Pyrolysis temperature matters: Biochar-derived dissolved organic matter modulates aging behavior and biotoxicity of microplastics.

Microplastics (MPs) have emerged as a novel and highly concerning contaminant that is ubiquitous in the aqueous environment. However, the aging of MPs induced by dissolved organic matter (DOM), especially biochar-derived dissolved organic matter (BDOM), and the biological toxicity after aging are not fully understood. In this study, the effects of biochar-derived BDOMs on the photoaging and biotoxicity of MPs were investigated at different pyrolysis temperatures using micro-scale polyethylene (PE) as an example. The results showed that the amount of ·OH generated by the BDOM/PE systems was related to the molecular composition and structure of BDOMs. High temperature BDOM7/9 with less lignin-like (34.33 % / 41.80 %) and more lipid (24.58 % / 19.88 %) content could produce more ·OH by itself, and its binding ability with PE was weaker due to its less hydrophobic components (SUVA260 = 0.10 / 0.11), which resulted in a weaker shading effect and less inhibition of the system, thus resulting in more ·OH production in the high temperature BDOM7/9/PE system. However, the involvement of BDOM, although favoring the long-term stable ·OH production of the system, did not significantly promote the photoaging of MPs. Furthermore, combined in vivo and in vitro biotoxicity studies of MPs showed that photoaging PE with the involvement of BDOM greatly improved systemic inflammation and tissue damage, as well as reactive oxygen species (ROS, such as ·OH and -OH)-induced cell death. For example, the addition of BDOM5/PE-light reduced the cell death of human lung, liver, and kidney cells from 54.70 %, 69.39 %, and 48.35 % to 22.78 %, 33.13 %, and 25.83 %, respectively, compared to the PE-light group. The results of this study contribute to an in-depth understanding of the environmental behavior of BDOM and MPs systems.

Temporal Changes in Functional and Structural Neuronal Activities in Auditory System in Non-Severe Blast-Induced Tinnitus.

Background and Objectives: Epidemiological data indicate that blast exposure is the most common morbidity responsible for mild TBI among Service Members (SMs) during recent military operations. Blast-induced tinnitus is a comorbidity frequently reported by veterans, and despite its wide prevalence, it is also one of the least understood. Tinnitus arising from blast exposure is usually associated with direct structural damage that results in a conductive and sensorineural impairment in the auditory system. Tinnitus is also believed to be initiated by abnormal neuronal activities and temporal changes in neuroplasticity. Clinically, it is observed that tinnitus is frequently accompanied by sleep disruption as well as increased anxiety. In this study, we elucidated some of the mechanistic aspects of sensorineural injury caused by exposure to both shock waves and impulsive noise. The isolated conductive auditory damage hypothesis was minimized by employing an animal model wherein both ears were protected. Materials and Methods: After the exposure, the animals' hearing circuitry status was evaluated via acoustic startle response (ASR) to distinguish between hearing loss and tinnitus. We also compared the blast-induced tinnitus against the well-established sodium salicylate-induced tinnitus model as the positive control. The state of the sensorineural auditory system was evaluated by auditory brainstem response (ABR), and this test helped examine the neuronal circuits between the cochlea and inferior colliculus. We then further evaluated the role of the excitatory and inhibitory neurotransmitter receptors and neuronal synapses in the auditory cortex (AC) injury after blast exposure. Results: We observed sustained elevated ABR thresholds in animals exposed to blast shock waves, while only transient ABR threshold shifts were observed in the impulsive noise group solely at the acute time point. These changes were in concert with the increased expression of ribbon synapses, which is suggestive of neuroinflammation and cellular energy metabolic disorder. It was also found that the onset of tinnitus was accompanied by anxiety, depression-like symptoms, and altered sleep patterns. By comparing the effects of shock wave exposure and impulsive noise exposure, we unveiled that the shock wave exerted more significant effects on tinnitus induction and sensorineural impairments when compared to impulsive noise. Conclusions: In this study, we systematically studied the auditory system structural and functional changes after blast injury, providing more significant insights into the pathophysiology of blast-induced tinnitus.

Effect of minocycline and its nano-formulation on central auditory system in blast-induced hearing loss rat model.

Blast injuries are common among the military service members and veterans. One of the devastating effects of blast wave induced TBI is either temporary or permanent hearing loss. Treating hearing loss using minocycline is restricted by optimal drug concentration, route of administration, and its half-life. Therefore, therapeutic approach using novel therapeutic delivery method is in great need. Among the different delivery methods, nanotechnology-based drug delivery is desirable, which can achieve longer systemic circulation, pass through some biological barriers and specifically targets desired sites. The current study aimed to examine therapeutic effect of minocycline and its nanoparticle formulation in moderate blast induced hearing loss rat model through central auditory system. The I.v. administered nanoparticle at reduced dose and frequency than regularly administered toxic dose. After moderate blast exposure, rats had hearing impairment as determined by ABR at 7- and 30-days post exposure. In chronic condition, free minocycline also showed the significant reduction in ABR threshold. In central auditory system, it is found in this study that minocycline nanoparticles ameliorate excitation in inferior colliculus; and astrocytes and microglia activation after the blast exposure is reduced by minocycline nanoparticles administration. The study demonstrated that in moderate blast induced hearing loss, minocycline and its nanoparticle formulation exhibited the optimal therapeutic effect on the recovery of the ABR impairment and a protective effect through central auditory system. In conclusion, targeted and non-targeted nanoparticle formulation have therapeutic effect on blast induced hearing loss.

Morphology-Tailored Hydroxyapatite Nanocarrier for Rhizosphere-Targeted Phosphorus Delivery.

High hydrophilicity and soil fixation collectively hamper the delivery of phosphorus (P) released from conventional chemical phosphorus fertilizers (CPFs) to plant rhizosphere for efficient uptake. Here, a phosphorus nutrient nanocarrier (PNC) based on morphology-tailored nanohydroxyapatite (HAP) is constructed. By virtue of kinetic control of building blocks with designed calcium phosphate intermediates, rod-like and hexagonal prism-like PNCs are synthesized, both having satisfactory hydrophobicity (water contact angle of 105.4- 132.9°) and zeta potential (-17.43 to -58.4 mV at pH range from 3 to 13). Greenhouse experiments demonstrate that the P contents increase by up to 183% in maize rhizosphere and up to 16% in maize biomass when compared to the CPF. Due to the water potential gradient driven by photosynthesis and transpiration, both PNCs are stably transported to maize rhizosphere, and they are capable to counteract soil fixation prior to uptake by plant roots. Within the synergies of the HAP morphological characteristics and triggered phosphate starvation response, root anatomy confirms that two pathways are elucidated to enhance plant P replenishment from the PNCs. Together with structure tunability and facile synthesis, our results offer a new nanodelivery prototype to accommodate plant physiological traits by tailoring the morphology of HAP.

Iron Phosphate Nanozyme-Hydrogel with Multienzyme-like Activity for Efficient Bacterial Sterilization.

Pathogenic bacteria infections have posed a threat to human health worldwide. Nanomaterials with natural enzymatic activity provide an opportunity for the development of new antibacterial pathways. We successfully constructed iron phosphate nanozyme-hydrogel (FePO4-HG) with the traits of positive charge and macropores. Interestingly, FePO4-HG displayed not only peroxidase-like activity under acidic bacterial infectious microenvironment but also superoxide dismutase-catalase-like synergistic effects in neutral or weak alkaline conditions, thus protecting normal tissues from the peroxidase-like protocol with exogenous H2O2 damage. Furthermore, the positive charge and macropore structure of FePO4-HG could capture and restrict bacteria in the range of ROS destruction. Obviously, FePO4-HG exhibited excellent antibacterial ability against MRSA and AREC with the assistance of H2O2. Significantly, the FePO4-HG + H2O2 system could efficiently disrupt the bacterial biofilm formation and facilitate the glutathione oxidation process to rapid bacterial death with low cytotoxicity. Moreover, FePO4-HG was unsusceptible to bacterial resistance development in MRSA. Animal experiments showed that the FePO4-HG + H2O2 group could efficiently eliminate the MRSA infection and present excellent wound healing without inflammation and tissue adhesions. With further development and optimization, FePO4-HG has great potential as a new class of antibacterial agents to fight antibiotic-resistant pathogens.

Animal model of repeated low-level blast traumatic brain injury displays acute and chronic neurobehavioral and neuropathological changes.

Blast-induced neurotrauma (BINT) is not only a signature injury to soldiers in combat field and training facilities but may also a growing concern in civilian population due to recent increases in the use of improvised explosives by insurgent groups. Unlike moderate or severe BINT, repeated low-level blast (rLLB) is different in its etiology as well as pathology. Due to the constant use of heavy weaponry as part of combat readiness, rLLB usually occurs in service members undergoing training as part of combat readiness. rLLB does not display overt pathological symptoms; however, earlier studies report chronic neurocognitive changes such as altered mood, irritability, and aggressive behavior, all of which may be caused by subtle neuropathological manifestations. Current animal models of rLLB for investigation of neurobehavioral and neuropathological alterations have not been adequate and do not sufficiently represent rLLB conditions. Here, we developed a rat model of rLLB by applying controlled low-level blast pressures (<10 psi) repeated successively five times to mimic the pressures experienced by service members. Using this model, we assessed anxiety-like symptoms, motor coordination, and short-term memory as a function of time. We also examined levels of superoxide-producing enzyme NADPH oxidase, microglial activation, and reactive astrocytosis as factors likely contributing to these neurobehavioral changes. Animals exposed to rLLB displayed acute and chronic anxiety-like symptoms, motor and short-term memory impairments. These changes were paralleled by increased microglial activation and reactive astrocytosis. Conversely, animals exposed to a single low-level blast did not display significant changes. Collectively, this study demonstrates that, unlike a single low-level blast, rLLB exerts a cumulative impact on different brain regions and produces chronic neuropathological changes in so doing, may be responsible for neurobehavioral alterations.

Metal-Organic Framework Modified MoS2 Nanozyme for Synergetic Combating Drug-Resistant Bacterial Infections via Photothermal Effect and Photodynamic Modulated Peroxidase-Mimic Activity.

Bacterial infections have become major threats to public health all over the world. With the emergence of antibiotic resistance, it is urgent to develop novel antimicrobial materials to efficiently overcome drug resistance with high bactericidal activity. In this work, UiO-66-NH-CO-MoS2 nanocomposites (UNMS NCs) are constructed through the amidation reaction. The UNMS NCs are positively charged which is beneficial for capturing and restricting bacteria. Significantly, UNMS NCs possess a synergistic bactericidal efficiency based on near-infrared irradiation (808 nm) regulated combination of photothermal, photodynamic, and peroxidase-like enzymatic activities. Both the photodynamic property and nanozymatic activity of UNMS NCs can lead to the generation of reactive oxygen species. The UNMS NCs show high catalytic activity in a wide pH range and exhibit excellent antibacterial ability against ampicillin-resistant Escherichia coli and methicillin-resistant Staphylococcus aureus with negligible cytotoxicity. Interestingly, due to the 808 nm irradiation-induced hyperthermia in the presence of UNMS NCs, the glutathione oxidation process can be accelerated, resulting in bacterial death more easily. Mice wound models are established to further manifest that UNMS NCs can promote wound healing with good biosafety in living systems.

Central and peripheral auditory abnormalities in chinchilla animal model of blast-injury.

Exposure to blast overpressure or high-intensity sound can cause injuries to the auditory system, which leads to hearing loss or tinnitus. In this study, we examined the involvement of peripheral auditory system (PAS), and central auditory system (CAS) changes after exposure to blast overpressure (15-25 psi) on Day 1 and additionally during 7 days of post blast time period in chinchillas. Auditory brainstem response (ABR), distortion product otoacoustic emission (DPOAE), and cochlear hair cell changes were measured or identified in post-blast period within 7 days to detect injuries in the PAS. In the CAS, changes in NMDAR1 (excitatory receptor) and GABAA (inhibitory receptor) as well as changes in serotonin (5-HT2A) and acetylcholine (AChR) receptors were examined in different brain regions: auditory cortex (AC), geniculate body (GB), inferior colliculus (IC) and amygdala by immunofluorescence staining. We observed the PAS abnormalities of increased ABR threshold and decreased DPOAE response in animals after blast exposure with hearing protection devices (e.g., earplug). Blast exposure also caused a reduction in both NMDAR1 and GABAA receptor levels in acute condition (post-blast or Day 1) in AC and IC, while serotonin and acetylcholine receptor levels displayed a biphasic response at Day 1 and Day 7 post-exposure. Results demonstrate that the earplug can protect the tympanic membrane and middle ear against structural damage, but the hearing level, cochlear outer hair cell, and the central auditory system (levels of excitatory and inhibitory neurotransmitter receptors) were only partially protected at the tested blast overpressure level. The findings in this study indicate that blast exposure can cause both peripheral and central auditory dysfunctions, and the central auditory response is independent of peripheral auditory damage. The CAS dysfunction is likely mediated by direct transmission of shockwaves in all the regions of central nervous system (CNS), including nerves and surrounding tissues along the auditory pathways. Hence, targeting central auditory neurotransmitter abnormalities may have a therapeutic benefit to attenuate blast-induced hearing loss and tinnitus.

Performance and mechanism of mold-pressing alkali-activated material from MSWI fly ash for its heavy metals solidification.

The safe disposal of municipal solid waste incineration fly ash (MSWIFA) has become the weakest link of the circular economy of MSW due to its hazardous nature. In this study, we focused on the heavy metals solidification of MSWIFA by using alkali-activation technology and introducing a mold-pressing method. The influence of alkaline activator (AA) including alkali concentration and dosage of sodium silicate solution were well designed and studied. MSWIFA before and after alkali-activation, as well as the sample treated by commercial chelating agent (CA), were contrastively studied the performance of heavy metals solidification. The results show that the alkali-activated MSWIFA exhibits superior solidification for heavy metals than the blank control and the CA treated ones. With mold-pressing technology, the alkali-activated MSWIFA shows a core-shell structure, in which a thin layer that is composed of mainly N-A-S-H gel is as the shell and acts as a protective layer to inhibit the leaching of heavy metals. Besides, the introduced mold-pressing technology is beneficial for the improvement of materials strength and the reduction of AA dosage. The optimal AA composition is that the net concentration of NaOH is ∼4 M and sodium silicate dosage is ∼65 wt% in alkaline activator, and the total alkaline activator requirement is only 32 wt% of MSWIFA, yielding 7.9 MPa compressive strength at 10.2 MPa molding pressure. In summary, this work paves a potential new way for safe and recycling use of hazardous MSWIFA, which will be of great significance to environmental sustainability.

Enhanced Piezocatalytic Activity of Sr0.5Ba0.5Nb2O6 Nanostructures by Engineering Surface Oxygen Vacancies and Self-Generated Heterojunctions.

Piezocatalysis provides a promising strategy for directly converting weak mechanical energy into chemical energy. In this work, we report a simple one-step hydrogen reduction route for the simultaneous generation of surface defects and heterojunctions in Sr0.5Ba0.5Nb2O6 nanorods fabricated by a molten salt synthesis method. The as-fabricated Sr0.5Ba0.5Nb2O6/Sr2Nb2O7 nanocomposites with controllable oxygen vacancies exhibited excellent piezocatalytic activity under ultrasonic vibration, with an about 7 times enhancement of the rate constant (k = 0.0395 min-1) for rhodamine B degradation and an about 10 times enhancement of the water-splitting efficiency for hydrogen generation (109.4 µmol g-1 h-1) for the optimized sample (H2 annealed at 500 °C) compared to pristine Sr0.5Ba0.5Nb2O6 nanorods. This work demonstrates the essential role of a well-modulated oxygen vacancy concentration in the piezocatalytic activity and provides an inspiring guide for designing self-generated heterojunction piezocatalysts.

Pollution emission characteristics, distribution of heavy metals, and particle morphologies in a hazardous waste incinerator processing phenolic waste.

Secondary pollution emitted from hazardous waste incinerators (HWIs) can pose potential risks to the surrounding populations and environment. An investigation was conducted on pollutant emission status in a HWI combusting homogenized phenolic waste, woodchips, and electroplating sludge during the sampling period. Morphologies and elemental compositions of particles in flue gas and indoor air of the incinerator were characterized by TEM-EDS. Eight types of single particles were classified, as organic, soot, K-rich, S-rich, Na-rich, Fe-rich, mineral and fly ash particles. In the indoor air near the fly ash collector, organic and S-rich particles were the two most observed particles, taking 56 % and 30 %, respectively. While near the bottom ash collector, Fe-rich particles took approximately 30 %. Besides, the partitioning behavior of heavy metals in the incinerating process were investigated. Hg, Cd and Pb were mainly enriched in fly ash through evaporation, condensation, and adsorption; while Cr, Cu, Mn, and Ni were mostly remained in the bottom ash due to their low volatilities. This study provides information for regional air pollution source apportionment, but also helps understand the partitioning behavior of heavy metals for the secondary pollution control. Meanwhile, the visualized micro-compositions of indoor particles pave a way for occupational exposure risk assessment.

Defective analcime/geopolymer composite membrane derived from fly ash for ultrafast and highly efficient filtration of organic pollutants.

Nanofiltration membranes (NFMs) are of great interest for water purification attributed by their excellent performance, while the high fabrication cost greatly limits their use. Herein, an ultra-low-cost zeolite-based NFM was developed by a simple hydrothermal method using fly ash as the raw material and used for the high-efficiency filtration of organic pollutants from wastewater. The as-obtained zeolite membrane was composed of crystalline analcime (ANA) type zeolite and amorphous geopolymer (GP) composite. Benefiting from the defects introduced large cavities and microporous channels in ANA, the ANA/GP composite membrane with a thickness of ∼60 µm exhibited permeation rates as high as 340-440 L/(m2·h·MPa), and the rejection rates are up to 97 % towards methylene blue. Moreover, the fabrication cost of the ANA/GP membrane is only $31.8/m2, far lower than the reported efficient NFMs. The development of the ANA/GP-NFM paves the way for developing commercially applicable membranes for organics separation and water purification.

Geopolymerization enhanced hydrothermal synthesis of analcime from steel slag and CFBC fly ash and heavy metal adsorption on analcime.

This work is focused on crystal phase transition of solid wastes and functional application of crystal analcime in waste water purification, which provide a new environment-friendly route. In this paper, analcime was synthesized from steel slag and Circulating fluidized bed combustion (CFBC) fly ash (CFA) by hydrothermal method enhanced via geopolymerization (non-crystallized process). Then the analcimes were used for the removal of heavy metal ions (Pb2+, Cu2+) in aqueous solutions. Both the raw materials and products were characterized by XRF, XRD, FT-IR, SEM-EDS, and TEM. The results showed that non-crystallized process reduced the time of hydrothermal reaction and promoted the purity of analcime. The adsorption kinetics of analcime were all well fitted the pseudo-second-order model, and adsorption isotherms were well described by the Langmuir model. The maximum adsorption capacity of analcime for Pb2+ and Cu2+ were around 75.76, and 21.83 mg/g, respectively. The preference order observed for adsorption is Pb2+ > Cu2+.

An all-in-one strategy for the adsorption of heavy metal ions and photodegradation of organic pollutants using steel slag-derived calcium silicate hydrate.

Low-cost and high-performance materials or techniques that could synergistically remove inorganic heavy metals and organic pollutants in a simple manner are highly desired. Herein, we report a simple and facile strategy by converting poisonous heavy metals into photocatalyst for the in-situ photodegradation of organic pollutants employing steel slag-derived calcium silicate hydrate (CSH). The CSH was synthesized by alkali activation method and showed hierarchical structure and amorphous phase. And, the material exhibited excellent adsorption performance towards all selected heavy metals. After adsorption, the heavy metals were converted into the corresponding amorphous metal hydroxides on the surface of CSH. The resulting CSH-supported amorphous metal hydroxides can act as visible-light photocatalysts for the photodegradation of organic pollutants. The optimal results for the whole water purification route using CSH are > 100 mg/g adsorption capacity for Cu2+ and ˜63% / 8 h photodegradation efficiency for methylene blue under visible light. The total cost for the whole route is < 0.1 $/g pollutants, much lower than traditional technologies. The strategy using steel slag derived-CSH not only meets the requirements for high-performance and low-cost materials, but also resolves the challenging issues of developing an all-in-one treatment for heavy metal ions and organic pollutants, which will be of great significance to wastewater purification.

Luffa sponge-derived hierarchical meso/macroporous boron nitride fibers as superior sorbents for heavy metal sequestration.

Boron nitride (BN) has received tremendous attention as a promising adsorbent material. However, unsatisfactory uptake capacities over heavy metal ions limit their practical applications. Herein, we have synthesized a novel hierarchical meso/macroporous BN fibers (MBNFs) via a simple carbothermal reduction method using luffa sponge as a template. The as-obtained MBNFs comprise densely arranged parallel macrochannels on a micrometer scale, with mesopores on the surface of the channel. The resulting MBNFs exhibited remarkable adsorption performance for different heavy metal ions including Cd2+, Zn2+, Cr3+, and Pb2+ with maximum uptake capacities as high as 2989, 1885, 723, and 453 mg/g, respectively. In particular, the adsorption capacity for Cd2+ and Zn2+ exceed the highest values reported for BN materials. In addition, the MBNFs showed excellent stability to re-use for a few times. The present MBNFs materials prepared using cheap and earth abundant luffa sponge may find broad applications such as adsorbent for environmental remediation applications.

Amino-functionalized sewage sludge-derived biochar as sustainable efficient adsorbent for Cu(II) removal.

Sludge biochar as promising low-cost adsorbent has increasingly gained interests, but its poor surface functionality severely undermines its adsorption capacity and selectivity. Here a facile amino functionalization strategy was first proposed to enhance the surface functionality of sewage sludge derived biochar (SSDB) via the combination of sol-gel process for mesoporous silica coating and silylation for highly selective removal of Cu(II). The prepared amino-functionalized SSDB showed excellent adsorption capacity of 74.51 mg/g at room temperature, increasing by nearly 118% with regard to the unfunctionalized SSDB, and prominent selectivity (minute separation factor SFCo, Ni, Zn/Cu) toward Cu(II) uptake. Characterizations demonstrated amine groups on the SSDB, the surface density of which reached 1.34 mg/m2. The adsorption kinetics of Cu(II) on amino-functionalized SSDB was well described by a pseudo-second order kinetic model while the adsorption isotherm data was well fitted by Sips model. The pH range in which the adsorption preferentially occurred was 3-5. The occurrence of amine group protonation undermined adsorption performance at a pH < 3. These effects of amino-functionalized SSDB toward Cu(II) uptake were a result of the grafted amine groups specifically complexing with Cu(II) in the tetrahedron. Hence, prominent adsorption performance and low-cost feedstock make amino-functionalized SSDB a sustainable adsorbent for Cu(II) removal in water resulting in a cleaner utilization of sewage sludge.

A Novel Capturing Method for Quantification of Extra-Cellular Nanovesicles.

Extracellular vesicles (EVs), secreted by cells and found in body fluids play important roles in intercellular communication. Therefore, EVs are receiving increasing attention as potential biomarkers in the diagnosis and prognosis of various diseases. However, the detection and the quantification of EVs are hampered by the nanometer scale of these particles and by the lack of optimized quantification methods. Atomic force microscopy (AFM) is a powerful technology that can detect small particles. Here we report a 3D capture method for sample preparation of AFM which improves the accuracy, sensitivity and reproducibility for EVs' detection, compared to conventional sample preparation methods. By shaking a mica plate in EV solution, all the EVs were captured onto the 2D surface. The majority of the captured particles have a size ranging from 10 to 120 nm, which correlates with size data obtained from transmission electron microscopy studies. This novel sample preparation method has high adaptability potential and can also be applied to other organic and inorganic nanoparticles.

[Studies on the chemical constituents of Portulaca oleracea].

OBJECTIVE: To study the chemical constituents of Portulaca oleracea. METHODS: The constituents were isolated by column chromatography and identified on the basis of physicochemical and spectral data. RESULTS: Five compounds were isolated from 70% ethanol extract of this plant and their structures were elucidated as cyclo (Phe-Ile) (1), cycle (Tyr-Ala) (2), adenine (3), friedelin (4) and isoselachoceric acid (5). CONCLUSION: Compounds 1-5 are isolated from Portulaca oleracea for the first time.