Facile nanoplastics formation from macro and microplastics in aqueous media.

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.

Sequestration of microfibers and other microplastics by green algae, Cladophora, in the US Great Lakes.

Daunting amounts of microplastics are present in surface waters worldwide. A main category of microplastics is synthetic microfibers, which originate from textiles. These microplastics are generated and released in laundering and are discharged by wastewater treatment plants or enter surface waters from other sources. The polymers that constitute many common synthetic microfibers are mostly denser than water, and eventually settle out in aquatic environments. The interaction of these microfibers with submerged aquatic vegetation has not been thoroughly investigated but is potentially an important aquatic sink in surface waters. In the Laurentian Great Lakes, prolific growth of macrophytic Cladophora creates submerged biomass with a large amount of surface area and the potential to collect and concentrate microplastics. To determine the number of synthetic microfibers in Great Lakes Cladophora, samples were collected from Lakes Erie and Michigan at multiple depths in the spring and summer of 2018. After rinsing and processing the algae, associated synthetic microfibers were quantified. The average loads of synthetic microfibers determined from the Lake Erie and Lake Michigan samples were 32,000 per kg (dry weight (dw)) and 34,000 per kg (dw), respectively, 2-4 orders of magnitude greater than loads previously reported in water and sediment. To further explore this sequestration of microplastics, fresh and aged Cladophora were mixed with aqueous mixtures of microfibers or microplastic in the laboratory to simulate pollution events. Microscopic analyses indicated that fresh Cladophora algae readily interacted with microplastics via adsorptive forces and physical entanglement. These interactions mostly cease upon algal senescence, with an expected release of microplastics in benthic sediments. Collectively, these findings suggest that synthetic microfibers are widespread in Cladophora algae and the affinity between microplastics and Cladophora may offer insights for removing microplastic pollution. Macroalgae in the Laurentian Great Lakes contain high loads of synthetic microfibers, both entangled and adsorbed, which likely account for an important fraction of microplastics in these surface waters.

Characterization and within-site variation of environmental metal concentrations around a contaminated site using a community-engaged approach.

Historic industrial activity led to extensive lead and arsenic contamination within residential areas of East Chicago, Indiana, United States. Although remediation is underway, community concerns about this contamination remain. Therefore, the goal for this analysis was to characterize environmental contamination in soil within and around these areas. A total of 228 samples from 32 different sites (addresses) were collected by community members or study staff. These were analyzed for metals using portable x-ray fluorescence or inductively coupled plasma ̶ optical emission spectroscopy. Concentrations exceeding EPA screening levels were found for 42% of the soil arsenic samples, 35% of the soil lead samples, and 79% of the soil manganese samples; a few samples also contained elevated copper or zinc. Concentrations above EPA screening levels were identified both within and outside of the formally designated contaminated area. Roughly 30% of all sites had at least one sample above and one sample below the screening level for arsenic, lead, and manganese. For sites within the contaminated area, more than 90% (arsenic), 60% (lead) and 60% (manganese) of the samples exceeded EPA screening levels. There was a significant association of proximity to the historic industrial site with elevated soil concentrations of arsenic and lead; a similar association was present for manganese. These results are consistent with existing data for lead and arsenic and we additionally report elevated concentrations of manganese and a high within-site variability of all metal concentrations. These findings should be considered in future remediation efforts.

Tracking the distribution of microfiber pollution in a southern Lake Michigan watershed through the analysis of water, sediment and air.

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. Synthetic microfibers, resulting from the release of microscopic fibers from synthetic textiles, constitute the most prevalent type of microplastics pollution in aquatic environments. This study investigated the origin and distribution of synthetic microfibers in a representative Lake Michigan watershed in Indiana (USA) by analyzing water, sediment and air samples above and below wastewater treatment plant discharges, downstream in the watershed and water from the Lake Michigan shoreline. Synthetic microfibers were also quantified in wastewater from a local wastewater treatment plant (WWTP) and in laundry effluent. Laboratory testing of numerous fabrics suggests that Fenton oxidation, used to break down natural fibers, effectively eliminates non-polluting, natural fibers from the samples. However, the hydroxyl radical-mediated oxidation bleaches the dye from certain synthetic microfibers, which likely leads to under-reported values for these microplastics in natural samples. The data collected from the watershed samples indicate that approximately 4 billion synthetic microfibers are transported daily through the Lake Michigan tributary. Wastewater effluent is not the only source of synthetic microfibers, since surface water samples above the WWTP contained a similar load to downstream samples. Repeated sampling exhibited variability in the number of microfibers detected, substantiating the heterogeneous distribution of these pollutants and the requirement for multiple samples for a given site. The average load of synthetic microfibers from water sampled at the Lake Michigan shoreline was higher than the tributary water, suggesting the shoreline functions as a repository for the microfibers. Given the extent and potential consequences of this pollution, quantification of the ubiquitous plastic fibers can be instituted as part of the traditional total suspended solids (TSS) water quality monitoring parameter.

31P NMR study of the activated radioprotection mechanism of octylphenyl-N,N-diisobutylcarbamoylmethyl phosphine oxide (CMPO) and analogues.

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.

Time-resolved and steady-state irradiation of hydrophilic sulfonated bis-triazinyl-(bi)pyridines - modelling radiolytic degradation.

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 (eaq-, 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.

Oxidative remediation of 4-methylcyclohexanemethanol (MCHM) and propylene glycol phenyl ether (PPh). Evidence of contaminant repair reaction pathways.

A large spill of 4-methylcyclohexanemethanol (MCHM) and propylene glycol phenyl ether (PPh) into the Elk River near Charleston, West Virginia on January 9, 2014 led to serious water contamination and public concerns about appropriate remediation. To assess the feasibility of advanced oxidation processes (AOPs) for remediation of waters contaminated with these compounds, we induced hydroxyl radical (HO˙) reactions using time-resolved and steady-state radiolysis methods. Detailed product analyses showed initial HO˙ attack was at the benzene ring of PPh, and occurred through H-atom abstraction reactions for MCHM. Pulse radiolysis and steady state radiolysis experiments conducted using pure compound solutions, mixtures of the compounds and real water solvents allowed us to obtain mechanistic insights of hydroxyl radical attack and establish the fate of the compounds using AOP remediation technologies. These results demonstrate that hydroxyl radical induced oxidization of PPh can lead to "repair-type" reactions, which regenerates this contaminant. The study further highlights the importance of such counterproductive reactions for the quantitative estimate of the required amount of oxidant in any large-scale treatment approaches.

Virulence and biodegradation potential of dynamic microbial communities associated with decaying Cladophora in Great Lakes.

Cladophora mats that accumulate and decompose along shorelines of the Great Lakes create potential threats to the health of humans and wildlife. The decaying algae create a low oxygen and redox potential environment favoring growth and persistence of anaerobic microbial populations, including Clostridium botulinum, the causal agent of botulism in humans, birds, and other wildlife. In addition to the diverse population of microbes, a dynamic chemical environment is generated, which involves production of numerous organic and inorganic substances, many of which are believed to be toxic to the sand and aquatic biotic communities. In this study, we used 16S-rDNA-based-amplicon sequencing and microfluidic-based quantitative PCR approaches to characterize the bacterial community structure and the abundances of human pathogens associated with Cladophora at different stages (up to 90days) of algal decay in laboratory microcosms. Oxygen levels were largely depleted after a few hours of incubation. As Cladophora decayed, the algal microbial biodiversity decreased within 24h, and the mat transitioned from an aerobic to anaerobic environment. There were increasing abundances of enteric and pathogenic bacteria during decomposition of Cladophora, including Acinetobacter, Enterobacter, Kluyvera, Cedecea, and others. In contrast, there were no or very few sequences (<0.07%) assigned to such groups in fresh Cladophora samples. Principal coordinate analysis indicated that the bacterial community structure was dynamic and changed significantly with decay time. Knowledge of microbial communities and chemical composition of decaying algal mats is critical to our further understanding of the role that Cladophora plays in a beach ecosystem's structure and function, including the algal role in trophic interactions. Based on these findings, public and environmental health concerns should be considered when decaying Cladophora mats accumulate Great Lakes shorelines.

Prevalence of toxin-producing Clostridium botulinum associated with the macroalga Cladophora in three Great Lakes: growth and management.

The reemergence of avian botulism caused by Clostridium botulinum type E has been observed across the Great Lakes in recent years. Evidence suggests an association between the nuisance algae, Cladophora spp., and C. botulinum in nearshore areas of the Great Lakes. However, the nature of the association between Cladophora and C. botulinum is not fully understood due, in part, to the complex food web interactions in this disease etiology. In this study, we extensively evaluated their association by quantitatively examining population size and serotypes of C. botulinum in algal mats collected from wide geographic areas in lakes Michigan, Ontario, and Erie in 2011-2012 and comparing them with frequencies in other matrices such as sand and water. A high prevalence (96%) of C. botulinum type E was observed in Cladophora mats collected from shorelines of the Great Lakes in 2012. Among the algae samples containing detectable C. botulinum, the population size of C. Botulinum type E was 10(0)-10(4) MPN/g dried algae, which was much greater (up to 10(3) fold) than that found in sand or the water column, indicating that Cladophora mats are sources of this pathogen. Mouse toxinantitoxin bioassays confirmed that the putative C. botulinum belonged to the type E serotype. Steam treatment was effective in reducing or eliminating C. botulinum type E viable cells in Cladophora mats, thereby breaking the potential transmission route of toxin up to the food chain. Consequently, our data suggest that steam treatment incorporated with a beach cleaning machine may be an effective treatment of Cladophora-borne C. botulinum and may reduce bird mortality and human health risks.

N-nitrosodimethylamine (NDMA) formation from the ozonation of model compounds.

Nitrosamines are a class of toxic disinfection byproducts commonly associated with chloramination, of which several were included on the most recent U.S. EPA Contaminant Candidate List. Nitrosamine formation may be a significant barrier to ozonation in water reuse applications, particularly for direct or indirect potable reuse, since recent studies show direct formation during ozonation of natural water and treated wastewaters. Only a few studies have identified precursors which react with ozone to form N-nitrosodimethylamine (NDMA). In this study, several precursor compound solutions, prepared in ultrapure water and treated wastewater, were subjected to a 10 M excess of ozone. In parallel experiments, the precursor solutions in ultrapure water were exposed to gamma radiation to determine NDMA formation as a byproduct of reactions of precursor compounds with hydroxyl radicals. The results show six new NDMA precursor compounds that have not been previously reported in the literature, including compounds with hydrazone and carbamate moieties. Molar yields in deionized water were 61-78% for 3 precursors, 12-23% for 5 precursors and <4% for 2 precursors. Bromide concentration was important for three compounds (1,1-dimethylhydrazine, acetone dimethylhydrazone and dimethylsulfamide), but did not enhance NDMA formation for the other precursors. NDMA formation due to chloramination was minimal compared to formation due to ozonation, suggesting distinct groups of precursor compounds for these two oxidants. Hydroxyl radical reactions with the precursors will produce NDMA, but formation is much greater in the presence of molecular ozone. Also, hydroxyl radical scavenging during ozonation leads to increased NDMA formation. Molar conversion yields were higher for several precursors in wastewater as compared to deionized water, which could be due to catalyzed reactions with constituents found in wastewater or hydroxyl radical scavenging.

Kinetics and mechanism of (•)OH mediated degradation of dimethyl phthalate in aqueous solution: experimental and theoretical studies.

The hydroxyl radical ((•)OH) is one of the main oxidative species in aqueous phase advanced oxidation processes, and its initial reactions with organic pollutants are important to understand the transformation and fate of organics in water environments. Insights into the kinetics and mechanism of (•)OH mediated degradation of the model environmental endocrine disruptor, dimethyl phthalate (DMP), have been obtained using radiolysis experiments and computational methods. The bimolecular rate constant for the (•)OH reaction with DMP was determined to be (3.2 ± 0.1) × 10(9) M(-1)s(-1). The possible reaction mechanisms of radical adduct formation (RAF), hydrogen atom transfer (HAT), and single electron transfer (SET) were considered. By comparing the experimental absorption spectra with the computational results, it was concluded that the RAF and HAT were the dominant reaction pathways, and OH-adducts ((•)DMPOH1, (•)DMPOH2) and methyl type radicals (•)DMP(-H)α were identified as dominated intermediates. Computational results confirmed the identification of transient species with maximum absorption around 260 nm as (•)DMPOH1 and (•)DMP(-H)α, and these radical intermediates then converted to monohydroxylated dimethyl phthalates and monomethyl phthalates. Experimental and computational analyses which elucidated the mechanism of (•)OH-mediated degradation of DMP are discussed in detail.

Association of toxin-producing Clostridium botulinum with the macroalga Cladophora in the Great Lakes.

Avian botulism, a paralytic disease of birds, often occurs on a yearly cycle and is increasingly becoming more common in the Great Lakes. Outbreaks are caused by bird ingestion of neurotoxins produced by Clostridium botulinum, a spore-forming, gram-positive, anaerobe. The nuisance, macrophytic, green alga Cladophora (Chlorophyta; mostly Cladophora glomerata L.) is a potential habitat for the growth of C. botulinum. A high incidence of botulism in shoreline birds at Sleeping Bear Dunes National Lakeshore (SLBE) in Lake Michigan coincides with increasingly massive accumulations of Cladophora in nearshore waters. In this study, free-floating algal mats were collected from SLBE and other shorelines of the Great Lakes between June and October 2011. The abundance of C. botulinum in algal mats was quantified and the type of botulism neurotoxin (bont) genes associated with this organism were determined by using most-probable-number PCR (MPN-PCR) and five distinct bont gene-specific primers (A, B, C, E, and F). The MPN-PCR results showed that 16 of 22 (73%) algal mats from the SLBE and 23 of 31(74%) algal mats from other shorelines of the Great Lakes contained the bont type E (bont/E) gene. C. botulinum was present up to 15000 MPN per gram dried algae based on gene copies of bont/E. In addition, genes for bont/A and bont/B, which are commonly associated with human diseases, were detected in a few algal samples. Moreover, C. botulinum was present as vegetative cells rather than as dormant spores in Cladophora mats. Mouse toxin assays done using supernatants from enrichment of Cladophora containing high densities of C. botulinum (>1000 MPN/g dried algae) showed that Cladophora-borne C. botulinum were toxin-producing species (BoNT/E). Our results indicate that Cladophora provides a habitat for C. botulinum, warranting additional studies to better understand the relationship between this bacterium and the alga, and how this interaction potentially contributes to botulism outbreaks in birds.

Free-radical-induced oxidative and reductive degradation of sulfa drugs in water: absolute kinetics and efficiencies of hydroxyl radical and hydrated electron reactions.

Absolute rate constants and degradation efficiencies for hydroxyl radical and hydrated electron reactions with four different sulfa drugs in water have been evaluated using a combination of electron pulse radiolysis/absorption spectroscopy and steady-state radiolysis/high-performance liquid chromatography measurements. For sulfamethazine, sulfamethizole, sulfamethoxazole, and sulfamerazine, absolute rate constants for hydroxyl radical oxidation were determined as (8.3 +/- 0.8) x 10(9), (7.9 +/- 0.4) x 10(9), (8.5 +/- 0.3) x 10(9), and (7.8 +/- 0.3) x 10(9) M(-1) s(-1), respectively, with corresponding degradation efficiencies of 36% +/- 6%, 46% +/- 8%, 53% +/- 8%, and 35% +/- 5%. The reduction of these four compounds by their reaction with the hydrated electron occurred with rate constants of (2.4 +/- 0.1) x 10(10), (2.0 +/- 0.1) x 10(10), (1.0 +/- 0.03) x 10(10), and (2.0 +/- 0.1) x 10(10) M(-1) s(-1), respectively, with efficiencies of 0.5% +/- 4%, 61% +/- 9%, 71% +/- 10%, and 19% +/- 5%. We propose that hydroxyl radical adds predominantly to the sulfanilic acid ring of the different sulfa drugs based on similar hydroxyl radical rate constants and transient absorption spectra. In contrast, the variation in the rate constants for hydrated electrons with the sulfa drugs suggests the reaction occurs at different reaction sites, likely the different heterocyclic rings. The results of this study provide fundamental mechanistic parameters, hydroxyl radical and hydrated electron rate constants, and degradation efficiencies that are critical for the evaluation and implementation of advanced oxidation processes (AOPs).

Radiolytic transformations of chlorinated phenols and chlorinated phenoxyacetic acids.

Hydroxyl radical reactions of selected chlorinated aromatic phenols (2,4-dichlorophenol, 2,4,6-trichlorophenol, and pentachlorophenol) and chlorinated phenoxyacetic acids [2,4-dichlorophenoxyacetic acid (2,4-D), 2,4-D methyl ester, 2-(2,4-dichlorophenoxy)propionic acid (2,4-DP)] were studied using the radiolysis techniques of pulse radiolysis and gamma radiolysis. Hydroxyl radical addition was the prominent reaction pathway for the chlorinated phenoxyacetic acids and also for the chlorinated phenols at pH values below the pK(a) of the compounds. A very prominent change in (*)OH reactivity was observed with the chlorinated phenoxide ions in high pH solutions. Two different reaction pathways were clearly present between the hydroxyl radical and the chlorinated phenoxide ions. One of the reaction pathways was suppressed when the concentration of chlorinated phenoxide ions was increased 10-fold. Amid a greater electron-withdrawing presence on the aromatic ring (higher chlorinated phenoxide ions), the hydroxyl radical reacted preferably by way of addition to the aromatic ring. Steady-state experiments utilizing gamma radiolysis also showed a substantial decrease in oxidation with an increase in pH of substrate.

Mechanism of hydroxyl radical-induced breakdown of the herbicide 2,4-dichlorophenoxyacetic acid (2,4-d).

Oxidative transformations by the hydroxyl radical are significant in advanced oxidation processes for the breakdown of organic pollutants, yet mechanistic details of the reactions are lacking. A combination of experimental and computational methods has been employed in this study to elucidate the reactivity of the hydroxyl radical with the widely used herbicide 2,4-D (2,4-dichlorophenoxyacetic acid). The experimental data on the reactivity of the hydroxyl radical in the degradation of the herbicide 2,4-D were obtained from gamma-radiolysis experiments with both (18)O-labeled and unlabeled water. These were complemented by computational studies of the (.)OH attack on 2,4-D and 2,4-DCP (2,4-dichlorophenol) in the gas phase and in solution. These studies firmly established the kinetically controlled attack ipso to the ether functionality as the main reaction pathway of (.)OH and 2,4-D, followed by homolytic elimination of the ether side chain. In addition, the majority of the early intermediates in the reaction between the hydroxyl radical and 2,4-DCP, the major intermediate, were identified experimentally. While the hydroxyl radical attacks 2,4-D by (.)OH-addition/elimination on the aromatic ring, the oxidative breakdown of 2,4-DCP occurs through (.)OH addition followed by either elimination of chlorine or formation of the ensuing dichlorophenoxyl radical.

Synergy of combining sonolysis and photocatalysis in the degradation and mineralization of chlorinated aromatic compounds.

Merits of using advanced oxidation processes such as sonolysis and photocatalysis as well as a combination of the two have been explored using model herbicides such as 2,4-dichlorophenoxy acetic acid and 2,4-dichlorophenoxypropionic acid and the chlorinated phenols 2,4-dichlorophenol and 2,4,6-trichlorophenol. Whereas sonolysis is quite effective in the initial degradation of chlorinated aromatic molecules, complete mineralization is difficult to achieve. Photocatalysis is selective toward the degradation of polar compounds but causes the build up of undesirable chemical intermediates. In contrast to sonolytic degradation, photocatalysis is very effective toward achieving complete mineralization. By simultaneously carrying out high-frequency sonolysis and photocatalysis we have succeeded in achieving faster and complete mineralization with no build up of toxic intermediates even at very low catalyst loadings. The synergy of combining the two advanced oxidation processes is discussed.