Doctor of Philosophy / Department of Civil Engineering / Alok Bhandari / Human activities generate large amounts of chlorinated phenolic chemicals that are often introduced into the soil environment during pesticide and insecticide application, industrial releases, and accidental spills. For example, 2,4-dichlorophenol (DCP), a derivative of the herbicide 2,4-dichlorophenoxyacetic acid (2,4-D) can been found in soil within 24 hours of 2,4- D application. Horseradish peroxidase (HRP)-mediated polymerization has been proposed as an approach to remediate soils and groundwater contaminated by phenolic pollutants. Treatment with HRP results in the transformation of phenols into polyphenolic oligomers that sorb strongly or precipitate on soils surfaces. Although HRP-mediated chlorophenol stabilization has been studied extensively in surface soils, very limited scientific data is available that supports the application of this technology in subsurface materials. Hence, the focus of this study was to evaluate sorption and binding of DCP and products of HRP-mediated polymerization of DCP to model geosorbents representing subsurface geomaterials. These sorbents included two humin-mineral geomaterials and one mineral geosorbent derived from surface soils. Soil-water phase distribution of total solute in the HRP-amended systems was observed to reach equilibrium within 7 days in woodland humin-mineral soil (WHM), and within 1 day in agricultural humin-mineral (AHM) and model mineral geomaterials. For all the geomaterials used, water extraction data indicated the development of contact time-dependent resistance to extraction/dissolution of soil-associated DCP and DPP. Solute associated with WHM geomaterial was higher at the end of the study than that associated with AHM. Contact time increased DCP stabilization at all initial aqueous DCP concentrations studied. Results of this study suggest that DCP stabilization in organic geosorbents results from a combination of sorption and cross-coupling of DCP and precipitation of DPP; in inorganic soils, precipitation of DPP macromolecules is the dominant process. HRP-mediated stabilization of DCP in soils was effective and independent of the solution ionic concentration. The amount of DCP stabilized in the mineral soil was comparable to that stabilized in humin-mineral geomaterials. The research reported in this dissertation demosntrates the potential of HRP enzyme to stabilize DCP in subsurface geomaterials under variable contaminant and salt concentrations, thereby restricting its transport in the environment.

<p>  </p> <p>Dicamba (3,6-dichloro-2-methoxybenzoic acid) and 2,4-D (2,4-dichlorophenoxyacetic acid) are two widely used herbicides for broadleaf weed control in soybeans. However, off-target application of dicamba and 2,4-D can cause severe damage to sensitive vegetation and crops. Early detection and assessment of off-target damage caused by these herbicides are necessary to help plant diagnostic labs and state regulatory agencies collect more information of the on-site conditions so to develop solutions to resolve the issue in the future. In 2021, the study was conducted to detect damage to soybean leaves caused by dicamba and 2,4-D by using LeafSpec, an accurate handheld hyperspectral leaf scanner. . High resolution single leaf hyperspectral images of 180 soybean plants in the greenhouse exposed to nine different herbicide treatments were taken 1, 7, 14, 21 and 28 days after herbicide spraying. Pairwise PLS-DA models based on spectral features were able to distinguish leaf damage caused by two different modes of action herbicides, specifically dicamba and 2,4-D, as early as 2 hours after herbicide spraying. In the spatial distribution analysis, texture and morphological features were selected for separating the dosages of herbicide treatments. Compared to the mean spectrum method, new models built upon the spectrum, texture, and morphological features, improved the overall accuracy to over 70% for all evaluation dates. The combined features are able to classify the correct dosage of the right herbicide as early as 7 days after herbicide sprays. Overall, this work has demonstrated the potential of using spectral and spatial features of LeafSpec hyperspectral images for early and accurate detection of dicamba and 2,4-D damage in soybean plants.</p> <p>   </p>

A new class of treatment processes called Advanced Reduction Processes (ARP) has been proposed. The ARPs combine activation methods and reducing agents to form highly reactive reducing radicals that degrade oxidized contaminants. Batch screening experiments were conducted to identify effective ARP by applying several combinations of activation methods (ultraviolet light, ultrasound, electron beam, microwaves) and reducing agents (dithionite, sulfite, ferrous iron, sulfide) to degradation of five target contaminants (perchlorate, nitrate, perfluorooctanoic acid, 2,4 dichlorophenol, 1,2 dichloroethane) at 3 pH levels (2.4, 7.0, 11.2). These experiments identified the combination of sulfite activated by ultraviolet light produced by a low pressure mercury vapor lamp as an effective ARP. More detailed kinetic experiments were conducted with nitrate and perchlorate as target compounds and nitrate was found to degrade more rapidly than perchlorate. The effects of pH, sulfite concentration, and light intensity on perchlorate and nitrate degradation were investigated. The effectiveness of the sulfite/UV-L treatment process improved with increasing pH for both perchlorate and nitrate.