Non-radical oxidation driven by iron-based materials without energy assistance in wastewater treatment.

Chemical oxidation is extensively utilized to mitigate the impact of organic pollutants in wastewater. The non-radical oxidation driven by iron-based materials is noted for its environmental friendliness and resistance to wastewater matrix, and it is a promising approach for practical wastewater treatment. However, the complexity of heterogeneous systems and the diversity of evolutionary pathways make the mechanisms of non-radical oxidation driven by iron-based materials elusive. This work provides a systematic review of various non-radical oxidation systems driven by iron-based materials, including singlet oxygen (1O2), reactive iron species (RFeS), and interfacial electron transfer. The unique mechanisms by which iron-based materials activate different oxidants (ozone, hydrogen peroxide, persulfate, periodate, and peracetic acid) to produce non-radical oxidation are described. The roles of active sites and the unique structures of iron-based materials in facilitating non-radical oxidation are discussed. Commonly employed identification methods in wastewater treatment are compared, such as quenching, chemical probes, spectroscopy, mass spectrometry, and electrochemical testing. According to the process of iron-based materials driving non-radical oxidation to remove organic pollutants, the driving factors at different stages are summarized. Finally, challenges and countermeasures are proposed in terms of mechanism exploration, detection methods and practical applications of non-radical oxidation driven by iron-based materials. This work provides valuable insights for understanding and developing non-radical oxidation systems.

Influence mechanism of anions on iron doping into swine bone char: Promoting non-radical oxidation of acetaminophen in a Fenton-like system.

The application of iron-doped biochar in peroxymonosulfate (PMS) activation systems has gained increasing attention due to their effectiveness and environmental friendliness in addressing environmental issues. However, the behavioral mechanism of iron doping and the detailed 1O2 generation mechanism in PMS activation systems remain ambiguous. Here, we investigated the effects of three anions (Cl-, NO3-and SO42-) on the process of iron doping into bone char, leading to the synthesis of three iron-doped bone char (Fe-ClBC, Fe-NBC and Fe -SBC). These iron-doped bone char were used to catalyze PMS to degrade acetaminophen (APAP) and exhibited the following activity order: Fe-ClBC > Fe-NBC > Fe-SBC. Characterization results indicated that iron doping primarily occurred through the substitution of calcium in hydroxyapatite within BC. In the course of the impregnation, the binding of SO42- and Ca2+ hindered the exchange of iron ions, resulting in lower catalytic activity of Fe-SBC. The primary reactive oxygen species in the Fe-ClBC/PMS and Fe-NBC/PMS systems were both 1O2. 1O2 is produced through O2•- conversion and PMS self-dissociation, which involves the generation of metastable iron intermediates and electron transfer within iron species. The presence of oxygen vacancies and more carbon defects in the Fe-ClBC catalyst facilitates 1O2 generation, thereby enhancing APAP degradation within the Fe-ClBC/PMS system. This study is dedicated to in-depth exploration of the mechanisms underlying iron doping and defect materials in promoting 1O2 generation.

Iron-doped swine bone char as hydrogen peroxide activator for efficient removal of acetaminophen in water.

Bone char is a functional material obtained by calcining animal bones and is widely used for environmental remediation. In this work, iron was inserted into porcine bone-derived bone char via ion exchange to synthesize iron-doped bone char (Fe-BC) for efficient catalysis of hydrogen peroxide. This is the first time that Fe-BC has been used as a catalyst for the activation of H2O2. The effectiveness of the Fe-BC catalyst was influenced by the annealing temperature and the amount of iron doping. The results showed that the activation of H2O2 by the Fe-BC catalyst with the best catalytic performance could achieve 97.6% of APAP degradation within 30 min. Insights from electron paramagnetic resonance (EPR), free radical scavenging experiments and linear sweep voltammetry (LSV) proposed a reaction mechanism based on free radicals dominated degradation pathways (OH and O2-). Iron served as the primary active site in Fe-BC, with defect sites and oxygen-containing groups in the catalyst also contributing to the removal of pollutants. The Fe-BC/H2O2 system demonstrated resilience to interference from common anions (Cl-, NO3-, SO42- and HCO3-) in water, but was less effective against humic acid (HA). Based on the detection of intermediates produced during APAP degradation, possible degradation pathways of APAP were proposed and the toxicity of intermediates was evaluated. This work provides fresh insights into the use of heterogeneous Fenton catalysts for the removal of organic pollutants from water.

Deterioration of single-use biodegradable plastics in high-humidity air and freshwaters over one year: Significant disparities in surface physicochemical characteristics and degradation rates.

More single-use plastics are accumulating in the environment, and likewise biodegradable plastics (BPs), which are being vigorously promoted, cannot escape the fate. Currently, studies on the actual degradation of BPs in open-air and freshwaters are underrepresented despite they are potentially headmost leakage and contamination sites for disposable BPs. Herein, we compared the degradation behavior of six BP materials and non-degradable polypropylene (PP) plastics over a 1-year in situ suspension in the high-humidity air, a eutrophic river, and an oligotrophic lake. Moreover, a 3-months laboratory incubation was performed to detect the release of dissolved organic carbon (DOC) from BPs. In both air and freshwaters, poly(p-dioxanone) (PPDO) degraded significantly while PP and polylactic acid (PLA) showed no signs of degradation. The average degradation rates of three poly(butylene adipate-co-terephthalate) (PBAT)-based films varied: 100% in river, 55% in lake, and 10% in air. In addition to PLA, surface chemical groups, hydrophilicity, and thermal stability of BPs changed, and microplastics were found on their surfaces. Correspondingly, BPs with faster degradation rates released relatively higher amounts of DOC. Environmental microbial and chemical characteristics may contribute to differences in BP degradation besides polymer specificity. Altogether, our results indicate the need for appropriate monitoring of BPs.

Iron colloidal transport mechanisms and sequestration of As, Ni, and Cu along AMD-induced environmental gradients.

Colloids are common in mine waters and their chemistry and interactions are critical aspects of metal(loid)s cycling. Previous studies mostly focus on the colloidal transport of metal(loid)s in zones where rivers and soil profiles receive acid mine drainage (AMD). However, there is limited knowledge of the colloid and the associated toxic element behavior as the effluent flows through the coal waste dump, where a geochemical gradient is produced due to AMD reacting with waste rocks which have high acid-neutralization effects. Here, we investigated the geochemistry of Fe and co-occurring elements As, Ni, and Cu along the coal waste dump, in aqueous, colloidal, and precipitate phases, using micro/ultrafiltration combined with STEM, AFM-nanoIR, SEM-EDS, XRD, and FTIR analysis. The results demonstrated that a fast attenuation of H+, SO42-, and metal(loid)s happened as the effluent flowed through the waste-rock dump. The Fe, As, Ni, and Cu were distributed across all colloidal sizes and primarily transported in the nano-colloidal phase (3 kDa-0.1 µm). An increasing pH induced a higher percentage of large Fe colloid fractions (> 0.1 µm) associated with greater sequestration of trace metals, and the values for As from 39.5 % to 54.4 %, Ni from 40.8 % to 75.7 %, and Cu from 43.7 % to 56.0 %, respectively. The Fe-bearing colloids in AMD upstream (pH ≤ 3.0) were primarily composed of Fe-O-S and Fe-O-C with minor Al-Si-O and Ca-O-S, while in less acidic and alkaline sections (pH ≥ 4.1), they were composed of Fe-O with minor Ca-O-S. The iron colloid agglomerates associated with As, Ni, and Cu precipitated coupling the transformation of jarosite, and schwertmannite to ferrihydrite, goethite, and gypsum. These results demonstrate that the formation and transformation of Fe-bearing colloids response to this unique geochemical gradient help to understand the natural metal(loid)s attenuation along the coal waste dump.

Enhanced anaerobic oxidation of methane with the coexistence of iron oxides and sulfate fertilizer in paddy soil.

Iron oxides and sulfate are usually abundant in paddy soil, but their role in reducing methane emissions is little known. In this work, paddy soil was anaerobically cultivated with ferrihydrite and sulfate for 380 days. An activity assay, inhibition experiment, and microbial analysis were conducted to evaluate the microbial activity, possible pathways, and community structure, respectively. The results showed that anaerobic oxidation of methane (AOM) was active in the paddy soil. The AOM activity was much higher with ferrihydrite than sulfate, and an extra 10% of AOM activity was stimulated when ferrihydrite and sulfate coexisted. The microbial community was highly similar to the duplicates but totally different with different electron acceptors. The microbial abundance and diversity decreased due to the oligotrophic condition, but mcrA-carrying archaea increased 2-3 times after 380 days. Both the microbial community and the inhibition experiment implied that there was an intersection between iron and sulfur cycles. A "cryptic sulfur cycle" might link the two cycles, in which sulfate was quickly regenerated by iron oxides, and it might contribute 33% of AOM in the tested paddy soil. Complex links between methane, iron, and sulfur geochemical cycles occur in paddy soil, which may be significant in reducing methane emissions from rice fields.

Insight into iron oxychloride composite bone char for peroxymonosulfate activation: Mechanism of singlet oxygen evolution for selective degradation of organic pollutants.

The activity of iron-based catalysts in advanced oxidation processes (AOPs) is limited by the redox cycle of Fe(III) and Fe(II). In this work, iron oxychloride (FeOCl) with a unique layered structure was loaded on the bone char (BC) to enhance the activation of peroxymonosulfate (PMS). Characterization of the FeOCl-BC catalyst reveals that the loading of FeOCl changed the composition and structure of BC and BC reduced the bond gap of FeOCl. Acetaminophen (APAP) as a target pollutant could be almost completely degraded at neutral pH, and the removal rate reached 0.6597 min-1. APAP could also be selectively oxidized by FeOCl-BC/PMS system in the presence of some inorganic anions (SO42-, NO3-, and Cl-) and humic acid. Quenching experiments, electron paramagnetic resonance (EPR), chemical probes, and linear sweep voltammetry (LSV) confirm that the primary oxidation mechanism of the FeOCl-BC/PMS system was dominated by 1O2. The 1O2 was generated from the conversion of O2•- and the self-dissociation of PMS, involving the formation of metastable iron intermediates and the redox cycle of Fe(III) and Fe(II). The unique structure of FeOCl, the transport of lattice oxygen and the enrichment of electrons by carbon defects play an essential role in generating reactive species. In this work, the limitation of the redox cycle of Fe(III) and Fe(II) was broken by loading FeOCl on the surface of BC, and a new catalytic mechanism was proposed. This work provides a new perspective for the construction of efficient iron-based catalysts and the practical application of PMS-based AOPs.

Natural iron minerals in an electrocatalytic oxidation system and in situ pollutant removal in groundwater: Applications, mechanisms, and challenges.

Natural iron-bearing minerals are widely distributed in the environment and show prominent catalytic performance in pollutant removal. This work provides an overview of groundwater restoration technologies utilizing heterogeneous electro-Fenton (HEF) techniques with the aid of different iron forms as catalysts. In particular, applications of natural iron-bearing minerals in groundwater in the HEF system have been thoroughly summarized from either the view of organic pollutant removal or degradation. Based on the analysis of the catalytic mechanism in the HEF process by pyrite (FeS2), goethite (α-FeOOH), and magnetite (Fe3O4) and the geochemistry analysis of these natural iron-bearing minerals in groundwater, the feasibility and challenges of HEF for organic degradation by using typical iron minerals in groundwater have been discussed, and natural factors affecting the HEF process have been analyzed so that appropriate in situ remedial measures can be applied to contaminated groundwater.

Synergistic mechanism and application of microbially induced carbonate precipitation (MICP) and inorganic additives for passivation of heavy metals in copper-nickel tailings.

Tailings are one of the largest quantities of hazardous waste in the world, and their treatment is difficult and expensive. In this work, a new, low-cost technique coupling microbially induced carbonate precipitation (MICP) and inorganic additives was proposed, optimized, and applied. The results showed that CaO was the best additive among the six tested, with an optimum dosage of 5%. A 90-day experiment indicated that the MICP-CaO coupled technique was highly effective for all the concerned heavy metals (Cu, Ni, Pb, and Cr) in the Cu-Ni tailings. During the stabilization period (20-90 days), the passivation rates were stable at 78.8 ± 2.9% (Cu), 78.1 ± 1.0% (Ni), 89.2 ± 1.0% (Pb), and 97.8 ± 0.5% (Cr), 2%-866% higher than the single technique of either MICP or CaO. Multiple analyses demonstrated that the synergistic effect of MICP and CaO produced a large amount of calcite (1.5% of the tailings). This calcite cemented the tailings particles, sequestrated heavy metal ions into the lattices, and played a key role in heavy metal passivation. Moreover, CaO and MICP improved the strength and compactness of solidified body, respectively. This work demonstrates the feasibility of the MICP-CaO coupled technique in tailings solidification, which can be applied in practical projects.

Temporospatial nano-heterogeneity of self-assembly of extracellular polymeric substances on microplastics and water environmental implications.

Environmental behavior and ecotoxicity of microplastics (MPs) are significantly influenced by the omnipresent self-assembly of microbial extracellular polymeric substances (EPS) on them. However, mechanisms of EPS self-assembly onto MPs at nanoscale resolution and effects of aging are unclear. For the first time, temporospatial nano-heterogeneity of self-assembly of EPS onto fresh and one-year aged polypropylene (PP) MPs were investigated by atomic-force-microscopy-infrared-spectroscopy (AFM-IR). Natural aging caused high degree nanoscale fragmentation of MPs physically and chemically. Self-assembly of EPS on MPs was aging-dependent. Polysaccharides were assembled on MP surface faster than proteins. Initially, regardless of the fresh or aged MPs, polysaccharides and proteins, with the former being predominant, were successively and separately assembled to different nanospaces because of their competition for binding sites. More and more proteins and polysaccharides were superimposed on each other with assembly time due to intermolecular forces. The nanochemical textural analysis showed that the nano-heterogeneity of EPS assembly to MPs was clearly correlated with the aging-induced nanochemical and nanomechanical heterogeneity of MP surface. The spontaneous self-assembly of EPS with temporospatial nano-heterogeneity on MPs have multiple impacts on behavior, ecotoxicity and fate of MPs and their associated pollutants as well as other key ecological processes in aquatic environment.

Interactions between polypropylene microplastics (PP-MPs) and humic acid influenced by aging of MPs.

As an emerging pollutant, microplastics (MPs) may interact with dissolved organic matter (DOM) which is prevalent in the aqueous environment. Meanwhile, the aging of MPs in the actual environment increases the uncertainty of their environmental fate. Here, the interaction mechanisms between pristine and aged polypropylene microplastics (PP-MPs) and humic acid (HA) at pH 7.0 were explored. Microstructural changes of HA were examined by fluorescence and Fourier transformation infrared (FT-IR) spectroscopy. Atomic force microscopy coupled with infrared (AFM-IR) and micro-Raman techniques were used to characterize and analyze the interacted PP-MPs. The addition of HA increased the surface roughness of both pristine and aged PP-MPs. Results of AFM-IR and Raman spectra showed that the interaction of PP-MPs with HA accelerated their surface oxidation and enhanced the characteristic signals. XPS spectra showed that the oxygen content ratio of pristine and aged PP-MPs increased by 0.95% and 1.48% after the addition of HA, respectively. PP-MPs after aging interacted more strongly with HA and there was a higher affinity between them. Two-dimensional correlation spectroscopy (2D-COS) combined with FT-IR spectra further elucidated the interaction mechanism at the molecular level. This work will help to evaluate the environmental impact of MPs in ecosystems and understand their interactions with DOM.

Microplastic Contamination in Urban, Farmland and Desert Environments along a Highway in Southern Xinjiang, China.

The different types of microplastics (MPs), including debris, fibers, particles, foams, films and others, have become a global environmental problem. However, there is still a lack of research and understanding of the pollution characteristics and main causes of MPs in the arid region of Xinjiang, China. In this survey, we focused on the occurrence and distribution of MPs in urban, farmland and desert areas along a highway in the survey area. Our results showed that the main types of MPs were polypropylene (PP) flakes, polyethylene (PE) films and both PE and PP fragments and fibers. The abundance levels of MPs in street dust of Korla, Alar and Hotan districts equaled 804, 307 and 1526 particles kg−1, respectively, and were positively correlated with the urban population. In farmland areas, there were only two types of MPs (films and fibers), of which the film particles dominated and accounted for 91% of the total on the average. The highest abundance rate of MPs reached 7292 particles kg−1 in the desert area along the highway. The minimum microplastic particle sizes were 51.8 ± 2.2 µm in urban street dust samples, 54.2 ± 5.3 µm in farmland soil samples and 67.8 ± 8.4 µm in samples from along the desert highway. Particle sizes < 500 µm were most common and accounted for 48−91% of the total in our survey. The abundance and shape distribution of the MPs were closely related to the different types of human activities.

Cadmium Caused Different Toxicity to Photosystem I and Photosystem II of Freshwater Unicellular Algae Chlorella pyrenoidosa (Chlorophyta)

Heavy metals such as Cd pose environmental problems and threats to a variety of organisms. The effects of cadmium (Cd) on the growth and activities of photosystem I (PSI) and photosystem II (PSII) of Chlorella pyrenoidosa were studied. The growth rate of cells treated with 25 and 100 µM of Cd for longer than 48 h were significantly lower than the control, accompanying with the inhibition of photosynthesis. The result of quantum yields and electron transport rates (ETRs) in PSI and PSII showed that Cd had a more serious inhibition on PSII than on PSI. Cd decreased the efficiency of PSII to use the energy under high light with increasing Cd concentration. In contrast, the quantum yield of PSI did not show a significant difference among different Cd treatments. The activation of cyclic electron flow (CEF) and the inhibition of linear electron flow (LEF) due to Cd treatment were observed. The photochemical quantum yield of PSI and the tolerance of ETR of PSI to Cd treatments were due to the activation of CEF around PSI. The activation of CEF also played an important role in induction of non-photochemical quenching (NPQ). The binding features of Cd ions and photosystem particles showed that Cd was easier to combine with PSII than PSI, which may explain the different toxicity of Cd on PSII and PSI.

Passivation of heavy metals in copper-nickel tailings by in-situ bio-mineralization: A pilot trial and mechanistic analysis.

Metal tailings contain a variety of toxic heavy metals and have potential environmental risks owing to long-term open piling. In the present study, a strain of ureolytic bacteria with bio-mineralization ability, Lysinibacillus fusiformis strain Lf, was isolated from copper-nickel mine tailings in Xinjiang and applied to a pilot trial of tailings solidification under field conditions. The results of the pilot trial (0.5 m3 in scale) showed that strain Lf effectively solidified the tailings. The compressive strength of the solidified tailings increased by 121 ± 9 % and the permeability coefficient decreased by 68 ± 3 %. Compared to the control, the leaching reduction of the solidified tailings of Cu and Ni was >98 %, and that of As was 92.5 ± 1.7 %. Two mechanisms of tailings solidification and heavy metal passivation were proposed based on the findings of Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HR-TEM), and energy-dispersive X-ray spectroscopy (EDS) mapping. Biogenic calcite filled the interstices of the tailings particles and cemented the adjacent particles. This improved the mechanical properties and reduced permeability. Moreover, heavy metal colloids were incorporated into large-sized calcite crystals, and heavy metal ions were sequestered within the calcite lattice. This method of using indigenous ureolytic bacteria to solidify tailings was successful in this work and may be replicated to remediate other tailings.

Binding of methylmercury to humic acids (HA): Influence of solar radiation and sulfide addition reaction of HA.

Methylmercury (MeHg) is a neurotoxin that bioaccumulates in organisms and it forms strong complexes with reduced sulfur-containing ligands in dissolved organic matter (DOM). In the present study, the influences of solar radiation and sulfide addition reaction of humic acids (HA) on MeHg binding to HA were investigated using synchronous fluorescence and FT-IR two-dimensional correlation spectroscopic (2DCOS) analysis. Results showed that the complexation of fluorescent fractions of HA and sulfur-reacted HA (S-HA) with MeHg was not significantly affected by photoreaction treatments and the affinity of fluorescent fractions followed the order of protein-like fractions > humic-like fractions > fulvic-like fractions for both HA and S-HA. FT-IR 2DCOS analysis showed that the affinity of various binding sites in DOM for MeHg changed under different photoreaction treatments. Under dark treatment, small molecular compounds with low humification degree such as aromatic amino acids may be the site with the strongest binding ability to MeHg in HA, whereas aliphatic amino acids and sulfur-containing groups from sulfide addition reactions play a role in complexing of S-HA and MeHg. Under BS treatment (irradiation of DOM before MeHg binding), aliphatic compounds in HA preferentially bind to MeHg and aliphatic amino acids are the components with the strongest complexing ability; but for S-HA binding to MeHg, unsaturated functional groups and aromatic groups are more sensitive (alkenes > alkanes, phenols > alcohols). Under AS treatment (irradiation of DOM after MeHg binding), unsaturated bonds and aromatic compounds in HA preferentially bind to MeHg and aromatic amino acids show the strongest complexing ability; but for S-HA binding to MeHg, aliphatic groups show the strongest complexing ability (alkanes, alkenes > aromatics). These findings help us to better understand the complexation mechanisms between MeHg and DOM.

Characteristics and distribution of microplastics in shoreline sediments of the Yangtze River, main tributaries and lakes in China-From upper reaches to the estuary.

Microplastics (MPs) pervade the environment and increasingly threaten both natural ecosystems and human health. In this study, we investigated MP particle concentrations in sediment samples collected from 54 sites along the banks of the Yangtze River and its major tributaries and on lakeshores. The main polymer types found in the samples were polypropylene (PP), polystyrene (PS) and polyethylene (PE). MP particle abundance in the various types of locations was 35-51,968 particles/kg dry weight (d.w.) on the banks of the main river, 52-1463 particles/kg (d.w.) on the banks of tributaries and 2574-23,685 particles/kg (d.w.) on lakeshores. Correlation between MP abundance and mean annual runoff of each upstream tributary was significant, which suggests that increased runoff brings more microplastic waste to streambank sediments. The most common shape of MP particles in all upstream samples was flake, and in downstream samples it was foam. Small microplastic particles (< 0.50 mm) were predominant at all sites in this study, and the minimum particle size in samples from the Yangtze river banks was 0.065 mm. Average abundance of MP particles on the shores of the source lake was 9069 particles/kg around the inlet but only 866 particles/kg around the outlet; the difference was due to interception associated with sedimentation and precipitation in the lake. Our study represents the large-scale study of MPs contamination in sediment along the Yangtze River and provides important data regarding the accumulation and distribution of MPs in shoreline sediments of the upper, middle and lower reaches of the Yangtze River, main tributaries and lakes in China.

Activation of peroxymonosulfate by iron oxychloride with hydroxylamine for ciprofloxacin degradation and bacterial disinfection.

Iron oxychloride (FeOCl) is a known effective iron-based catalyst and has been used in advanced oxidation processes (AOPs). This study intends to achieve more facile free radicals generation from peroxymonosulfate (PMS) activation by exploring the Fe(III)/Fe(II) cycle of FeOCl in the presence of hydroxylamine (HA). With 0.2 g/L FeOCl, 1.5 mM PMS, and 1 mM HA, the PMS/FeOCl/HA system could effectively achieve 98.88% of the oxidative degradation of 5 mg/L ciprofloxacin (CIP) in 15 min and quickly inactivate 99.99% of E. coli (108 CFU/mL) in 5 min at near-neutral pH. HA played an important role in promoting the Fe(III)/Fe(II) cycle, thereby greatly improving the oxidation activity of the system. The reactive oxygen species (ROS) such as HO, SO4- and O2- were identified as the dominated free radicals produced in the system. The intermediate products of CIP detected by liquid chromatograph-mass spectrometer (LC-MS) and three possible degradation pathways of CIP were proposed. The presence of common anions in the PMS/FeOCl/HA system, including HCO3-, Cl-, SO42-, and NO3-, enhanced the degradation efficiency of CIP to varying degrees at the concentrations of 10 mM. Moreover, FeOCl maintained a high degradation capability for CIP after several recycles. This work offers a new promising means of catalyzing the PMS-based AOPs in the degradation of refractory organics.

Photocatalytic aging process of Nano-TiO2 coated polypropylene microplastics: Combining atomic force microscopy and infrared spectroscopy (AFM-IR) for nanoscale chemical characterization.

Microplastics (MPs) are considered to have greater environmental hazards than large plastics. Most MPs undergo different degrees of aging and aged MPs exhibit different physicochemical properties from pristine ones. This study successfully prepared a nano-TiO2 coated polypropylene MPs, and explored the nanoscale infrared, thermal, and mechanical properties of MPs before and after photo-aging using a combined AFM-IR technique. Surface height range of MPs was ± 25 nm. The signal intensity of the absorption peak at 1654 cm-1 in terms of vinylidene end groups gradually increased as the irradiation time prolonged. The softening temperature of MPs decreased from 126.7 °C to 108.5 °C as the irradiation time increased from 0 h to 4 h. The MPs after photo-aging became stiffer, especially for the components surrounding the nano-TiO2 particle, indicating that photocatalytic reaction accelerated the aging process of MPs. The resonance frequency of MPs surrounding the nano-TiO2 particle was stronger after photo-aging and the stiffer components were uniformly distributed, confirming that the thermal and mechanical properties of MPs changed after photo-aging. These novel findings are essential to better understand the changes in the surface microstructures, physical properties, and chemical compositions of MPs during aging process.

Microplastics generated under simulated fire scenarios: Characteristics, antimony leaching, and toxicity.

Intentional or incidental thermal changes inevitably occur during the lifecycle of plastics. High temperatures accelerate the aging of plastics and promote their fragmentation to microplastics (MPs). However, there is little information available on the release of MPs after fires. In this study, an atomic force microscope combined with nanoscale infrared analysis was used to demonstrate the physicochemical properties of polypropylene (PP) plastics under simulated fire scenarios. Results showed that the chemical composition and relative stiffness of heat-treated plastic surfaces changed, significantly enhancing the generation of MPs under external forces; over (2.1 ± 0.2) × 105 items/kg abundance of MPs released from PP which were burned at 250 °C in air and trampled by a person. The leaching of antimony (Sb) from MPs in different solutions first increased and then decreased with increasing temperature, reaching a maximum at 250 °C. Higher concentrations of humic acid (10 vs 1 mg/L) caused a greater release of Sb. Furthermore, the tap water leachates of PP burned at 250 °C had the greatest effect on the growth and photosynthetic activity of Microcystis aeruginosa. Our results suggest fires as a potential source of MPs and calls for increased focus on burning plastics in future research.

Characteristics and removal of microplastics in rural domestic wastewater treatment facilities of China.

The environment of the countryside is different from that of the city. Studying the abundance, characteristics, and removal of microplastics (MPs) in rural domestic wastewater treatment facilities (RD-WWTFs) is of great significance for understanding the impacts of human activities on the environment of the countryside. Therefore, we studied five such facilities in the Hangzhou region of China. The abundance of MPs in the influent was 430-2154 items/m3. Micro-Raman spectroscopic analysis indicates that the main type of polymer in the influent is polypropylene (PP, 54.6%), followed by polystyrene (PS, 29.7%) and polyethylene terephthalate (PET, 9.7%). The color of MPs is mainly white and clear (62.9%), red (13.3%) and gray (12.0%). Our results show that fragments (71.3%) are the dominant shape of MPs, followed by fibers (21.5%). The characteristics of MPs, such as sizes, shapes, and types, along with the treatment process, affect the removal of MPs in RD-WWTFs. Large MPs are easily removed by anaerobic processes, while small MPs are better removed by anaerobic/anoxic/oxic processes. Fibrous MPs are more difficult to be removed than the fragmented ones. Constructed wetlands play an important role in the removal of MPs.