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  • Phytomanagement of Soil and Groundwater at the Niagara Falls Storage Site (NFSS) Using Hybridized Trees

    Abstract: The Manhattan Engineer District previously used the 191-acre Niagara Falls Storage Site (NFSS) in Niagara County, New York, to store radioactive residues and wastes from uranium (U) ore processing. At present, management practices will determine whether enhanced evapotranspiration rates produced by hybridized shrub willow cuttings planted in 2016 will affect groundwater hydrology. Two shrub willow varieties were planted in an approximately one-half acre area to examine growth performance along a U impacted sanitary sewer line. Additionally, control plots will compare the effectiveness of shrub willows to unplanted areas. Observations of the planted area after 18 months showed success of shrub willow growth with increasing biomass. Chemical analysis from tree tissue samples of the field study showed no significant uptake of U or thorium (Th) to date. A greenhouse study conducted in parallel to the field study tested the willows under controlled greenhouse conditions and evaluated their ability to grow and accumulate contaminants under controlled conditions. Results from the greenhouse study demonstrated that U accumulation was minimal. Thus, this study demonstrates that the shrub willows are not accumulators of U or Th, an advantageous characteristic that implies stabilized contaminants in the soil and no translocation of U into the aboveground biomass.
  • Leveraging Chemical Actinometry and Optical Radiometry to Reduce Uncertainty in Photochemical Research

    Abstract: Subtle aspects of illumination sources and their characterization methods can introduce significant uncertainty into the data gathered from light-activated experiments, limiting their reproducibility and technology transition. Degradation kinetics of methyl orange (MO) and carbamazepine (CM) under illumination with TiO2 were used as a case study for investigating the role of incident photon flux on photocatalytic degradation rates. Valerophenone and ferrioxalate actinometry were paired with optical radiometry in three different illumination systems: xenon arc (XE), tungsten halogen (W-H), and UV fluorescent (UV-F). Degradation rate constants for MO and CM varied similarly among the three light systems as k W-H < kiv-F < kXE, implying the same relative photon flux emission by each light. However, the apparent relative photon flux emitted by the different lights varied depending on the light characterization method. This discrepancy is shown to be caused by the spectral distribution present in light emission profiles, as well as absorption behavior of chemical actinometers and optical sensors. Data and calculations for the determination of photon flux from chemical and calibrated optical light characterization is presented, allowing us to interpret photo-degradation rate constants as a function of incident photon flux. This approach enabled the derivation of a calibrated ‘rate-flux’ metric for evaluating and translating data from photocatalysis studies.
  • Efficacy of Florpyrauxifen-benzyl for Eurasian Watermilfoil Control and Nontarget Illinois Pondweed, Elodea, and Coontail Response

    Purpose: This research evaluated low concentrations and short exposure times of the recently registered aquatic herbicide florpyrauxifen-benzyl (4-amino-3-chloro-6-(4-chloro-2-fluoro-3-methoxyphenyl)-5-fluoro-pyridine-2-benzyl ester) on the target plant Eurasian watermilfoil (Myriophyllum spicatum L., hereafter referred to as EWM) as well as selectivity towards the nontarget submersed species Illinois pondweed (Potamogeton illinoensis Morong), elodea (Elodea canadensis Michx.), and coontail (Ceratophyllum demersum L.)
  • Efficacy of Florpyrauxifen-benzyl on Dioecious Hydrilla and Hybrid Water Milfoil - Concentration and Exposure Time Requirements

    Abstract: This study conducted small-scale trials under various concentration and exposure time (CET) scenarios to determine florpyrauxifen-benzyl activity on dioecious hydrilla and hybrid watermilfoil and determine impact on water stargrass and elodea. Hydrilla treated with 12, 24, or 36 μg active ingredient (a.i.) L⁻¹ florpyrauxifen-benzyl and exposed for 12, 24, or 48 hr under outdoor mesocosm conditions was reduced in biomass by 30-75% at 8 weeks after treatment (WAT). An additional hydrilla trial at the same herbicide concentrations, but under longer exposures (24, 72, or 168 hr), resulted in 33–85% plant control. Under indoor conditions, hybrid watermilfoil dry weight decreased 98–100% with subsurface applications of florpyrauxifen-benzyl under CET scenarios of 3–12 μg a.i. L⁻¹ at 3–24 hr exposure times in a growth chamber trial. Under shorter exposure periods (0.5–4 hr) in a follow-up trial, low doses (3–9 μg a.i. L⁻¹) achieved 50–100% control of hybrid watermilfoil. In the same trial, the nontarget species water stargrass and elodea proved relatively tolerant to the florpyrauxifen-benzyl at doses up to 6 μg a.i. L⁻¹ (4 hr exposure) and 9 μg a.i. L⁻¹ (1 hr exposure). These small-scale trials demonstrate florpyrauxifen-benzyl’s potential to selectively manage invasive species.
  • Comparison of Generic and Proprietary Aquatic Herbicides for Control of Invasive Vegetation; Part 3: Submersed Plants

    Abstract: Herbicide selection is key to efficiently managing nuisance vegetation in our nation’s waterways. After selecting the active ingredient, there still remains multiple proprietary and generic products to choose from. Recent small-scale research has been conducted to compare the efficacy of these herbicides against floating and emergent species. Therefore, a series of mesocosm and growth chamber trials were conducted to evaluate subsurface applications of the following herbicides against submersed plants: diquat versus coontail (Ceratophyllum demersum L.), hydrilla (Hydrilla verticillata L.f. Royle), southern naiad (Najas guadalupensis (Sprengel) Magnus), and Eurasian watermilfoil (Myriophyllum spicatum L.); flumioxazin versus coontail, hydrilla, and Eurasian watermilfoil; and triclopyr against Eurasian watermilfoil. All active ingredients were applied at concentrations commonly used to manage these species in public waters. Visually, all herbicides within a particular active ingredient performed similarly with regard to the onset and severity of injury symptoms throughout the trials. All trials, except diquat versus Eurasian watermilfoil, resulted in no differences in efficacy among the 14 proprietary and generic herbicides tested, and all herbicides provided 43%–100% control, regardless of active ingredient and trial. Under mesocosm and growth chamber conditions, the majority of the generic and proprietary herbicides evaluated against submersed plants provided similar control.
  • Field Site Analysis of Giant Salvinia Nitrogen Content and Salvinia Weevil Density

    Abstract: In 2012, a giant salvinia (Salvinia molesta Mitchell) biological control project was initiated in Louisiana. Although similar quantities of salvinia weevils (Cyrtobagous salviniae Calder and Sands) were released at all sites, weevil densities were highly variable among sites. Additionally, signs of plant nitrogen depletion (yellowing plants) were observed at some sites. Because it is well known that plant nutrition can affect the success of a biocontrol agent because of slowed development and/or reduced fecundity, the correlation between giant salvinia nitrogen content and Salvinia weevil density was investigated during the growing seasons of the second and fourth years. During 2013, weevils were reintroduced to sites, and the magnitude of adult weevil density increase varied by site. Giant salvinia nitrogen content varied among sites and sampling dates. Upper Big Break plants had greater nitrogen than all other sites during 75% of sampling dates. Additionally, adult and larval densities were significantly correlated to plant nitrogen content. During 2015, trends were less distinct and weevil densities and nitrogen content varied based on the interaction between sampling date and site, but a significant correlation was not detected. Results confirmed published reports of the importance of plant nitrogen content to salvinia weevil productivity. Additional studies are warranted to evaluate and understand the role of nitrogen at giant salvinia biocontrol field sites.
  • Extra-Wide-Angle Parabolic Equations in Motionless and Moving Media

    Abstract: Wide-angle parabolic equations (WAPEs) play an important role in physics. They are derived by an expansion of a square-root pseudo-differential operator in one-way wave equations, and then solved by finite-difference techniques. In the present paper, a different approach is suggested. The starting point is an extra-wide-angle parabolic equation (EWAPE) valid for small variations of the refractive index of a medium. This equation is written in an integral form, solved by a perturbation technique, and transformed to the spectral domain. The resulting split-step spectral algorithm for the EWAPE accounts for the propagation angles up to 90􀀁 with respect to the nominal direction. This EWAPE is also generalized to large variations in the refractive index. It is shown that WAPEs known in the literature are particular cases of the two EWAPEs. This provides an alternative derivation of the WAPEs, enables a better understanding of the underlying physics and ranges of their applicability, and opens an opportunity for innovative algorithms. Sound propagation in both motionless and moving media is considered. The split-step spectral algorithm is particularly useful in the latter case since complicated partial derivatives of the sound pressure and medium velocity reduce to wave vectors (essentially, propagation angles) in the spectral domain.
  • Chemical Management Strategies for Starry Stonewort: A Mesocosm Study

    Abstract: US Environmental Protection Agency (USEPA) approved algaecides and herbicides are frequently utilized to manage nuisance algae and aquatic macrophytes. However, there is limited information available on the effectiveness of these products for the management of starry stonewort. Thus, the goal of this research was to discern effective chemical control products for later growth stages of starry stonewort using mesocosm studies. Eleven treatments were evaluated using various combinations of four copper-based products, endothall, diquat, and carfentrazone – all with USEPA registrations for use in aquatic sites. To assess treatment efficacy, water quality, photophysiology, biomass changes, and bulbil viability were evaluated. Nine of the eleven treatments yielded lower dissolved oxygen concentrations and higher specific conductance when compared to the control. Photophysiological response varied by condition, but seven of eleven treatments resulted in significantly lower fluorescent and maximum fluorescent yield. Five of these also exhibited significantly lower average photosynthetic yields, with combination treatments resulting in more drastic decreases. Ten of the eleven treatments had significantly less biomass compared to the control when measured via wet weight; however, only four treatments were significant when measured via dry weight. Lastly, all conditions utilizing copper-based products significantly reduced bulbil viability while non-copper products had no impact.
  • Initial Survey of Microplastics in Bottom Sediments from United States Waterways

    Abstract: Given the reported extent of microplastics in the aquatic environment, environmentally relevant exposure information for sediments dredged by the US Army Corps of Engineers will lend context to the risks posed by this contaminant during dredging. We measured the occurrence, abundance, and polymer composition of microplastics in sediments collected from nine dredged waterways and two non-dredged reference areas. The number of particles in sediment samples ranged from 162 to 6110 particles/kg dry wt., with a mean of 1636 particles/kg dry wt. Fragments were the most prevalent shape observed among the 11 study sites (100% frequency of occurrence), followed by fibers (81%), spheres (75%), foams (38%) and films (34%). Based on analyses of chemical composition of the particles using Fourier transform infrared spectroscopy, polyethylene:propylene was the most common polymer type observed. Consistent with results presented by other investigators microplastic concentrations and polymer types in bottom sediments in this study were also aligned with the most widely used plastics worldwide.
  • Identifying Degradation Products Responsible for Increased Toxicity of UV-Degraded Insensitive Munitions

    Abstract: Degradation of insensitive munitions (IMs) by ultraviolet (UV) light has become a concern following observations that some UV-degradation products have increased toxicity relative to parent compounds in aquatic organisms. This investigation focused on the Army's IM formulation, IMX101, composed of three IM constituents: 2,4-dinitroanisole (DNAN), 3-nitro-1,2,4-triazol-5-one (NTO), and nitroguanidine (NQ). The IM constituents and IMX101 were irradiated in a UV photo-reactor and then administered to Daphnia pulex in acute (48 h) exposures comparing toxicities relative to the parent materials. UV-degradation of DNAN had little effect on mortality whereas mortality for UV-degraded NTO and NQ increased by factors of 40.3 and 1240, making UV-degraded NQ the principle driver of toxicity when IMX101 is UV-degraded. Toxicity investigations for specific products formed during UV-degradation of NQ, confirmed greater toxicity than the parent NQ for degradation products. Summation of the individual toxic units for the complete set of individually measured UV-degradation products identified for NQ only accounted for 25% of the overall toxicity measured in the exposures to the UV-degraded NQ product mixture. Given the underestimation of toxicity using the sum toxic units for the individually measured UV-degradation products of NQ, we conclude that: (1) other unidentified NQ degradation products contributed principally to toxicity and/or (2) synergistic toxicological interactions occurred among the NQ degradation product mixture that exacerbated toxicity.