Environmentally persistent free radicals (EPFRs) are produced during biochar pyrolysis and, depending on biochar application, can be either detrimental or beneficial. High levels of EPFRs may interfere with cellular metabolism and be toxic, because EPFR-generated reactive oxygen species (e.g., hydroxyl radicals (center dot OH)) attack organic molecules. However, center dot OH can be useful in remediating recalcitrant organic contaminants in soils. Understanding the (system-specific) safe range of EPFRs produced by biochars requires knowing both the context of their use and their overall significance in the existing suite of environmental radicals, which has rarely been addressed. Here we place EPFRs in a broader environmental context, showing that biochar can have EPFR concentrations from 108-fold lower to 109-fold higher than EPFRs from other environmental sources, depending on feedstock, production conditions, and degree of environmental aging. We also demonstrate that center dot OH radical concentrations from biochar EPFRs can be from 104-fold lower to 1017-fold higher than other environmental sources, depending on EPFR type and concentration, reaction time, oxidant concentration, and extent of environmental EPFR persistence. For both EPFR and center dot OH concentrations, major uncertainties derive from the range of biochar properties and the range of data reporting practices. Controlling feedstock lignin content and pyrolysis conditions are the most immediate options for managing EPFRs. Co-application of compost to provide organics may serve as a postpyrolysis method to quench and reduce biochar EPFRs.

During the excavation of large-scale rock slopes and deep hard rock engineering, the induced rapid unloading serves as the primary cause of rock mass deformation and failure. The essence of this phenomenon lies in the opening-shear failure process triggered by the normal stress unloading of fractured rock mass. In this study, we focus on local-scale rock fracture and conduct direct shear tests under different normal stress unloading rates on five types of non-persistent fractured hard rocks. The aim is to analyze the influence of normal stress unloading rates on the failure modes and shear mechanical characteristics of non-persistent fractured rocks. The results indicate that the normal unloading displacement decreases gradually with increasing normal stress unloading rate, while the influence of normal stress unloading rate on shear displacement is not significant. As the normal stress unloading rate increases, the rocks brittle failure process accelerates, and the degree of rocks damage decreases. Analysis of the stress state on rock fracture surfaces reveals that increasing the normal stress unloading rate enhances the compressive stress on rocks, leading to a transition in the failure mode from shear failure to tensile failure. A negative exponential strength formula was proposed, which effectively fits the relationship between failure normal stress and normal stress unloading rate. The findings enrich the theoretical foundation of unloading rock mechanics and provide theoretical support for disasters prevention and control in rock engineering excavations. (c) 2025 Institute of Rock and Soil Mechanics, Chinese Academy of Sciences. Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/ 4.0/).

The accumulation of allelochemicals in farming land has attracted a great deal of research attention, and biochar has shown positive effects in alleviating allelopathy. This study investigated how oligotrophic biochar application modulated salicylic acid (SA) generation in soybean roots through nutrient and oxidative stress pathways. Biochars were applied to soybean cultivation, with analyses conducted on nutrient adsorption, allelochemical profiles, and plant growth parameters. Results revealed that biochar suppressed benzoic acid (BA) while elevating SA levels, which correlated with the presence of persistent free radicals (PFRs) and nutrient retention. The retention of phosphorus (P) and ammonium (NH4+-N) dominated plant height reduction, surpassing oxidative stress effects linked to PFRs. Multivariate linear regression (MLR) identified P retention as the primary driver of SA generation, linked to adaptive phosphorus solubilization via acid secretion. Conversely, malondialdehyde (MDA) accumulation resulted from lipoxygenasemediated lipid peroxidation under nutrient stress and PFRs-induced oxidative stress. The strong adsorption of P and nitrate (NO3--N) by biochar exacerbated soil oligotrophy, triggering SA overproduction as a stress compensation mechanism. The significant correlation between SA and MDA indicated bidirectional stress signaling, wherein allelochemicals exacerbate oxidative damage while activating defense responses. These findings emphasize the dual role of biochar as both a stress inducer and an allelopathy modulator, highlighting the necessity for optimizing pyrolysis and developing soil-specific strategies to balance agricultural benefits with ecological risks.

This study investigates the effect of different in situ conditions like flaw infill, heat-treatment temperatures, and sample porosities on the anisotropic compressive response of jointed samples with an impersistent flaw. Jointed samples of different porosities are prepared by mixing Plaster of Paris (POP) with different water contents, i.e. 60% (i.e. for lower porosity) and 80% (i.e. for higher porosity). These samples are grouted with different infill materials, i.e. un-grouted, cement and sand-cement (3:1)-bioconcrete (SCB) mix and subsequently subjected to different temperatures, i.e. 100 degrees C, 200 degrees C and 300 degrees C. The results reveal the distinct stages in the stress-strain responses of samples characterized by initial micro-cracks closure, elastic transition, and non-linear response till peak followed by a post-peak behaviour. The un-grouted samples exhibit their lowest strength at 30 degrees joint orientation. The ratios of maximum to minimum strength are 3.11 and 3.22 with varying joint orientations for lower and higher porosity samples, respectively. Strengths of cement and SCB mix grouted samples are increased for all joint orientations ranging between 16.13%-69.83% and 18.04%-73% at low porosity and 22%-48.66% and 27.77%-51.57% at high porosity, respectively as compared to the un-grouted samples. However, the strength of the grouted samples is decreased by 66.94%-75.47% and 77.17%-81.05% at lower porosity, and 79.37%-82.86% and 81.29%-95.55% at higher porosity for cement and for SCB grouts with an increase in the heating temperature from 30 degrees C to 300 degrees C, respectively. These observations could be due to the suppression of favourable crack initiation locations, i.e. flaw tips along the samples due to the filling of the crack by grouting and generation of thermal cracks with temperature. The mechanism of strength behaviour is elucidated in detail based on fracture propagation analysis and the anisotropic response of with or, without grouted samples. (c) 2025 Institute of Rock and Soil Mechanics, Chinese Academy of Sciences. Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/ 4.0/).

The existing lunar exploration activities and associated equipment interactions are limited to the surface environment, where the stress state of the lunar regolith is significantly lower than that in laboratory tests conducted on Earth. To address this, this paper proposes a new framework for discrete modeling of large-scale triaxial tests on lunar regolith under low confining pressure. The framework incorporates particle shapes from the Chang'E-5 mission (CE-5) and flexible boundary conditions. Firstly, the shape characteristics of the lunar regolith particles were adopted in the Discrete Element Method (DEM) model to reproduce the mechanical properties of the lunar regolith as accurately as possible. Then, experiments with varying membrane particle stiffness ratios were conducted to explore the effect of the rubber membrane's properties on the mechanical characteristics of lunar regolith under low effective confining pressure. Topological Data Analysis (TDA) tools from persistent homology were utilized to quantify the dynamic response of particles during the onset and development of strain localization. The results indicate that under low effective confining pressure, selecting appropriate rubber membrane types is crucial for accurately determining the mechanical properties of lunar regolith. (c) 2024 COSPAR. Published by Elsevier B.V. All rights are reserved, including those for text and data mining, AI training, and similar technologies.

Environmentally persistent free radicals are long-lived pollutants that maintain stability in air, soil, and water. They contribute to the production of reactive oxygen species in environmental media, leading to oxidative stress in biological organisms. This stress can provoke inflammation and damage to biological macromolecules, potentially resulting in cardiopulmonary dysfunction. In this review, we discuss the formation and classification of EPFRs. Typically, EPFRs form through electron transfer from organic compounds to transition metals during thermal processes. In metal-free environments, however, organic compounds can undergo bond cleavage, generating EPFRs under thermal conditions and light exposure. EPFRs are generally categorized into three types: oxygen-centered, carbon-centered, and those containing heteroatoms centered on either oxygen or carbon. We also provide a detailed summary of the fundamental characteristics of EPFRs in different environments such as air, soil, and water. Given their role as electron donors, EPFRs have potential applications in degrading organic pollutants in the environment. The review comprehensively addresses the deleterious impacts of EPFRs on organism health, highlighting risks to metabolic functions and cardiopulmonary health. Furthermore, it underscores the potential involvement of EPFRs as electron donors in atmospheric chemical reactions. The pivotal role of EPFRs in environmental pollutant transformation warrants more studies in future research endeavors.

Various pollutants are released into environment due to extensive anthropogenic activities. Polycyclic Aromatic Hydrocarbons (PAHs) are one such pollutants that causes great damaging effect to ecology and living creatures. PAHs are known to have carcinogenic, mutagenic, teratogenic, genotoxic effects on plants and animals. In order to reduce the level of PAHs in environment and to remediate the contaminated areas (soil), various techniques such as ozonation, coagulation, electroremediation etc. have been designed. One environment friendly, green technology is Phytoremediation in which plants play a key role on decontaminating the PAHs contaminated area. Phytoremediation of PAHs is an alternate to conventional methods owing to latter's disadvantages. In Phytoremediation, plants accumulate, stabilize, transform and volatilize the pollutants, thus helping in reclaiming the area. In view of increasing global concern towards PAHs pollution in environment, present review highlights the mechanism and efficiency of phytoremediation in reclamation of PAH contaminated area.

The prevalence of organophosphate esters (OPEs) in the global environment is increasing, which aligns with the decline in the usage of polybrominated diphenyl ethers (PBDEs). PBDEs, a category of flame retardants, were banned and classified as persistent organic pollutants (POPs) through the Stockholm Convention due to their toxic and persistent properties. Despite a lack of comprehensive understanding of their ecological and health consequences, OPEs were adopted as replacements for PBDEs. This research aims to offer a comparative assessment of PBDEs and OPEs in various domains, specifically focusing on their persistence, bioaccumulation, and toxicity (PBT) properties. This study explored physicochemical properties (such as molecular weight, octanol-water partition coefficient, octanol-air partition coefficient, Henry's law constant, and vapor pressures), environmental behaviors, global concentrations in environmental matrices (air, water, and soil), toxicities, bioaccumulation, and trophic transfer mechanisms of both groups of compounds. Based on the comparison and analysis of environmental and toxicological data, we evaluate whether OPEs represent another instance of regrettable substitution and global contamination as much as PBDEs. Our findings indicate that the physical and chemical characteristics, environmental behaviors, and global concentrations of PBDEs and OPEs, are similar and overlap in many instances. Notably, OPE concentrations have even surged by orders of several magnitude compared to PBDEs in certain pristine regions like the Arctic and Antarctic, implying long-range transport. In many instances, air and water concentrations of OPEs have been increased than PBDEs. While the bioaccumulation factors (BAFs) of PBDEs (ranging from 4.8 to 7.5) are slightly elevated compared to OPEs (-0.5 to 5.36) in aquatic environments, both groups of compounds exhibit BAF values beyond the threshold of 5000 L/kg (log10 BAF > 3.7). Similarly, the trophic magnification factors (TMFs) for PBDEs (ranging from 0.39 to 4.44) slightly surpass those for OPEs (ranging from 1.06 to 3.5) in all cases. Metabolic biotransformation rates (LogK(M)) and hydrophobicity are potentially major factors deciding their trophic magnification potential. However, many compounds of PBDEs and OPEs show TMF values higher than 1, indicating biomagnification potential. Collectively, all data suggest that PBDEs and OPEs have the potential to bioaccumulate and transfer through the food chain. OPEs and PBDEs present a myriad of toxicity endpoints, with notable overlaps encompassing reproductive issues, oxidative stress, developmental defects, liver dysfunction, DNA damage, neurological toxicity, reproductive anomalies, carcinogenic effects, and behavior changes. Based on our investigation and comparative analysis, we conclude that substituting PBDEs with OPEs is regrettable based on PBT properties, underscoring the urgency for policy reforms and effective management strategies. Addressing this predicament before an exacerbation of global contamination is imperative.

Biochar is a promising soil conditioner and environmental remediation material. However, the amount, type, and environmental effect and risk of persistent free radicals (PFRs) associated with biochar need to be better understood. Thus, this study characterized PFRs in a range of biochar types and their effects on the growth and oxidative stress of wheat seedlings. Among the biochars prepared by pyrolysis of different types of biomass at 500 degrees C, the concentrations of PFRs in cow dung and egg shell biochar were the highest and the lowest, respectively. They both increased with artificial weathering treatment but decreased with aging. The dominant types of biochar PFRs were transformed from carbon-centered to oxygen and carbon/oxygen-centered free radicals with weathering. The amount and type of biochar PFRs in mixtures of biochar and soil varied with soil type and biochar dose. After 30 d incubation in different soil-biochar mixtures, measures of wheat plant germination and growth and antioxidant enzyme activity showed increases at lower biochar doses but decreases at higher doses. Catalase activity was 38.1 % greater at 20 g center dot kg(-1) biochar dosage and 25.2 % less at 80 g center dot kg(-1) dosage, on average. In contrast, leaf malondialdehyde content and staining by Evans Blue, both indicators of plant cell membrane damage, generally increased with increasing biochar dosages. Finally, soil hydrolase enzyme activity also displayed an inverted U-shaped dose response. The toxicity indicators showed an increasing trend with higher PFR concentrations in the soil-biochar combinations. While these findings provide evidence for significant potential agricultural and ecological risks associated with the application of biochar due to PFRs damage, it also points to ways that these risks could be mediated such as through biochar dosage restrictions and pre-aging. This study provides new insights into the potential toxicological mechanism and ecological risks associated with the application of biochar in agricultural and environmental settings.

Potential relationships among heavy air pollution, weather conditions, and meteorological effects are unclear and require further investigation, especially for areas with complex terrains, such as the Sichuan Basin (SCB), one of the most polluted regions in China. In this study, air pollution in the SCB was examined and 18 regional persistent heavy pollution events (RPHEs) were identified for the winters of 2014-2018. The average persistent period of the RPHEs was 8.89 days, and the number of affected cities was 17. Based on ground-based observations, CALIPSO satellite data, reanalysis data, and backward trajectory calculations, the synergistic effects of the thermodynamic structures, synoptic circulations and the radiative feedback of aerosols on the formation of RPHEs were revealed. The results can be summarized as follows: (1) An abnormal warming center, attributing to the warm southerly advection in the upper layer and the cold air dammed by the topography near the surface, always presented around 800-700 hPa to form a deep stable layer. (2) The diurnal variations in vertical motions triggered by the thermodynamic structures could regulate the pollution episodes. During the daytime, pollutants accumulated rapidly and thoroughly mixed under the control of sinking airflow from 800 hPa layer to the ground. At night, pollutants sometimes slowly diffused when weak ascending airflow appeared. (3) Forced by the stable layer and topography of the Tibetan Plateau, the local circulation was confined within SCB, resulting in the intensive mixing of local emissions and transport pollutants from other regions. This situation could be maintained for a long time with stable synoptic circulation in winter, leading to the formation of RPHEs. (4) The pollution episodes were featured with multi-layer pollutants above SCB according to the CALIPSO observations, including the local anthropogenic aerosols near the surface, dust aerosols originating from the Taklamakan Desert, and biomass burning aerosols from Southeast Asia. Solar absorption aerosols, including black carbon and dust above the region, could cause meteorological feedback, making the vertical layer more stable and enhancing the persistence and intensity of the pollution episodes. This study highlights the appreciable effects of synoptic circulations on the vertical thermodynamic structures of the atmosphere and air quality, and raises the understanding of the environmental and climate impacts of RPHEs in complex terrains.