No abstract

Metabolomics and biochemical assays were employed to identify physiological perturbations induced by a commercial formulation of glyphosate in susceptible (S) and resistant (R) biotypes of Amaranthus palmeri. At 8 h after treatment (HAT), compared to the respective water-treated control, cellular metabolism of both biotypes were similarly perturbed by glyphosate, resulting in abundance of most metabolites including shikimic acid, amino acids, organic acids and sugars. However, by 80 HAT the metabolite pool of glyphosate-treated R-biotype was similar to that of the control S- and R-biotypes, indicating a potential physiological recovery. Furthermore, the glyphosate-treated R-biotype had lower reactive oxygen species (ROS) damage, higher ROS scavenging activity, and higher levels of potential antioxidant compounds derived from the phenylpropanoid pathway. Thus, metabolomics, in conjunction with biochemical assays, indicate that glyphosate-induced metabolic perturbations are not limited to the shikimate pathway, and the oxidant quenching efficiency could potentially complement the glyphosate resistance in this R-biotype.

Per-and polyfluoroalkyl substances (PFAS) are ubiquitous in many consumer products and present serious environmental challenges due to their persistent nature. Currently, conventional water treatment methods fail to remove PFAS, and other newly proposed materials/techniques face challenges when employed under realistic conditions. This study reports on poly(ethylenimine)-functionalized cellulose microcrystals (PEI-f-CMC) that showed a near-instant and high removal of PFAS under concentrations relevant to their actual occurrence in the natural environment (i.e., <1000 ng/L). The selective removal efficiency of 22 PFAS from different classes (i.e., legacy carboxylic and sulfonated PFAS, emerging carboxylic and sulfonated PFAS, and PFAS-precursors) using PEI-f-CMC was confirmed in lake water as well as solutions codosed with two additional types of natural organic matter. The performance of PEI-f-CMC was maintained in eight consecutive adsorption/regeneration cycles to remove PFAS. The PEI-f-CMC with its unique fast kinetics and high adsorption activity toward PFAS exhibits a great potential for being a promising alternative adsorbent for PFAS control.

Water treatment techniques for destructive removal of perfluoroalkyl substances (PFAS) have only recently begun to emerge in the research literature, comprising unconventional advanced oxidation and reduction methods. Photocatalytic degradation of PFAS has not been widely pursued, which is a result of the limited ability of common semiconductor materials to induce C−F bond cleavage in aqueous systems. Herein, degradation of perfluorooctanoic acid (PFOA) by bismuth phosphate photocatalysts under ultraviolet irradiation has been investigated for the first time, including the relatively well-known monoclinic BiPO 4 wide band gap semiconductor, as well as a novel Bi 3 O(OH)(PO 4 ) 2 (BOHP) composition. Compared to BiPO 4 and a β-Ga 2 O 3 nanomaterial reference catalyst, BOHP microparticles achieved dramatically faster PFOA degradation and mineralization, despite both a smaller surface area and a lower band gap energy. The rate constant for degradation of PFOA by BOHP in a pure water solution was ∼15 times greater than those of both BiPO 4 and β-Ga 2 O 3 (∼20−30 times greater when normalized for surface area) and was on the same order of magnitude as that of phenol degradation by P25 TiO 2 in the same photoreactor. The superior performance of BOHP was primarily related to the surface charge and adsorption behavior of PFOA, in combination with the favorable redox potentials of BOHP charge carriers. The catalyst was further tested at low PFOA concentrations (i.e., microgram per liter range) in the presence of natural organic matter, and rapid degradation of PFOA was also observed, indicating the potential of BOHP to enable practical ex situ destructive treatment of PFAS-contaminated groundwater.

Biotic and abiotic stressors often result in the buildup of amino acid pools in plants, which serve as potential stress mitigators. However, the role of anabolic (de novo amino acid synthesis) versus catabolic (proteolytic) processes in contributing to free amino acid pools is less understood. Using stable isotope-resolved metabolomics (SIRM), we measured the de novo amino acid synthesis in glyphosate susceptible (S-) and resistant (R-) Amaranthus palmeri biotypes. In the S-biotype, glyphosate treatment at 0.4 kg ae/ha resulted in an increase in total amino acids, a proportional increase in both (14)N and (15)N amino acids, and a decrease in soluble proteins. This indicates a potential increase in de novo amino acid synthesis, coupled with a lower protein synthesis and a higher protein catabolism following glyphosate treatment in the S-biotype. Furthermore, the ratio of glutamine/glutamic acid (Gln/Glu) in the glyphosate-treated S- and R-biotypes indicated that the initial assimilation of inorganic nitrogen to organic forms is less affected by glyphosate. However, amino acid biosynthesis downstream of glutamine is disproportionately disrupted in the glyphosate treated S-biotype. It is thus concluded that the herbicide-induced amino acid abundance in the S-biotype is contributed by both protein catabolism and de novo synthesis of amino acids such as glutamine and asparagine.

Modern high-throughput molecular and analytical tools offer exciting opportunities to gain a mechanistic understanding of unique traits of weeds. During the past decade, tremendous progress has been made within the weed science discipline using genomic techniques to gain deeper insights into weedy traits such as invasiveness, hybridization, and herbicide resistance. Though the adoption of newer “omics” techniques such as proteomics, metabolomics, and physionomics has been slow, applications of these omics platforms to study plants, especially agriculturally important crops and weeds, have been increasing over the years. In weed science, these platforms are now used more frequently to understand mechanisms of herbicide resistance, weed resistance evolution, and crop–weed interactions. Use of these techniques could help weed scientists to further reduce the knowledge gaps in understanding weedy traits. Although these techniques can provide robust insights about the molecular functioning of plants, employing a single omics platform can rarely elucidate the gene-level regulation and the associated real-time expression of weedy traits due to the complex and overlapping nature of biological interactions. Therefore, it is desirable to integrate the different omics technologies to give a better understanding of molecular functioning of biological systems. This multidimensional integrated approach can therefore offer new avenues for better understanding of questions of interest to weed scientists. This review offers a retrospective and prospective examination of omics platforms employed to investigate weed physiology and novel approaches and new technologies that can provide holistic and knowledge-based weed management strategies for future.

Apparent deficiency of soil mineral nutrients often triggers specific physio-morphological changes in plants, and some of these changes could also inadvertently increase the ability of plants to mobilize radionuclides from stable mineral forms. This work, through a series of sand-culture, hydroponics, and batch-equilibration experiments, investigated the differential ability of root exudates of Andropogon virginicus grown under conditions with variable phosphorus (P) availability (KHPO, FePO, Ca(PO), and no P) to solubilize uranium (U) from the uranyl phosphate mineral Chernikovite. The mineral form of P, and hence the bioavailability of P, affected the overall composition of the root exudates. The lower bioavailable forms of P (FePO and Ca(PO)), but not the complete absence of P, resulted in a higher abundance of root metabolites with chelating capacity at 72 hrs after treatment application. In treatments with lower P-bioavailability, the physiological amino acid concentration inside of the roots increased, whereas the concentration of organic acids in the roots decreased due to the active exudation. In batch dissolution experiments, the organic acids, but not amino acids, increase the dissolution U from Chernikovite. The root exudate matrix of plants exposed to low available forms of P induced a >60% increase in U dissolution from Chernikovite due to 5-16 times greater abundance of organic acids in these treatments. However, this was ca. 70% of the theoretical dissolution achievable by this exudate matrix. These results highlight the potential of using active management of soil P as an effective tool to alter the plant-mediated mobilization of U in contaminated soil.

Glyphosate-tolerant Ipomoea lacunosa is emerging as a problematic weed in the southeastern United States. Metabolomic profiling was conducted to examine the innate physiology and the glyphosate induced perturbations in two biotypes of I. lacunosa (WAS and QUI) that had contrasting glyphosate tolerance. Compared to the less tolerant QUI-biotype, the innate metabolism of the more tolerant WAS-biotype was characterized by a higher abundance of amino acids, and pyruvate; whereas the sugar profile of the QUI biotype was dominated by the transport sugar sucrose. Glyphosate application (80 g ae/ha) caused similar shikimate accumulation in both biotypes. Compared to QUI, in WAS, the content of aromatic amino acids was less affected by glyphosate treatment, and the content of Ala, Val, Ile, and Pro increased. However, the total sugars decreased by ∼75% in WAS, compared to ∼50% decrease in QUI. The innate, higher proportional abundance, of the transport-sugar sucrose in QUI coud partly explain the higher translocation and greater sensitivity of this biotype to glyphosate. The decrease in sugars, accompanied by an increase in amino acids could delay feedback regulation of upstream enzymes of the shikimate acid pathway in WAS, which could contribute to a greater glyphosate tolerance. Our study, through a metabolomics approach, provides complementary data that elucidates the cellular physiology of herbicide tolerance in Ipomoea lacunosa biotypes.