The immense production of plastic polymers combined with their discordancy with nature has led to vast plastic waste contamination across the geosphere, from the oceans to freshwater reservoirs, wetlands, remote snowpacks, sediments, air and multiple other environments. These environmental pollutants include microplastics (MP), typically defined as small and fragmented plastics less than 5 mm in size, and nanoplastics (NP), particles smaller than a micrometer. The formation of micro and nanoplastics in aqueous media to date has been largely attributed to fragmentation of plastics by natural (i.e., abrasion, photolysis, biotic) or industrial processes. We present a novel method to create small microplastics (≲ 5 μm) and nanoplastics in water from a wide variety of plastic materials using a small volume of a solubilizer liquid, such as n-dodecane, in combination with vigorous mixing. When the suspensions or solutions are subjected to ultrasonic mixing, the particle sizes decrease. Small micro- and nanoparticles were made from commercial, real world and waste (aged) polyethylene, polystyrene, polycarbonate and polyethylene terephthalate, in addition to other plastic materials and were analyzed using dark field microscopy, Raman spectroscopy and particle size measurements. The presented method provides a new and simple way to create specific size distributions of micro- and nanoparticles, which will enable expanded research on these plastic particles in water, especially those made from real world and aged plastics. The ease of NP and small MP formation upon initial mixing simulates real world environments, thereby providing further insight into the behavior of plastics in natural settings.

Microplastic waste is a worldwide problem, heavily afflicting marine and freshwater environments; the loading of this pollution in water, sediment and living organisms continues to escalate.

Efficient separation of the actinides from the lanthanides is a critical challenge in the development of a more sophisticated spent nuclear fuel recycling process. Based upon the slight differences in f-orbital distribution, a new class of soft nitrogen-donor ligands, the sulfonated bis-triazinyl-(bi)pyridines, has been identified and shown to be successful for this separation under anticipated, large-scale treatment conditions. The radiation robustness of these ligands is key to their implementation; however, current stability studies have yielded conflicting results. Here we report on the radiolytic degradation of the sulfonated 2,6-bis(1,2,4-triazin-3-yl)pyridine (BTP(S)) and 6,6′-bis(1,2,4-triazin-3-yl)-2,2′-bipyridine (BTBP(S)) in aerated, aqueous solutions using a combination of time-resolved pulsed electron techniques to ascertain their reaction kinetics with key aqueous radiolysis products (e_aq ⁻, H˙, ˙OH, and ˙NO₃), and steady state gamma radiolysis in conjunction with liquid chromatography for identification and quantification of both ligands as a function of absorbed dose. These data were used to construct a predictive deterministic model to provide critical insight into the fundamental radiolysis mechanisms responsible for the ligands’ radiolytic stability. The first-order decays of BTP(S) and BTBP(S) are predominantly driven by oxidative processes (˙OH and, to a lesser extent, H₂O₂), for which calculations demonstrate that the rate of degradation is inhibited by the formation of ligand degradation products that undergo secondary reactions with the primary products of water radiolysis. Overall, BTP(S) is ∼20% more radiolytically stable than BTBP(S), but over 90% of either ligand is consumed within 1 kGy.

We report a ³¹P NMR investigation into the activated radioprotection mechanism of octylphenyl-N,N-diisobutyl-carbamoylmethyl phosphine oxide (CMPO) and analogues in the presence of a gamma radiation field. CMPO exhibits significantly enhanced radiation resistance in the presence of high nitric acid concentrations, compared to other ligands proposed for recovery of the trivalent actinides from spent nuclear fuel. The fundamental mechanism behind this activated radioprotection has been investigated using ³¹P NMR and other supporting analytical techniques (GCMS and LCMS) in conjunction with systematic gamma irradiation studies, covering solvent system formulation and structural effects through the use of the CMPO analogues, dioctylphenylphospine oxide (DOPPO) and trioctylphosphine oxide (TOPO). These experiments have demonstrated that the acid-dependent, radioprotection mechanism requires a protonated phenyl-phosphine oxide motif to activate. Further, contacting these three ligand loaded organic phases with a range of mineral acids (nitric, sulfuric, hydrochloric, and perchloric acids) shows specificity for nitric acid (HNO₃), and the formation of a distinct [ligand·HNO₃] complex for CMPO and DOPPO, as identified by ³¹P NMR, and predicted by DFT calculations. We propose that this complex is capable of sequential n-dodecane excited state quenching through the conjugated aromatic functionalities on the constituent CMPO and DOPPO molecules.

Polyethylene (PE) is an intensely utilized polymer, which has consequently led to it becoming a common environmental contaminant. PE and other plastic waste are known to be highly persistent in surface waters; however, chemical and physical changes do take place over time, dependent mostly on highly variable natural conditions, such as oxygen (O₂) availability. Gamma radiation was used to generate reactive oxygen species, namely hydroxyl radicals, in initially aerated aqueous solutions to simulate the natural weathering of microplastics in waters where there are fluctuations and often depletions in dissolved O₂. The headspace of the irradiated PE-containing solutions was probed for the formation of degradation products using solid-phase microextraction (SPME) fibers in combination with gas chromatography mass spectrometry (GCMS). The major species detected were n-dodecane, with trace levels of tridecane, 2-dodecanone, and hexadecane, which were believed to be predominately adsorbed in the PE microplastics in excess of their aqueous solubility limits. Surface characterization by Raman spectroscopy and light and dark field microscopy indicated no change in the chemical composition of the irradiated PE microplastics under low O₂ to anaerobic conditions. However, morphological changes were observed, indicating radical combination reactions.