements from soils to living organisms. 5. Recently another breakthrough viz., ionomics initiated the correlation of elements to specific genes, uncovering the function that the element performed in the plant. More recently, this has been extended from plants to fungi as well as fungi growing in symbiotic relations with plants.

09 BIOMASS FUELS↗

DOE OSTI2020

Water-dispersible nanocolloids and higher temperatures promote the release of carbon from riparian soil

Increasing temperatures in alpine regions accompanied by glacial retreat is occurring rapidly due to climate change. This may affect riparian soils by increasing weathering rates, resulting in greater organic carbon (OC) release to rivers via movement of iron-containing colloids and nanonminerals. Increased concentrations of iron- or silcate-nanominerals would result in higher surface area for OC adsorption. To test the influence of temperature on OC leaching, we examined mineral weathering and nanocolloid facilitated release of OC through a series of controlled laboratory batch and column experiments using sediment from the banks of the Nisqually River, Mount Rainier in Washington State (USA). Additional experiments were conduscted using the same sediments, but with an illite amendment added to test the influence of additional surface area and nanominerals that many sediments along the Nisqually River contain. These higher- and lower-surface-area sediments (i.e., sediments with and with the illite amendment) were incubated for three months at 4 or 20 °C, followed by batch and column OC leaching tests. Results show that OC leaching rates for 20 °C were two to three times greater than for 4 °C. Further, our results suggest that nanocolloids are responsible for moving this increased OC load from these sediments. When hydrologically connected, OC is released from back sediments to rivers faster than presently anticipated in fluvial environments experiencing climate change-induced glacial retreat. Further, a one-dimensional, finite-element computational model developed for this study estimates that a 1 °C increase in temperature over a 3-mo summer runoff period increases the OC release rate from sediments by 79%.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2024

Federal Facility Agreement and Consent Order: Nevada National Security Site Use Restriction Management Plan with ROTC 1

This Use Restriction Management Plan (URMP) provides the information needed to create, modify, and manage use restrictions (URs) for sites on the Nevada National Security Site (NNSS), and sites accessed through the NNSS main gate, that were closed using the corrective action alternative (CAA) of closure in place under the Federal Facility Agreement and Consent Order (FFACO) (1996, as amended). (Note: This pertains to those FFACO sites not managed by the U.S. Department of Energy [DOE], Legacy Management.) The closure in place alternative is used for sites closed with residual contamination at levels requiring corrective action as determined using the FFACO process. The URs contain and control all requirements for long-term monitoring. This URMP also serves as the single repository of the URs implemented under the FFACO that identify use restricted areas and contain the current requirements for inspections, maintenance, and monitoring of the UR. The requirements in these URs replace all requirements listed in previous documentation. This consolidates post-closure monitoring requirements into a single source that ensures completeness and consistency of UR requirements and information. Standardized UR forms were developed to clearly document post-closure requirements that are consistent with current protocols and to ensure consistent information is contained in the URs. Standard notification, summary, and site controls statements were developed for all URs with provisions to insert site-specific options in the text. Current protocols for Industrial Sites and Soils URs are defined in this document and in the Soils Risk-Based Corrective Action (RBCA) Evaluation Process (DOE/EMNV, 2018). The standardized UR forms that have been approved to date are listed in Appendix A. Additional UR forms will be added once the review and approval process has been completed.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2026

The Interactions Between Shading and Organic Fertilizer Application on Dry-farmed Tomato Grown Between Photovoltaic Panels

Agrivoltaic systems are mixed systems of solar photovoltaic (PV) panels and agricultural production, where shade from the panels can result in lower evapotranspiration for crops, which is of particular interest for dryland agriculture. Dry-farmed tomato (Solanum lycopersicum) production in the Willamette Valley of Oregon has lower total yields and higher rates of blossom-end rot (BER) than irrigated tomato production, resulting in reduced marketable yields. To determine how dry-farmed ‘Early Girl’ tomato performed in an agrivoltaics system, a trial was conducted at the Valley Creek Solar Project (Salem, OR, USA) in 2020, using three different amendment treatments and three levels of shading from the panels. Amendment treatments were 0N (receiving no fertilizer), 84N (receiving 84 kg·ha −1 N), and 168N (receiving 168 kg·ha −1 N), applied as processed chicken manure. Plants were estimated to receive an irradiance factor of 30%, 76%, and 89% for full-shade, partial-shade, and full-sun treatments respectively. There was an interaction between amendment treatments and shading treatments in their effects on unblemished yield (yield of fruit without BER or sunscald). The optimum fertilizer application for full-shade and partial-shade rows was 84N, the optimum for full-sun rows was 0N. Fertilizing these rows at these rates resulted in an unblemished yield for the aisle of 11.1 t·ha −1 , which was lower than unblemished yields reported in previous experiments and trials in open fields. However, these results are from a single location and a single year, and other solar sites may behave more similar to open-field conditions. Shading from the panels increased average fruit weight and decreased incidence of BER and sunscald, suggesting that crops were less drought stressed. This resulted in similar unblemished yields for the full-shade and full-sun plots at 84N and 168N. Applying fertilizer resulted in higher total yields, smaller average fruit weight, increased BER incidence, and decreased sunscald incidence. The results suggest a possible synergy between dry-farmed tomato production and agrivoltaics, although several concerns remain, including difficulties managing the vegetation under panels, rules restricting PVs on high-value agricultural soils, and the possibility of soil compaction during PV installation.

14 SOLAR ENERGY↗

DOE OSTI2026

Fe(III) reducing bacterial activities in Old Woman Creek wetland sediments, June 2023

To evaluate the Fe(III) reducing microbiological activities in Old Woman Creek Nature Preserve (OWC) wetland sediments, we incubated OWC sediments under anoxic and oxic conditions and with or without Fe(III) amendment [as hydrous ferric oxide (HFO)]. No Fe(III) reduction was observed in heat-deactivated incubations. In non-sterile anoxic incubations, measurement of 0.5 M HCl-extractable Fe(II) indicated that Fe(III) reduction occurred in both Fe(III)-amended and -unamended incubations, indicating that abundant Fe(III) is associated with the OWC sediments. Little Fe(II) accumulated in solution, indicating that the most biogenic Fe(II) adsorbs to the sediments. When air was added to the headspace of non-sterile incubations, Fe(III) reduction was halted and any biogenic Fe(II) that accumulated was oxidized. These experiments were used to guide preparation and analyses of incubations to determine if electrochemical measuements can be used to detect microbiological activities in contrasting terminal electron accepting regimes (i.e., aerobic and Fe(III) reducing conditions). Data package includes methods and data from experiments, including dissolved anion concentrations, dissolved Fe(II) concentrations, and 0.5 M HCl-extractable Fe(II) concentrations. All files are either .txt or .csv and can be opened by any plain text editor application.

EARTH SCIENCE↗