A review of functions and mechanisms of clay soil conditioners and catalysts in thermal remediation compared to emerging photo-thermal catalysis.

High temperatures and providing sufficient time for the thermal desorption of persistent organic pollutants (POPs) from contaminated clay soils can lead to intensive energy consumption. Therefore, this article provides a critical review of the potential additives which can improve soil texture and increase the volatility of POPs, and then discusses their enhanced mechanisms for contributing to a green economy. Ca-based additives have been used to reduce plasticity of bentonite clay, absorb water and replenish system heat. In contrast, non-Ca-based additives have been used to decrease the plasticity of kaolin clay. The soil structure and soil plasticity can be changed through cation exchange and flocculation processes. The transition metal oxides and alkali metal oxides can be applied to catalyze and oxidize polycyclic aromatic hydrocarbons, petroleum and emerging contaminants. In this system, reactive oxygen species (•O2- and •OH) are generated from thermal excitation without strong chemical oxidants. Moreover, multiple active ingredients in recycled solid wastes can be controlled to reduce soil plasticity and enhance thermal catalysis. Alternatively, the alkali, nano zero-valent iron and nano-TiN can catalyze hydrodechlorination of POPs under reductive conditions. Especially, photo and photo-thermal catalysis are discussed to accelerate replacement of fossil fuels by renewable energy in thermal remediation.

Predicting the efficiency of arsenic immobilization in soils by biochar using machine learning.

Arsenic (As) pollution in soils is a pervasive environmental issue. Biochar immobilization offers a promising solution for addressing soil As contamination. The efficiency of biochar in immobilizing As in soils primarily hinges on the characteristics of both the soil and the biochar. However, the influence of a specific property on As immobilization varies among different studies, and the development and application of arsenic passivation materials based on biochar often rely on empirical knowledge. To enhance immobilization efficiency and reduce labor and time costs, a machine learning (ML) model was employed to predict As immobilization efficiency before biochar application. In this study, we collected a dataset comprising 182 data points on As immobilization efficiency from 17 publications to construct three ML models. The results demonstrated that the random forest (RF) model outperformed gradient boost regression tree and support vector regression models in predictive performance. Relative importance analysis and partial dependence plots based on the RF model were conducted to identify the most crucial factors influencing As immobilization. These findings highlighted the significant roles of biochar application time and biochar pH in As immobilization efficiency in soils. Furthermore, the study revealed that Fe-modified biochar exhibited a substantial improvement in As immobilization. These insights can facilitate targeted biochar property design and optimization of biochar application conditions to enhance As immobilization efficiency.

Synthesis of ternary geopolymers using prediction for effective solidification of mercury in tailings.

This study used steel slag, fly ash, and metakaolin as raw materials (SFM materials) to create silica-alumina-based geopolymers that can solidify Hg2+ when activated with sodium-based water glass. The experiments began with a triangular lattice point mixing design experiment, and the results were fitted, analyzed, and predicted. The optimum SFM material mass ratio was found to be 70% steel slag, 25% fly ash, and 5% metakaolin. The optimum modulus of the activator was identified by comparing the unconfined compressive strength and solidifying impact on Hg2+of geosynthetics with different modulus. The SFM geopolymer was then applied in the form of potting to cure the granulated mercury tailings. The inclusion of 50% SFM material generated a geosynthetic that reduced mercury transport to the surface soil by roughly 90%. The mercury concentration of herbaceous plant samples was also reduced by 78%. It indicates that the SFM material can effectively attenuate the migration transformation of mercury. Finally, characterization methods such as XPS and FTIR were used to investigate the mechanism of Hg2+ solidification by geopolymers generated by SFM materials. The possible solidification mechanisms were proposed as alkaline environment-induced mercury precipitation, chemical bonding s, surface adsorption of Hg2+ and its precipitates by the geopolymer, and physical encapsulation.

Hybrid and enhanced electrokinetic system for soil remediation from heavy metals and organic matter.

The electrokinetic (EK) process has been proposed for soil decontamination from heavy metals and organic matter. The advantages of the EK process include the low operating energy, suitability for fine-grained soil decontamination, and no need for excavation. During the last three decades, enhanced and hybrid EK systems were developed and tested for improving the efficiency of contaminants removal from soils. Chemically enhanced-EK processes exhibited excellent efficiency in removing contaminants by controlling the soil pH or the chemical reaction of contaminants. EK hybrid systems were tested to overcome environmental hurdles or technical drawbacks of decontamination technologies. Hybridization of the EK process with phytoremediation, bioremediation, or reactive filter media (RFM) improved the remediation process performance by capturing contaminants or facilitating biological agents' movement in the soil. Also, EK process coupling with solar energy was proposed to treat off-grid contaminated soils or reduce the EK energy requirements. This study reviews recent advancements in the enhancement and hybrid EK systems for soil remediation and the type of contaminants targeted by the process. The study also covered the impact of operating parameters, imperfect pollution separation, and differences in the physicochemical characteristics and microstructure of soil/sediment on the EK performance. Finally, a comparison between various remediation processes was presented to highlight the pros and cons of these technologies.

Efficient remediation of different concentrations of Cr-contaminated soils by nano zero-valent iron modified with carboxymethyl cellulose and biochar.

Nano zero-valent iron (nZVI) is widely used in soil remediation due to its high reactivity. However, the easy agglomeration, poor antioxidant ability and passivation layer of Fe-Cr coprecipitates of nZVI have limited its application scale in Cr-contaminated soil remediation, especially in high concentration of Cr-contaminated soil. Herein, we found that the carboxymethyl cellulose on nZVI particles could increase the zeta potential value of soil and change the phase of nZVI. Along with the presence of biochar, 97.0% and 96.6% Cr immobilization efficiency through CMC-nZVI/BC were respectively achieved in high and low concentrations of Cr-contaminated soils after 90-days remediation. In addition, the immobilization efficiency of Cr(VI) only decreased by 5.1% through CMC-nZVI/BC treatment after 10 weeks aging in air, attributing to the strong antioxidation ability. As for the surrounding Cr-contaminated groundwater, the Cr(VI) removal capacity of CMC-nZVI/BC was evaluated under different reaction conditions through column experiments and COMSOL Multiphysics. CMC-nZVI/BC could efficiently remove 85% of Cr(VI) in about 400 hr when the initial Cr(VI) concentration was 40 mg/L and the flow rate was 0.5 mL/min. This study demonstrates that uniformly dispersed CMC-nZVI/BC has an excellent remediation effect on different concentrations of Cr-contaminated soils.

Oxygen atmosphere enhances ball milling remediation of petroleum-contaminated soil and reuse as adsorptive/catalytic materials for wastewater treatment.

Ball milling is an environmentally friendly technology for the remediation of petroleum-contaminated soil (PCS), but the cleanup of organic pollutants requires a long time, and the post-remediation soil needs an economically viable disposal/reuse strategy due to its vast volume. The present paper develops a ball milling process under oxygen atmosphere to enhance PCS remediation and reuse the obtained carbonized soil (BCS-O) as wastewater treatment materials. The total petroleum hydrocarbon removal rates by ball milling under vacuum, air, and oxygen atmospheres are 39.83%, 55.21%, and 93.84%, respectively. The Langmuir and pseudo second-order models satisfactorily describe the adsorption capacity and behavior of BCS-O for transition metals. The Cu2+, Ni2+, and Mn2+ adsorbed onto BCS-O were mainly bound to metal carbonates and metal oxides. Furthermore, BCS-O can effectively activate persulfate (PDS) oxidation to degrade aniline, while BCS-O loaded with transition metal (BCS-O-Me) shows better activation efficiency and reusability. BCS-O and BCS-O-Me activated PDS oxidation systems are dominated by 1O2 oxidation and electron transfer. The main active sites are oxygen-containing functional groups, vacancy defects, and graphitized carbon. The oxygen-containing functional groups and vacancy defects primarily activate PDS to generate 1O2 and attack aniline. Graphitized carbon promotes aniline degradation by accelerating electron transfer. The paper develops an innovative strategy to simultaneously realize efficient remediation of PCS and sequential reuse of the post-remediation soil.

Soil colloids can significantly enhance spreading of polybromodiphenyl ethers in groundwater by serving as an effective carrier.

Polybromodiphenyl ethers (PBDEs), the widely used flame retardants, are common contaminants in surface soils at e-waste recycling sites. The association of PBDEs with soil colloids has been observed, indicating the potential risk to groundwater due to colloid-facilitated transport. However, the extent to which soil colloids may enhance the spreading of PBDEs in groundwater is largely unknown. Herein, we report the co-transport of decabromodiphenyl ester (BDE-209) and soil colloids in saturated porous media. The colloids released from a soil sample collected at an e-waste recycling site in Tianjin, China, contain high concentration of PBDEs, with BDE-209 being the most abundant conger (320 ± 30 mg/kg). The colloids exhibit relatively high mobility in saturated sand columns, under conditions commonly observed in groundwater environments. Notably, under all the tested conditions (i.e., varying flow velocity, pH, ionic species and ionic strength), the mass of eluted BDE-209 correlates linearly with that of eluted soil colloids, even though the mobility of the colloids varies markedly depending on the specific hydrodynamic and solution chemistry conditions involved. Additionally, the mass of BDE-209 retained in the columns also correlates strongly with the mass of retained colloids. Apparently, the PBDEs remain bound to soil colloids during transport in porous media. Findings in this study indicate that soil colloids may significantly promote the transport of PBDEs in groundwater by serving as an effective carrier. This might be the reason why the highly insoluble and adsorptive PBDEs are found in groundwater at some PBDE-contaminated sites.

Insight into the sorption and desorption pattern of pyrrolizidine alkaloids and their N-oxides in acidic tea (Camellia sinensis) plantation soils.

Pyrrolizidine alkaloids (PAs) and their N-oxides (PANOs) are phytotoxins produced by various plant species and have been emerged as environmental pollutants. The sorption/desorption behaviors of PAs/PANOs in soil are crucial due to the horizontal transfer of these natural products from PA-producing plants to soil and subsequently absorbed by plant roots. This study firstly investigated the sorption/desorption behaviors of PAs/PANOs in tea plantation soils with distinct characteristics. Sorption amounts for seneciphylline (Sp) and seneciphylline-N-oxide (SpNO) in three acidic soils ranged from 2.9 to 5.9 µg/g and 1.7 to 2.8 µg/g, respectively. Desorption percentages for Sp and SpNO were from 22.2% to 30.5% and 36.1% to 43.9%. In the mixed PAs/PANOs systems, stronger sorption of PAs over PANOs was occurred in tested soils. Additionally, the Freundlich models more precisely described the sorption/desorption isotherms. Cation exchange capacity, sand content and total nitrogen were identified as major influencing factors by linear regression models. Overall, the soils exhibiting higher sorption capacities for compounds with greater hydrophobicity. PANOs were more likely to migrate within soils and be absorbed by tea plants. It contributes to the understanding of environmental fate of PAs/PANOs in tea plantations and provides basic data and clues for the development of PAs/PANOs reduction technology.

A new insight into the straw decomposition associated with minerals: Promoting straw humification and Cd immobilization.

Organic matter (OM) derived from the decomposition of crop residues plays a key role as a sorbent for cadmium (Cd) immobilization. Few studies have explored the straw decomposition processes with the presence of minerals, and the effect of newly generated organo-mineral complexes on heavy metal adsorption. In this study, we investigated the variations in structure and composition during the rice straw decomposition with or without minerals (goethite and kaolinite), as well as the adsorption behavior and mechanisms by which straw decomposition affects Cd immobilization. The degree of humification of extracted straw organic matter was assessed using excitation-emission matrix (EEM) fluorescence and Ultraviolet-visible spectroscopy (UV-vis), while employing FTIR spectroscopy and XPS to characterize the adsorption mechanisms. The spectra analysis revealed the enrichment of highly aromatic and hydrophobic components, indicating that the degree of straw decomposition and humification were further intensified during incubation. Additionally, the existence of goethite (SG) accelerated the humification of OM. Sorption experiments revealed that the straw humification increased Cd adsorption capacity. Notably, SG exhibited significantly higher adsorption performance compared to the organic matter without minerals (RS) and the existence of kaolinite (SK). Further analysis using FT-IR spectroscopy and XPS verified that the primary mechanisms involved in Cd immobilization were complexion with -OH and -COOH, as well as the formation of Cd-π binds with aromatic C=C on the surface of solid OMs. These findings will facilitate understanding the interactions of the rice straw decomposing with soil minerals and its remediation effect on Cd-contaminated farmland.

Sorption and degradation processes of imidacloprid in Florida soils.

Imidacloprid (IDP) is an active ingredient of the Admire brand pesticide used to control the vector (Asian citrus psyllid) that transmits the causative organism Candidatus Liberibacter asiaticus (CLas) for citrus greening or huanglongbing disease. Imidacloprid products are applied via soil drench where citrus roots are mostly concentrated which is between 0 and 60 cm depth. These soil depths exhibit different characteristics that may affect IDP leaching beyond the rooting zone. Representative soil samples were collected from Entisols and Ultisols, which are the dominant soil orders under citrus production in central Florida, at 15 cm increments up to 60 cm to estimate and understand the batch sorption, kinetics, equilibria, and degradation of IDP. Results showed that the equilibrium time for IDP at 0-15 cm depth (10 hours) was 2 times faster than at 15-60 cm (20 hours) for the Entisol. Nevertheless, all depths reached equilibrium within 24 hours for the Entisol. The 0-30 cm depth adsorbed 2 times more IDP than the 30-60 cm depth for both soils. Nevertheless, the adsorption coefficient was approximately ≤ 1 mL g-1 for both soils. The half-life of IDP in both soils ranged from 10 to 17 days. The Entisol showed higher adsorption than the Ultisol at both depths, probably due to relatively lower organic carbon (OC) content in the Ultisol compared to the Entisol. Thus, the Ultisol showed high IDP leaching vulnerability compared to the Entisol. Movement of IDP is affected by the amount of OC in the citrus critical zone.

Application of synthesized metal-trimesic acid frameworks for the remediation of a multi-metal polluted soil and investigation of quinoa responses.

Metal-organic frameworks (MOFs) are structures with high surface area that can be used to remove heavy metals (HMs) efficiently from the environment. The effect of MOFs on HMs removal from contaminated soils has not been already investigated. Monometallic MOFs are easier to synthesize with high efficiency, and it is also important to compare their structures. In the present study, Zn-BTC, Cu-BTC, and Fe-BTC as three metal-trimesic acid MOFs were synthesized from the combination of zinc (Zn), copper (Cu), and iron (Fe) nitrates with benzene-1,3,5-tricarboxylic acid (H3BTC) by solvothermal method. BET analysis showed that the specific surface areas of the Zn-BTC, Cu-BTC, and Fe-BTC were 502.63, 768.39 and 92.4 m2g-1, respectively. The synthesized MOFs were added at the rates of 0.5 and 1% by weight to the soils contaminated with 100 mgkg-1 of Zn, nickel (Ni), lead (Pb), and cadmium (Cd). Then quinoa seeds were sown in the treated soils. According to the results, the uptakes of all four HMs by quinoa were the lowest in the Cu-BTC 1% treated pots and the lowest uptakes were observed for Pb in shoot and root (4.87 and 0.39, µgpot-1, respectively). The lowest concentration of metal extracted with EDTA in the post-harvest soils was for Pb (11.86 mgkg-1) in the Cu-BTC 1% treatment. The lowest metal pollution indices were observed after the application of Cu-BTC 1%, which were 20.29 and 11.53 for shoot and root, respectively. With equal molar ratios, highly porous and honeycomb-shaped structure, the most crystallized and the smallest constituent particle size (34.64 nm) were obtained only from the combination of Cu ions with H3BTC. The lowest porosity, crystallinity, and a semi-gel like feature was found for the Fe-BTC. The synthesized Cu-BTC showed the highest capacity of stabilizing HMs, especially Pb in the soil compared to the Zn-BTC and the Fe-BTC. The highly porous characteristic of the Cu-BTC can make the application of this MOF as a suitable environmental solution for the remediation of high Pb-contaminated soils.

Concurrent Analysis of Tiafenacil and Its Transformation Products in Soil by Using Newly Developed UHPLC-QTOF-MS/MS-Based Approaches.

As new pesticides continue to emerge in agricultural systems, understanding their environmental behavior is crucial for effective risk assessment. Tiafenacil (TFA), a promising novel pyrimidinedione herbicide, was the focus of this study. We developed an efficient QuEChERS-UHPLC-QTOF-MS/MS method to measure TFA and its transformation products (TP1, TP2, TP3, TP4, and TP5) in soil. Our calibration curves exhibited strong linearity (R2 ≥ 0.9949) ranging from 0.015 to 2.0 mg/kg within a low limit of quantification (LOQ) of 2.0 µg/kg. Inter-day and intra-day recoveries (0.10 to 2.0 mg/kg, 80.59% to 110.05%, RSD from 0.28% to 12.93%) demonstrated high sensitivity and accuracy. Additionally, TFA dissipation under aerobic conditions followed first-order kinetics, mainly yielding TP1 and TP4. In contrast, TP1 and TP2 were mainly found under sterilized and anaerobic conditions, and TFA dissipation followed second-order kinetics. Moreover, we predicted the transformation pathways of TFA using density functional theory (DFT) and assessed the toxicity levels of TFA and its TPs to aquatic organisms using ECOSAR. Collectively, these findings hold significant implications for a better understanding of TFA fate in diversified soil, benefiting its risk assessment and rational utilization.

Enhancing soil health, microbial count, and hydrophilic methomyl and hydrophobic lambda-cyhalothrin remediation with biochar and nano-biochar.

Pesticide contamination and soil degradation present significant challenges in agricultural ecosystems, driving extensive exploration of biochar (BC) and nano-biochar (NBC) as potential solutions. This study examines their effects on soil properties, microbial communities, and the fate of two key pesticides: the hydrophilic methomyl (MET) and the hydrophobic lambda-cyhalothrin (LCT), at different concentrations (1%, 3%, and 5% w w-1) in agricultural soil. Through a carefully designed seven-week black bean pot experiment, the results indicated that the addition of BC/NBC significantly influenced soil dynamics. Soil pH and moisture content (MC) notably increased, accompanied by a general rise in soil organic carbon (SOC) content. However, in BC5/NBC5 treatments, SOC declined after the 2nd or 3rd week. Microbial populations, including total plate count (TPC), phosphate-solubilizing bacteria (PSB), and nitrogen-fixing bacteria (NFB), showed dynamic responses to BC/NBC applications. BC1/NBC1 and BC3/NBC3 applications led to a significant increase in microbial populations, whereas BC5/NBC5 treatments experienced a decline after the initial surge. Furthermore, the removal efficiency of both MET and LCT increased with higher BC/NBC concentrations, with NBC demonstrating greater efficacy than BC. Degradation kinetics, modeled by a first-order equation, revealed that MET degraded faster than LCT. These findings underscore the profound impact of BC/NBC on pesticide dynamics and microbial communities, highlighting their potential to transform sustainable agricultural practices.

The analysis of release and percolation rate of nutrients from regular and obsidian-based slow-release fertilizers.

Research on the observation of nutrient release rates from slow-release and regular fertilizers combined with the percolation rate in the soil is scarce. This work aims to observe potassium and phosphate release behavior from slow-release and regular fertilizer, followed by the percolation of that nutrient in the soil. The characteristics of the soil were analyzed using X-ray Diffraction (XRD), X-ray Fluorescence (XRF), and Scanning Electron Microscope (SEM). The concentration of potassium and phosphate in soil is analyzed using Atomic Absorption Spectroscopy (AAS) and Ultraviolet-Visible Spectroscopy (UV-Vis), respectively. The release rate of nutrients from slow-release fertilizer is 6 to 8 times slower than regular fertilizer. Meanwhile, the rate of nutrients released from slow-release and regular fertilizer followed by soil percolation matches the quadratic equation. Potassium adsorption on the soil surface is significantly higher than that of potassium. The negativity of soil polarity contributed to the high level of potassium adsorption on soil particle surfaces. The low phosphate adsorption capability of magnetite and the negativity of soil polarity contributed to the soil's low phosphate adsorption.

Remediation on antimony-contaminated soil from mine area using zero-valent-iron doped biochar and their effect on the bioavailability of antimony.

Due to the bioavailability and movement of antimony in trophic web, the overexploitation of antimony mine resulted in antimony contamination that harmed the ecology nearby, raising concerns for public health. Whereas, most researches focused on the removal of antimony in the aqueous instead of the immobilization of antimony in the soil. Herein, the immobilized performance of biochar (BC) loaded with nano zero-valent iron (nZVI-BC) on antimony in the soil near the smelting area was researched through pot experiments for the first time, and its stabilization mechanism on antimony was investigated by valent state variation of antimony. The results demonstrated that BC restricted the cation exchange capacity and catalase activity in the soil, while nZVI-BC had a favorable and negative impact on two variables, respectively. The nZVI-BC showed more stable immobilization capacity on antimony over time than BC, whose exchangeable speciation only marginally rose (2%-6%), although the exchangeable speciation of antimony fell both from 15% to 2% after adding the BC and nZVI-BC, The electron attraction force between nZVI-BC and antimony was also intensified owing to the oxidation-reduction process, which was considered as the stabilizing principle of nZVI-BC on antimony in soil. Furthermore, the decreased bioaccumulation factor for the perennial ryegrass (0.46-0.21) and Galinsoga parviflora Cav. (0.26-0.17) stated that the BC effectively mitigated the bioaccumulation risk of antimony.

Effects of biodegradable microplastics coexistence with biochars produced at low and high temperatures on bacterial community structure and phenanthrene degradation in soil.

The increasing use of biodegradable plastics may result in more serious pollution of microplastics which often coexist with biochar in soil, this will affect how organic pollutants move and transform in the soil. This work investigated the effect of biodegradable polybutylene adipate-co-terephthalate (PBAT) coexistence with biochars produced at temperatures of 400 and 700 °C (W4 and W7) on soil bacterial communities and phenanthrene degradation. The results showed that coexistence of PBAT and biochar paticles greatly boosted the relative abundance of Nocardioides while decreased the relative abundance of Sphingomonas as compared to soils with a single addition of PBAT or biochar. Changes in soil Eh values were the most influential factor in bacterial communities (more than 40% contribution). The degradation ratio of phenanthrene when PBAT coexisted with W7 (39.6 ± 3.6%) was not significantly different from the treatment with a single W7 addition (35.0 ± 2.3%, P＞0.05), and was related to phenanthrene degradation in the adsorbed state of W7 in soil. In contrast, the degradation ratio of phenanthrene in PBAT coexisting with W4 (35.1 ± 3.5%) was intermediate between that of single PBAT (49.8 ± 0.9%) and W4 (13.7 ± 5.8%) treatments. This was primarily due to changes in the experiment's initial bioavailable phenanthrene content. Furthermore, after the introduction of earthworms, phenanthrene degradation ratio in coexistence treatments were very similar to that described above in the absence of earthworms. Except for two treatments that contain W7, phenanthrene degradation ratio in the other treatments was increased by the presence of earthworms (up to 23%), which is related to the enhanced relative abundance of polycyclic aromatic hydrocarbon-degraders. Our findings indicated that PBAT coexistence with high-temperature or low-temperature biochar had a completely different impact on bacterial communities and phenanthrene degradation in soil.

Adsorption mechanism and remediation of heavy metals from soil amended with hyperthermophilic composting products: Exploration of waste utilization.

Due to high humification, hyperthermophilic composting products (HP) show potential for remediating heavy metal pollution. However, the interaction between HP and heavy metals remains unclear. This study investigated the adsorption mechanism and soil remediation effect of HP on heavy metals. The results showed that the maximum adsorption capacity of HP increased by an average of 30.74 % compared to conventional composting products. HP transformed 34.87 % of copper, 42.55 % of zinc, and 35.63 % of lead from exchangeable and reducible forms into residual and oxidizable forms, thus reducing the soil risk level. In conclusion, HP significantly enhanced the adsorption of heavy metals and their transformation from unstable to stable forms, primarily due to the higher content of hydroxyl and carboxyl groups. This study aims to demonstrate the effectiveness of HP for remediating heavy metal pollution and to enhance the understanding of the underlying mechanism, which lays a foundation for waste utilization.

The fate and impact of Co3O4 nanoparticles in the soil environment: Observing the dose effect of nanoparticles on soybeans.

The widespread presence and distribution of metal-based nanoparticles (NPs) in soil is threatening crop growth and food security. However, little is known about the fate of Co3O4 NPs in the soil-soybean system and their phytotoxicity. The study demonstrated the effects of Co3O4 NPs on soybean growth and yield in soil after 60 days and 140 days, and compared them with the phytotoxic effects of Co2+. The results showed that Co3O4 NPs (10-500 mg/kg) had no significant toxic effect on soybeans. Soil available Co content was significantly increased under 500 mg/kg Co3O4 NPs treatment. Compared with Co2+, Co3O4 NPs mainly accumulated in roots and had limited transport to the shoots, which was related to the particle size, surface charge and chemical stability of Co3O4 NPs. The significant accumulation of Co3O4 NPs in roots further led to a significant decrease in root antioxidant enzyme activity and changes in functional gene expression. Co3O4 NPs reduced soybean yield after 140 days, but interestingly, at specific doses, it increased grain nutrients (Fe content increased by 17.38% at 100 mg/kg, soluble protein and vitamin E increased by 14.34% and 16.81% at 10 mg/kg). Target hazard quotient (THQ) assessment results showed that consuming soybean seeds exposed to Co3O4 NPs (≥100 mg/kg) and Co2+ (≥10 mg/kg) would pose potential health risks. Generally, Co3O4 NPs could exist stably in the environment and had lower environmental risks than Co2+. These results help to better understand the environmental behavior and plant effect mechanisms of Co3O4 NPs in soil-plant systems.

Machine Learning Allowed Interpreting Toxicity of a Fe-Doped CuO NM Library Large Data Set─An Environmental In Vivo Case Study.

The wide variation of nanomaterial (NM) characters (size, shape, and properties) and the related impacts on living organisms make it virtually impossible to assess their safety; the need for modeling has been urged for long. We here investigate the custom-designed 1-10% Fe-doped CuO NM library. Effects were assessed using the soil ecotoxicology model Enchytraeus crypticus (Oligochaeta) in the standard 21 days plus its extension (49 days). Results showed that 10%Fe-CuO was the most toxic (21 days reproduction EC50 = 650 mg NM/kg soil) and Fe3O4 NM was the least toxic (no effects up to 3200 mg NM/kg soil). All other NMs caused similar effects to E. crypticus (21 days reproduction EC50 ranging from 875 to 1923 mg NM/kg soil, with overlapping confidence intervals). Aiming to identify the key NM characteristics responsible for the toxicity, machine learning (ML) modeling was used to analyze the large data set [9 NMs, 68 descriptors, 6 concentrations, 2 exposure times (21 and 49 days), 2 endpoints (survival and reproduction)]. ML allowed us to separate experimental related parameters (e.g., zeta potential) from particle-specific descriptors (e.g., force vectors) for the best identification of important descriptors. We observed that concentration-dependent descriptors (environmental parameters, e.g., zeta potential) were the most important under standard test duration (21 day) but not for longer exposure (closer representation of real-world conditions). In the longer exposure (49 days), the particle-specific descriptors were more important than the concentration-dependent parameters. The longer-term exposure showed that the steepness of the concentration-response decreased with an increased Fe content in the NMs. Longer-term exposure should be a requirement in the hazard assessment of NMs in addition to the standard in OECD guidelines for chemicals. The progress toward ML analysis is desirable given its need for such large data sets and significant power to link NM descriptors to effects in animals. This is beyond the current univariate and concentration-response modeling analysis.

Degradation of Isopyrazam in Soil: Kinetics, Microbial Mechanism, and Ecotoxicity of the Transformation Product.

The degradation of isopyrazam in soils was investigated through kinetics, microbial contributions, and transformation products (TPs). Then the acute toxicity of isopyrazam and its TP to Chlorella pyrenoidosa was explored. The half-lives of isopyrazam in cinnamon soil, red soil, and black soil were 82.2, 141.7, and 120.3 days, respectively. A strain (Bacillus sp. A01) isolated from cinnamon soil could degrade 72.9% of isopyrazam at 10 mg/L after 6 days in a Luria-Bertani medium. Six TPs were observed with Bacillus sp. A01, and three of them were found in soil as well. Through the inhibition of cytochrome P450 enzymes, the production of oxidized isopyrazam was blocked. Microbial mediated hydroxylation, epoxidation, and dehydration were the main degradation pathways of isopyrazam. The acute toxicity results showed that the EC50 of 3-(difluoromethyl)-N-(9-(2-hydroxypropan-2-yl)-1,2,3,4-tetrahydro-1,4-methanonaphthalen-6-yl)-1-methyl-1H-pyrazole-4-carboxamide to Chlorella pyrenoidosa was 40 times higher than that of the parent. This work provides new insights for understanding the degradation behavior of isopyrazam in soil.