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1. Copper oxide nanoparticle dissolution at alkaline pH is controlled by dissolved organic matter: influence of soil-derived organic matter, wheat, bacteria, and nanoparticle coating

   https://doi.org/10.1039/d0en00574f  

   Hortin, J. M.; Anderson, A. J.; Britt, D. W.; Jacobson, A. R.; McLean, J. E. (January 2020, Environmental Science: Nano)

   Dissolution of CuO nanoparticles, releasing Cu ions, is a primary mechanism of Cu interaction in the rooting zone of plants. CuO dissolution is sometimes incorrectly considered negligible at high pH, since complexation of Cu with dissolved organic matter may enhance nanoparticle dissolution. Therefore data on the effects of plant-microbial-soil interactions on nanoparticle dissolution, particularly in alkaline soils, are needed. Dissolution of CuO nanoparticles (100 mg kg −1 Cu) was studied in sand supplemented with factorial combinations of wheat growth, a root-colonizing bacterium, and saturated paste extracts (SPEs) from three alkaline, calcareous soils. In control sand systems with 3.34 mM Ca(NO 3 ) 2 solution, dissolved Cu was low (266 μg L −1 Cu). Addition of dissolved organic matter via wheat root metabolites and/or soil SPEs increased dissolved Cu to 795–6250 μg L −1 Cu. Dissolution was correlated with dissolved organic carbon ( R = 0.916, p < 0.0001). Ligands >3 kDa, presumably fulvic acid from the SPEs, complexed Cu driving solubility; the addition of plant exudates further increased solubility 1.5–3.5×. The root-colonizing bacterium decreased dissolved Cu in sand pore waters from planted systems due to metabolism of root exudates. Batch solubility studies (10 mg L −1 Cu) with the soil SPEs and defined solutions containing bicarbonate or fulvic acid confirmed elevated CuO nanoparticle solubility at >7.5 pH. Nanoparticle dissolution was suppressed in batch experiments compared to sand, via nanoparticle organic matter coating or homoconjugation of dissolved organic matter. Alterations of CuO nanoparticles by soil organic matter, plant exudates, and bacteria will affect dissolution and bioavailability of the CuO nanoparticles in alkaline soils. 

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2. Review of Oxidative Dissolution and Sulfidation of Select Nanoparticles in the Environment: Impact on Applications

   https://doi.org/10.1021/acsanm.3c06227  

   O’Keefe, Tana L.; Haynes, Christy L. (April 2024, ACS Applied Nano Materials)

   Nanoparticles (NPs) are increasingly being used in medical, electronic, energy, and agricultural applications due to their unique properties that often arise due to the high surface area-to-volume ratio. However, this characteristic along with the high reactivity of NPs make these materials highly dynamic in environmental settings. Thus, several transformations can take place when these materials enter the environment that determines their transport, toxicity, and fate of them in our environment. These transformations, and more specifically oxidative dissolution and sulfidation, are directly impacted by the characteristics that a NP has in addition to the surrounding environmental conditions. Therefore, this review aims to summarize how NP characteristics (size, coatings, etc.) and other important environmentally relevant conditions (oxic/anoxic waters, natural organic matter, etc.) impact the oxidative dissolution and sulfidation of several metal and metal oxide NPs. The impact of these factors is crucial to understanding and predicting the environmental risks of these materials in a wide range of applications. 

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3. Soil-derived fulvic acid and root exudates, modified by soil bacteria, alter CuO nanoparticle-induced root stunting of wheat via Cu complexation

   https://doi.org/10.1039/c9en00728h  

   Hortin, J. M.; Anderson, A. J.; Britt, D. W.; Jacobson, A. R.; McLean, J. E. (December 2019, Environmental Science: Nano)

   CuO nanoparticles (NPs) are explored as fungicides and fertilizers, and are increasingly likely to be applied to agricultural soils. Consequently, interactions of CuO NPs with soil pore water (SPW) components, plants, and microbes must be understood. These experiments examined whether dissolved natural organic matter (DNOM) from SPW, or root/bacterial exudates, changed wheat ( Triticum aestivum L. v. Deloris) responses to 100 mg kg −1 (Cu/sand) as CuO NPs. Seedlings were grown in sand with 3.34 mM Ca(NO 3 ) 2 or one of three SPWs, differing in DNOM concentration and composition. At 10 days post-germination, CuO NPs stunted roots by 59% in the 3.34 mM Ca(NO 3 ) 2 and 26–35% in the three SPWs compared to plants grown without NPs. Malate, citrate, gluconate, and 2′-deoxymugineic acid (DMA), were elevated 1.3 to 5-fold in the rhizosphere with CuO NPs present. Cu was bioavailable through metallo-organic complexes, including Cu–DMA and Cu–gluconate. Fulvic acid in SPWs mitigated CuO NP-induced wheat root shortening. Pseudomonas chlororaphis O6 eliminated malate and citrate in the rhizospheres, reduced rhizosphere dissolved Cu ∼18–66%, and reduced root Cu 39% across all SPWs while enhancing root stunting ∼17% more across all SPWs than non-inoculated wheat grown with CuO NPs. Thus, both SPW components and root microbial colonization influenced wheat responses to CuO NPs. These interactions are likely in agricultural soils with additional processes, such as ion sorption, to influence CuO NP phytotoxicity, highlighting the importance of considering not just the target plant, but soil properties and associated microbiomes when evaluating impacts of NPs in agricultural usage. 

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4. Organic Coatings Reduce Dissolution Rate by an Order of Magnitude for Carbonate Minerals Produced by Marine Fish

   https://doi.org/10.1029/2024GB008176  

   Oehlert, Amanda_M; Walls, Sarah; Arista, Katelyn; Garza, Jazmin; Folkerts, Erik_J; Vitek, Brooke_E; Tale_Masoule, Sadegh; Pollier, Clément_G_L; Duchâtellier, Gaëlle; Stieglitz, John_D; et al (November 2024, Global Biogeochemical Cycles)

   Abstract Marine carbonate production and dissolution are important components of the global carbon cycle and the marine alkalinity budget. Global carbonate production by marine fish (ichthyocarbonate) has been estimated to be as high as 9.03 Pg CaCO₃ yr⁻¹; however, the fate of ichthyocarbonate is poorly understood. High magnesium concentrations in ichthyocarbonate would traditionally suggest rapid dissolution under current marine conditions, but a correlation between dissolution rate and mol%MgCO₃has not been observed. Here, we aim to determine the role of organic coatings on dissolution rates of ichthyocarbonate in marine environments. We applied a combination of petrographic, geochemical, and microCT approaches to assess the quantity and distribution of organic matter in ichthyocarbonate produced by two species of marine fish, the Gulf toadfish (Opsanus beta) and the Olive flounder (Paralichthys olivaceus). We show that organic matter, including external coatings and embedded organic material, is volumetrically significant, ranging from 8.5% to 32.3% of ichthyocarbonate by volume. Bleach oxidation of external organic matter coatings increased the dissolution rate of ichthyocarbonate by more than an order of magnitude, suggesting these coatings serve to reduce reactive surface area of the mineral fraction in ichthyocarbonate. Assuming that organic coatings do not influence sinking rates, external coatings extend the depth of ichthyocarbonate persistence in the water column by ∼12–15×. Therefore, organic coatings are an important determinant of the role of ichthyocarbonate in the marine carbon cycle. 

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5. Biomolecular corona formation on CuO nanoparticles in plant xylem fluid

   https://doi.org/10.1039/D1EN00140J  

   Borgatta, Jaya R.; Lochbaum, Christian A.; Elmer, Wade H.; White, Jason C.; Pedersen, Joel A.; Hamers, Robert J. (January 2021, Environmental Science: Nano)

   null (Ed.)

   Biomolecular coatings (coronas) that form on nanomaterials have been widely investigated in animal and bacterial cell culture and in the extracellular and intracellular fluids of animals. Such coronas influence the distribution of nanoparticles within organisms, their uptake by cells, and their storage in intracellular compartments. Plants can be exposed to nanoparticles via either intentional application of nanomaterials in agriculture or inadvertently due, for example, to biosolids amendment of soils. Development of a mechanistic understanding of nanoparticle transport and fate within plants requires consideration of corona acquisition within plants, particularly within the vascular fluids that transport nanoparticles throughout plants. Here, we examine the interactions between copper oxide (CuO) nanoparticles and pumpkin xylem fluid to understand corona formation in an important part of the plant vasculature system. We used CuO nanoparticles because they have emerged as a promising micronutrient source for the suppression of fungal diseases. The corona was composed primarily of proteins, despite the higher abundance of carbohydrates in xylem fluid. We used X-ray photoelectron spectroscopy to determine the thickness of the protein corona. Polyacrylamide gel electrophoresis revealed that protein binding to the CuO nanoparticle surface was selective; the most abundant proteins in the corona were not the most abundant ones in the xylem fluid. We used in situ attenuated total reflectance Fourier-transform infrared spectroscopy to show that the protein–CuO NP interactions were quasi-irreversible, while carbohydrate–CuO interactions were reversible. Corona formation is expected to influence the distribution and transformation of nanomaterials in plants. 

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