Erosion of rigid plastics in turbid (sandy) water: quantitative assessment for marine environments and formation of microplastics.

Mechanical degradation (erosion) of plastics in the marine environment has been reported in many literature studies but without quantitative information. This type of degradation is crucial as it accounts for most of the initial microplastic products, in marine environments (e.g., rivers and oceans). Here, we quantify the erosion of plastics by water-borne sediments under typical perpendicular water velocities and sand loads of turbid rivers and coastal oceans. Polypropylene (PP) shows the highest response to water-borne erosion, with a surface degradation rate of 5160 µm per year (4.44 mg per mm2 per year), compared with high-density polyethylene (HDPE) with a degradation rate of 1874 µm per year (1.79 mg per mm2 per year), resulting in the formation of microplastics (MPs). The rate of formation of such microplastic particles (>10 µm), as characterised by a laser direct infrared (LDIR) chemical imaging system, amounts to 669 particles per mm2 per year for PP and 187 particles per mm2 per year for HDPE, exhibiting average particle sizes of 60 µm and 23 µm in the same order. Furthermore, surface microscopy provided valuable insights into the dominant erosion mechanisms, revealing three distinct zones and the surface features reveal the brittle erosion behaviours. These results will enable a better assessment of degradation and lifetime prediction of plastics in turbid rivers and coastal oceans, allowing precise estimation of the rate of formation of MPs.

Pilot-scale performance of gravity-driven ultra-high flux fabric membrane systems for removing small-sized microplastics in wastewater treatment plant effluents.

The ubiquitous nature and environmental impacts of microplastic particles and fibers demand effective solutions to remove such micropollutants from sizable point sources, including wastewater treatment plants and road runoff facilities. While advanced methods, e.g., microfiltration and ultrafiltration, have shown high removal efficiencies of small-sized microplastics (<150 µm), the low flux encountered in these systems implies high operation costs and makes them less effective in high-capacity wastewater facilities. The issue presents new opportunities for developing cheap high-flux membrane systems, deployable in low-to high-income economies, to remove small-sized microplastic and nanoplastics in wastewater. Here, we report on developing an ultra-high flux gravity-driven fabric membrane system, assessed through a laboratory-scale filtration and large-scale performance in an actual wastewater treatment plant (WWTP). The method followed a carefully designed water sampling, pre-treatment protocol, and analytical measurements involving Fourier transform infrared (FTIR) spectroscopy and laser direct infrared (LDIR) imaging. The result shows that the ultra-high flux (permeance = 550,000 L/m2h⋅bar) fabric membrane system can effectively remove small-sized microplastics (10-300 µm) in the secondary effluent of an actual WWTP at high efficiency greater than 96 %. The pilot system demonstrated a continuous treatment capacity of 300,000 L/day through a 1 m2 surface area disc, with steady removal rates of microplastics. These findings demonstrate the practical, cheap, and sustainable removal of small-sized microplastics in wastewater treatment plants, and their potential value for other large-scale point sources, e.g., stormwater treatment facilities.

Quantifying annual microplastic emissions of an urban catchment: Surface runoff vs wastewater sources.

Urban clusters are recognized as hotspots of microplastic pollution, and the associated urban rivers convey microplastics into the global oceans. Despite this knowledge, the relative contributions of various sources to the annual microplastic emissions from urban catchments remain scarcely quantified. Here, we quantified microplastic emissions from a riverine urban catchment in Japan. The total microplastics (size range: 10-5000 µm) released from the catchment amounted to 269.1 tons/annum, of which 78.1% is contributed by surface runoff and other uncontrolled emissions (UCE), and 21.1% emerges from the regulated wastewater (controlled emissions; CE), implying that approximately one-fifth is intercepted and removed by the wastewater treatment plants (WWTPs). This further indicated higher microplastic pollution by unmanaged surface runoff compared to untreated wastewater. In the dry season, WWTPs contributed significantly to the reduction of total microplastic emissions (95%) compared to wet periods (8%). On an annual scale, the treated effluent occupies only 0.1% of the total microplastics released to the river network (212.4 tons/annum), while the remaining portion is dominated by UCE, i.e., primarily surface runoff emissions (98.9%), and trivially by the background microplastic inputs that are potentially derived through atmospheric depositions in dry days (1.0%). It was shown that moderate and heavy rainfall events which occur during 18% of the year (within the context of Japan), leading to 95% of the annual microplastic emissions, are crucial for pollution control of urban rivers. Furthermore, our study demonstrated that surface area-normalized microplastic emissions from an urban catchment (∼0.8 tons/km2/annum) is globally relevant, especially for planning microplastic interventions for developed cities.

Inter-event and intra-event dynamics of microplastic emissions in an urban river during rainfall episodes.

Urban rivers represent the major conduits for land-sourced microplastics in the global oceans, yet the real-time dynamics of their emissions in rivers during rainfall (and runoff) events are poorly understood. Herein, we report the results of high-frequency sampling of microplastic particles (MPs) and fibers (MPFs) in the surface water of an urban river in Japan over the course of three rainfall events (i.e., light, moderate, and heavy rainfalls). The event mean concentrations (EMCs) of MPs amounted to 35,000 items/m3, 929,000 items/m3, and 331,000 items/m3; and the corresponding total loads were 0.5 kg, 19.8 kg, and 35.0 kg for light, moderate and heavy rainfalls, respectively. The inter-event total loads of MPs correlate well with the total rainfall, while the concentrations were linked with the number of antecedent dry days. The dynamic trends show that <2000 µm MPs displayed first flush effects during light to moderate rainfall events (>50% mass discharged with the initial 20-40% of flow). Small-sized MPs (10-40 µm) mobilized rapidly at lower rainfall intensities, whereas MPs over 2000 µm discharged immediately after the peak rainfall intensity. Moreover, <70 µm MPs depicted a surge following heavy rainfall events due to turbulent flow conditions reverting the deposited MPs into suspension. Overall, the three events increased the loads by 4-110 folds, and EMCs by 10-350 folds compared to the concentrations during dry weather while portraying a significant impact on 300-1000 µm MPs. The dynamics of MPs were correlated with those of suspended solids in river water, and the characteristics were comparable to the same of road dust sampled in Japan. Although the dynamic trends between MPs and MPFs in river water were comparable, MPFs were relatively less impacted by rain, likely due to the intervention of separate sewer systems in the study area.

Occurrence and distribution of plastic particles (10-25,000 µm) and microfibers in the surface water of an urban river network in Japan.

Urban rivers remain the key conduits conveying land-sourced plastics into the ocean. However, detailed information is limited on the concurrent evaluation over a wide array of particle size-specific abundances, characteristics, and distribution patterns of plastics in riverine environments. Therefore, this study provides a comprehensive assessment of plastic pollution in an urban river network in Japan by analyzing mesoplastics (5000-25,000 µm), large microplastics (300-5000 µm), small microplastics (SMPs, 10-300 µm), and microplastic-fibers (MPFs, 10-5000 µm) concurrently, for the first time. Sampling was conducted at seven stations in the Kamo and Katsura Rivers flowing across metropolitan Kyoto City. The analytical procedures involved infrared spectroscopy and fluorescence-staining microscopy. The concentrations of plastics were moderate compared to the global reports and gradually increased along the river flow (3550-15,840 items/m3; 180-13,180 µg/m3), mostly due to urban discharges via non-point sources. The number concentrations increased with decreasing particle size, marking 99.94% of SMPs, including 50% smaller than 40 µm. Conversely, mass concentrations decreased, exhibiting 96% larger than 1000 µm (64% mesoplastics including 20% around 5000 µm), along with 2% SMPs. Polyethylene (PE) and polyvinyl alcohol were distinct among SMPs, with PE indicating higher susceptibility to fragmentation compared to polypropylene and other polymer types. MPF concentrations were homogeneous throughout the watershed (1470-3600 items/m3; 520-1060 µg/m3), with a higher proportion of fibers smaller than 1000 µm (86%), apparently originating from polyethylene terephthalate/nylon/acrylic-like textile fibers. The proportion of MPFs surpassed particles within 100-3000 µm and was considerably high around 300 µm (> 98%). The river network of Kyoto conveys billions of tiny microplastics to the Yodo River, the primary water resource downstream, within a dry day.

Degradation and lifetime prediction of plastics in subsea and offshore infrastructures.

Engineering and civil developments have relied on synthetic polymers and plastics (including polyethylene, polypropylene, polyamide, etc.) for decades, especially where their durability protects engineering structures against corrosion and other environmental stimuli. Offshore oil and gas infrastructure and renewable energy platforms are typical examples, where these plastics (100,000 s of metric tonnes worldwide) are used primarily as functional material to protect metallic flowlines and subsea equipment against seawater corrosion. Despite this, the current literature on polymers is limited to sea-surface environments, and a model for subsea degradation of plastics is needed. In this review, we collate relevant studies on the degradation of plastics and synthetic polymers in marine environments to gain insight into the fate of these materials when left in subsea conditions. We present a new mathematical model that accounts for various physicochemical changes in the oceanic environment as a function of depth to predict the lifespan of synthetic plastics and the possible formation of plastic debris, e.g., microplastics. We found that the degradation rate of the plastics decreases significantly as a function of water depth and can be estimated quantitatively by the mathematical model that accounts for the effect (and sensitivity) of geographical location, temperature, light intensity, hydrostatic pressure, and marine sediments. For instance, it takes a subsea polyethylene coating about 800 years to degrade on ocean floor (as opposed to <400 years in shallow coastal waters), generating 1000s of particles per g of degradation under certain conditions. Our results demonstrate how suspended sediments in the water column are likely to compensate for the decreasing depth-corrected degradation rates, resulting in surface abrasion and the formation of plastic debris such as microplastics. This review, and the complementing data, will be significant for the environmental impact assessment of plastics in subsea infrastructures. Moreover, as these infrastructures reach the end of their service life, the management of the plastic components becomes of great interest to environmental regulators, industry, and the community, considering the known sizeable impacts of plastics on global biogeochemical cycles.

Review of Chemical Reactivity of Singlet Oxygen with Organic Fuels and Contaminants.

Singlet oxygen represents a form of reactive oxygen species (ROS), produced by electronic excitation of molecular triplet oxygen. In general, highly reactive oxygen-bearing molecules remain the backbone of diverse ground-breaking technologies, driving the waves of scientific development in environmental, biotechnology, materials, medical and defence sciences. Singlet oxygen has a relatively high energy of about 94 kJ/mol compared to the ground state molecular O2 and therefore initiates low-temperature oxidation of electron-rich hydrocarbons. Such reactivity of singlet oxygen has inspired a wide array of emerging applications in chemical, biochemical and combustion phenomena. This paper reviews the intrinsic properties of singlet oxygen, emphasising the physical aspects of its natural occurrences, production techniques, as well as chemical reactivity with organic fuels and contaminants. The review assembles critical scientific studies on the implications of singlet oxygen in initiating chemical reactions, identifying, and quantitating the consequential effects on combustion, fire safety, as well as on the low-temperature treatment of organic wastes and contaminants. Moreover, the content of this review appraises computational efforts, such as DFT quantum mechanical modelling, in developing mechanistic (i. e., both thermodynamic and kinetic) insights into the reaction of singlet oxygen with hydrocarbons.

Interfacial and bulk properties of concentrated solutions of ammonium nitrate.

We conducted molecular dynamics (MD) simulations to calculate the density and surface tension of concentrated ammonium nitrate (AN) solutions up to the solubility limit of ammonium nitrate in water, by combining the SPC/E, SPCE/F and TIP4P/2005 water models with OPLS model for ammonium and nitrate ions. This is the first time that the properties of concentrated solutions of nitrates, especially AN, have been studied by molecular dynamics. We effectively account for the polarisation effects by the electronic continuum correction (ECC), practically realised via rescaling of the ionic charges. We found that, the full-charge force field MD simulations overestimate the experimental results, as the ions experience repulsion from the interface and prefer to remain in the subsurface layer and the bulk solution. In contrast, reducing the ionic charges results in the behaviour that fits well with the experimental data. The nitrate anions display a greater propensity for the interface than the ammonium cations. We accurately predict both the density and the rise in the surface tension of concentrated solutions of AN, recommending TIP4P/2005 for water and the scaled-charge OPLS model (OPLS/ECC) for the ions in the solutions. We observe that, the adsorption of anions to the interface accompanies their depletion in the subsurface layer, which is preferentially occupied by cations, resulting in the formation of the electric double layer. We demonstrate the ion deficiency for up to 3 Å below the surface and establish the requirement to include the polarisability effects in the OPLS model for AN. While these results confirmed the findings of the previous studies for dilute solutions, they are new in the solubility limit. Concentrated solutions exhibit a strong effect of the abundance of solute on the coordination numbers of ions and on the degree of ion pairing. Surprisingly, ion pairing decreases significantly at the interface compared with the bulk. The present study identifies OPLS/ECC, along with TIP4P/2005, to yield accurate predictions of physical properties of concentrated AN, with precision required for industrial applications, such as a formulation of emulsion and fuel-oil explosives that now predominate the civilian use of AN. An application of this model will allow one to predict the surface properties of supersaturated solutions of AN which fall outside the capability of the present laboratory experiments but are important industrially.

Kinetics of Photo-Oxidation of Oxazole and its Substituents by Singlet Oxygen.

Oxazole has critical roles not only in heterocycle (bio)chemistry research, but also as the backbone of many active natural and medicinal species. These diverse and specialised functions can be attributed to the unique physicochemical properties of oxazole. This contribution investigates the reaction of oxazole and its derivatives with singlet oxygen, employing density functional theory DFT-B3LYP calculations. The absence of allylic hydrogen in oxazole eliminates the ene-mode addition of singlet oxygen to the aromatic ring. Therefore, the primary reaction pathway constitutes the [4 + 2]-cycloaddition of singlet oxygen to oxazole ring, favouring an energetically accessible corridor of 57 kJ/mol to produce imino-anhydride which is postulated to convert to triamide end-product in subsequent steps. The pseudo-first-order reaction rate for substituted oxazole (e.g., 4-methyl-2,5-diphenyloxazole, 1.14 × 106 M-1 s-1) appears slightly higher than that of unsubstituted oxazole (0.94 × 106 M-1 s-1) considering the same initial concentration of the species at 300 K, due to the electronic effect of the functional groups. The global reactivity descriptors have justified the relative influence of the functional groups along with their respective physiochemical properties.

Destruction of dioxin and furan pollutants via electrophilic attack of singlet oxygen.

Polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) remain of particular concern owing to their extensive toxicity towards health and accumulation in the environment. Atmospheric oxidation (by ambient oxygen molecules) of this class of persistent environmental pollutants has little to no kinetic feasibility due to very sizable activation energies in the entrance channel. The current control measures involve energy-intensive source incineration of contaminated materials at high temperatures as high as 850 °C. This study finds an alternative low-energy approach of destroying dioxin-like compounds, proposing that advanced oxidation by highly reactive singlet oxygen (O21Δg, originated from chemical, surface-mediated and photochemical processes) can initiate low-temperature remediation of these pollutants. This contribution completes the first milestone in mapping out the mechanisms of the electrophilic addition of singlet oxygen to unsubstituted and chlorinated dibenzo-p-dioxin (DBD) and dibenzofuran (DBF) structures, according to density functional theory DFT-B3LYP method in conjunction with the 6-311+g(d,p) basis set, as well as energy refinements based on the approximate spin-projection scheme. The [2+2]-cycloaddition mechanism appears dominant for singlet oxidation of dibenzo-p-dioxin with a fitted rate constant of k(T) = 5.01 × 10-14 exp(-98000/RT). On the other hand, the addition of singlet oxygen to the aromatic ring of dibenzofuran primarily transpires via [4+2]-cycloaddition channel with a fitted rate constant of k(T) = 2.16 × 10-13 exp(-119000/RT). The results suggest that application of singlet oxygen can reduce the energy cost of recycling halogenated and flame retarded materials.

Probing the Reactivity of Singlet Oxygen with Cyclic Monoterpenes.

Monoterpenes represent a class of hydrocarbons consisting of two isoprene units. Like many other terpenes, monoterpenes emerge mainly from vegetation, indicating their significance in both atmospheric chemistry and pharmaceutical and food industries. The atmospheric recycling of monoterpenes constitutes a major source of secondary organic aerosols. Therefore, this contribution focuses on the mechanism and kinetics of atmospheric oxidation of five dominant monoterpenes (i.e., limonene, α-pinene, ß-pinene, sabinene, and camphene) by singlet oxygen. The reactions are initiated via the ene-type addition of singlet oxygen (O2 1Δg) to the electron-rich double bond, progressing favorably through the concerted reaction mechanisms. The physical analyses of the frontier molecular orbitals agree well with the thermodynamic properties of the selected reagents, and the computed reaction rate parameters. The reactivity of monoterpenes with O2 1Δg follows the order of α-pinene > sabinene > limonene > ß-pinene > camphene, i.e., α-pinene and camphene retain the highest and lowest reactivity toward singlet oxygen, with rate expressions of k(T) (M-1 s-1) = 1.13 × 108 exp(-48(kJ)/RT(K)) and 6.93 × 108 exp(-139(kJ)/RT(K)), respectively. The effect of solvent on the primary reaction pathways triggers a slight reduction in energy, ranging between 12 and 34 kJ/mol.

Reaction of phenol with singlet oxygen.

Photo-degradation of organic pollutants plays an important role in their removal from the environment. This study provides an experimental and theoretical account of the reaction of singlet oxygen O2(1Δg) with the biodegradable-resistant species of phenol in an aqueous medium. The experiments combine customised LED-photoreactors, high-performance liquid chromatography (HPLC), and electron paramagnetic resonance (EPR) imaging, employing rose bengal as a sensitiser. Guided by density functional theory (DFT) calculations at the M062X level, we report the mechanism of the reaction and its kinetic model. Addition of O2(1Δg) to the phenol molecule branches into two competitive 1,4-cycloaddition and ortho ene-type routes, yielding 2,3-dioxabicyclo[2.2.2]octa-5,7-dien-1-ol (i.e., 1,4-endoperoxide 1-hydroxy-2,5-cyclohexadiene) and 2-hydroperoxycyclohexa-3,5-dien-1-one, respectively. Unimolecular rearrangements of the 1,4-endoperoxide proceed in a facile exothermic reaction to form the only experimentally detected product, para-benzoquinone. EPR revealed the nature of the oxidation intermediates and corroborated the appearance of O2(1Δg) as the only active radical participating in the photosensitised reaction. Additional experiments excluded the formation of hydroxyl (HO˙), hydroperoxyl (HO2˙), and phenoxy intermediates. We detected for the first time the para-semibenzoquinone anion (PSBQ), supporting the reaction pathway leading to the formation of para-benzoquinone. Our experiments and the water-solvation model result in the overall reaction rates of kr-solvation = 1.21 × 104 M-1 s-1 and kr = 1.14 × 104 M-1 s-1, respectively. These results have practical application to quantify the degradation of phenol in wastewater treatment.

Thermal Reduction of NOx with Recycled Plastics.

This study develops technology for mitigation of NOx formed in thermal processes using recycled plastics such as polyethylene (PE). Experiments involve sample characterization, and thermogravimetric decomposition of PE under controlled atmospheres, with NOx concentration relevant to industrial applications. TGA-Fourier transform infrared (FTIR) spectroscopy and NOx chemiluminescence serve to obtain the removal efficiency of NOx by fragments of pyrolyzing PE. Typical NOx removal efficiency amounts to 80%. We apply the isoconversional method to derive the kinetic parameters, and observe an increasing dependency of activation energy on the reaction progress. The activation energies of the process span 135 kJ/mol to 226 kJ/mol, and 188 kJ/mol to 268 kJ/mol, for neat and recycled PE, respectively, and the so-called compensation effect accounts for the natural logarithmic pre-exponential ln (A/min-1) factors of ca. 19-35 and 28-41, in the same order, depending on the PE conversion in the experimental interval of between 5 and 95%. The observed delay in thermal events of recycled PE reflects different types of PE in the plastic, as measurements of intrinsic viscosity indicate that, the recycled PE comprises longer linear chains. The present evaluation of isoconversional activation energies affords accurate kinetic modeling of both isothermal and nonisothermal decomposition of PE in NOx-doped atmosphere. Subsequent investigations will focus on the effect of mass transfer and the presence of oxygen, as reburning of NOx in large-scale combustors take place at higher temperatures than those included in the current study.

Inhibition and Promotion of Pyrolysis by Hydrogen Sulfide (H2S) and Sulfanyl Radical (SH).

This study resolves the interaction of sulfanyl radical (SH) with aliphatic (C1-C4) hydrocarbons, using CBS-QB3 based calculations. We obtained the C-H dissociation enthalpies and located the weakest link in each hydrocarbon. Subsequent computations revealed that, H abstraction by SH from the weakest C-H sites in alkenes and alkynes, except for ethylene, appears noticeably exothermic. Furthermore, abstraction of H from propene, 1-butene, and iso-butene displays pronounced spontaneity (i.e., ΔrG° < -20 kJ mol-1 between 300-1200 K) due to the relatively weak allylic hydrogen bond. However, an alkyl radical readily abstracts H atom from H2S, with H2S acting as a potent scavenger for alkyl radicals in combustion processes. That is, these reactions proceed in the opposite direction than those involving SH and alkene or alkyne species, exhibiting shallow barriers and strong spontaneity. Our findings demonstrate that the documented inhibition effect of hydrogen sulfide (H2S) on pyrolysis of alkanes does not apply to alkenes and alkynes. During interaction with hydrocarbons, the inhibitive effect of H2S and promoting interaction of SH radical depend on the reversibility of the H abstraction processes. For the three groups of hydrocarbon, Evans-Polanyi plots display linear correlations between the bond dissociation enthalpies of the abstracted hydrogens and the relevant activation energies. In the case of methane, we demonstrated that the reactivity of SH radicals toward abstracting H atoms exceeds that of HO2 but falls below those of OH and NH2 radicals.

Formation of Environmentally Persistent Free Radicals on α-Al2O3.

Metal oxides exhibit catalytic activity for the formation of environmentally persistent free radicals (EPFRs). Here, we investigate, via first-principles calculations, the activity of alumina α-Al2O3(0001) surface toward formation of phenolic EPFRs, under conditions relevant to cooling down zones of combustion systems. We show that, molecular adsorption of phenol on α-Al2O3(0001) entails binding energies in the range of -202 kJ/mol to -127 kJ/mol. The dehydroxylated alumina catalyzes the conversion of phenol into its phenolate moiety with a modest activation energy of 48 kJ/mol. Kinetic rate parameters, established over the temperature range of 300 to 1000 K, confirm the formation of the phenolate as the preferred pathways for the adsorption of phenol on alumina surfaces, corroborating the role of particulate matter in the cooling down zone of combustion systems in the generation of EFPRs.