Role of Phosphorus Type and Biodegradable Polymer on Phosphorus Fate and Efficacy in a Plant-Soil System.

Phosphorus (P) is critical for crop production but has a high nutrient use inefficiency. Tomato was grown in soil amended with five P-sources, used as-is, or embedded within a biodegradable polymer, polyhydroxyalkanoate (PHA). Correlation analysis identified treatments that maintain plant growth, improve bioavailable soil P, and reduce P loss. Three performance classes were identified: (i) micro- and nanohydroxyapatite, which did not increase bioavailable P, plant P-uptake, or change P in runoff/leaching compared to controls; (ii) monocalcium phosphate (MCP), dicalcium phosphate (DCP), calcium pyrophosphate nanoparticles (CAP), and PHA-MCP that increased P-uptake and/or bioavailable P but also increased P loss in runoff/leaching; and (iii) PHA-DCP and PHA-CAP, where increased bioavailable P and plant P-uptake were achieved with minimal P loss in runoff/leaching. In addition to identifying treatments that maintain plant growth, increase bioavailable P, and minimize nutrient loss, correlation plots also revealed that (i) bioavailable P was a good indicator of plant P-uptake; (ii) leached P could be predicted from water solubility; and (iii) P loss through runoff versus leaching showed similar trends. This study highlights that biopolymers can promote plant P-uptake and improve bioavailable soil P, with implications for mitigating the negative environmental impacts of P loss from agricultural systems.

Influence of Oxygen-Containing Functional Groups on the Environmental Properties, Transformations, and Toxicity of Carbon Nanotubes.

Carbon nanotubes (CNTs) have unique physical and chemical properties that drive their use in a variety of commercial and industrial applications. CNTs are commonly oxidized prior to their use to enhance dispersion in polar solvents by deliberately grafting oxygen-containing functional groups onto CNT surfaces. In addition, CNT surface oxides can be unintentionally formed or modified after CNTs are released into the environment through exposure to reactive oxygen species and/or ultraviolet irradiation. Consequently, it is important to understand the impact of CNT surface oxidation on the environmental fate, transport, and toxicity of CNTs. In this review, we describe the specific role of oxygen-containing functional groups on the important environmental behaviors of CNTs in aqueous media (e.g., colloidal stability, adsorption, and photochemistry) as well as their biological impact. We place special emphasis on the value of systematically varying and quantifying surface oxides as a route to identifying quantitative structure-property relationships. The role of oxygen-containing functional groups in regulating the efficacy of CNT-enabled water treatment technologies and the influence of surface oxides on other carbon-based nanomaterials are also evaluated and discussed.

Photochemical Transformations of Carbon Dots in Aqueous Environments.

The unique physicochemical and luminescent properties of carbon dots (CDs) have motivated research efforts toward their incorporation into commercial products. Increased use of CDs will inevitably lead to their release into the environment where their fate and persistence will be influenced by photochemical transformations, the nature of which is poorly understood. This knowledge gap motivated the present investigation of the effects of direct and indirect photolysis on citric and malic acid-based CDs. Our results indicate that natural sunlight will rapidly and non-destructively photobleach CDs into optically inactive carbon nanoparticles. We demonstrate that after photobleaching, •OH exposure degrades CDs in a two-step process that will span several decades in natural waters. The first step, occurring over several years of •OH exposure, involves depolymerization of the CD structure, characterized by volatilization of over 60% of nascent carbon atoms and the oxidation of nitrogen atoms into nitro groups. This is followed by a slower oxidation of residual carbon atoms first into carboxylic acids and then volatile carbon species, while nitrogen atoms are oxidized into nitrate ions. Considered alongside related CD studies, our findings suggest that the environmental behavior of CDs will be strongly influenced by the molecular precursors used in their synthesis.