The recently recognized adverse environmental and toxic effects of neonicotinoid insecticides (NNIs) on non-target organisms are alarming. A comprehensive design, screening, and regulatory system was developed to generate NNI derivatives and mutant receptors with selective-ecotoxicological effects to overcome such adverse effects. For ligand design, taking ACE-09 derivative as an example, the toxicity on non-target animals (aboveground: bees; underground: earthworms), plant absorption, and soil absorption decreased by 4.80% and 13.7%, 10.0%, and 121%, while the toxicity on target animals (aboveground: aphids; underground: B. odoriphagas), plant metabolism, and soil degradation increased by 70.2% and 51.7%, 5.08%, and 8.28%. For receptor modification, the ability of mutants to absorb ACE-09 derivative decreased by 31.0%, while the ability of mutants to metabolize ACE-09 derivative increased by 28.0% in scenario 2 (mainly plant selectivity); the ability of mutants to degrade ACE-09 derivative increased by 11.6% in scenario 3 (mainly soil selectivity). The above results indicated that the selective-ecotoxicological effects of ligand design and receptor modification were both improved. Additionally, the combined effects of the ACE-09 derivative on plant absorption and metabolic mutants improved by 31.1% and 31.4% in scenario 2, respectively, while the effect on microbial degradation mutant improved by 14.9%, indicating that there was a synergistic effect between ligand design and receptor modification. Finally, based on the interaction between the ACE-09 derivative and mutants, the optimal environmental factors that improved the selectivity of their ecotoxicological effects were determined. For example, alternate application of nitrogen and phosphorus fertilizers effectively reduced the oxidative damage to plants caused by NNI residues. The novel ligand-receptor joint modification method, combined with the regulation of environmental factors under multiple scenarios, can biochemically address the ecotoxicological concern and highlight the harmful effects of pesticides on the environment and non-target organisms.

The heavy-metal adsorbent ε-MnO₂ was produced through a simple, one-step oxidation-reduction reaction at three different synthesis temperatures (25 °C, 50 °C and 75 °C) and their morphology and chemical-physical properties were compared. Of the three materials, MnO₂-25 had the largest specific surface area and the highest surface hydroxyl concentration. Its optimal performance was demonstrated by batch adsorption experiments with Pb²⁺, Cd²⁺ and Cu²⁺. Of the three metals, Pb²⁺ was adsorbed best (339.15 mg/g), followed by Cd²⁺ (107.50 mg/g) and Cu²⁺ (86.30 mg/g). When all three metals were present, Pb²⁺ was still absorbed best but now more Cu²⁺ was adsorbed than Cd²⁺. In order to explore the mechanism for the inconsistent adsorption order of Cd²⁺ and Cu²⁺ in single and competitive adsorption, we combined experimental data with density functional theory (DFT) calculations to elucidate the distinct adsorption nature of MnO₂-25 towards these three metals. This revealed that the adsorption affinity of the (100) facet was superior to (001), and since the surface complexes were also more stable on (100), this facet was most likely determining the adsorption order for the single metals. When the metals were present in combination, Pb²⁺ preferentially occupied the active adsorption sites of (100), forcing Cu²⁺ to be adsorbed on the (001) facet where Cd²⁺ was only poorly bound. Thus, the adsorption behavior was affected by MnO₂-25 surface chemistry at a molecular scale. This study provides an in-depth understanding of the adsorption mechanisms of the heavy metals on this adsorbent and offers theoretical guidance for production of adsorbent with improved removal efficiency.

The massive generation of medical waste (MW) results in a series of environmental, social, and ecological problems. Pyrolysis is one such approach that has attracted more attention because of the production of value-added products with lesser environmental risk. In this study, the activated biochar (ABC600) was obtained from MW pyrolysis and activated with KOH. The adsorption mechanism of activated biochar on cationic (methylene blue) and anionic (reactive yellow) dyes were studied. The physicochemical characterization of biochar showed that increasing pyrolysis temperature and KOH activation resulted in increased surface area, a rough surface with a clear porous structure, and sufficient functional groups. MB and RYD-145 adsorption on ABC600 was more consistent with Langmuir isotherm (R² ≥ 0.996) and pseudo-second-order kinetics (R² ≥ 0.998), indicating chemisorption with monolayer characteristics. The Langmuir model fitting demonstrated that MB and RYD-145 had maximum uptake capacities of 922.2 and 343.4 mg⋅g⁻¹. The thermodynamics study of both dyes showed a positive change in enthalpy (ΔH°) and entropy (ΔS°), revealing the endothermic adsorption behavior and randomness in dye molecule arrangement on activated-biochar/solution surface. The activated biochar has excellent adsorption potential for cationic and anionic dyes; hence, it can be considered an economical and efficient adsorbent.

To better evaluate the potential risks of aquatic polycyclic aromatic compounds (PACs), multiple approaches have been implemented in this study to assess the human health and ecological risks of parent, nitrated and oxygenated polycyclic aromatic hydrocarbons (PAHs, NPAHs and OPAHs) in the surface water of Jialing and Yangtze Rivers in downtown Chongqing in southwestern China. The concentrations of ∑PAHs (334 ± 125 ng L⁻¹) were much higher than those of ∑OPAHs (20.2 ± 7.49 ng L⁻¹) in the two rivers, while NPAHs were barely detected. Concentrations of detected PACs were higher in wet season than dry season, probably resulted from the elevated particle input due to heavy rainfall in wet season. Concentrations of PAHs were higher in the particulate phase than dissolved phase, while OPAHs levels showed a reverse pattern. The partition coefficients (Kₚ) of PACs in the water-SPM (suspended particulate matter) system were mainly affected by SPM concentrations and octanol/water partition coefficients of specific PACs. Human health risks calculated from non-probabilistic risk assessment model and probabilistic risk assessment model based on Monte Carlo simulation showed similar data pattern with slight difference in absolute values. Both models revealed potential or even severe human health risks contributed mainly by dermal exposure to aquatic PACs in this study. Furthermore, these models also manifested that infant stage was highly sensitive for PAC exposure. Sensitivity analysis indicated that health risk results was most sensitive to Benzo[a]pyrene equivalent toxic concentration (BaPₑq), followed by showering time and daily water intake volume. Levels of ecological risks and contributions of individual PACs differed from models based on different quality values. The adequacy of toxicity data was crucial for the reliability of ecological risk assessment.

Globally distributed karstic soils are characterized by the high accumulation of heavy metal(loid)s, such as Cd. Biogeochemistries and transferability of metal(loid)s in such soils are notably different from that in soils of anthropogenic pollution as evidenced by increasing studies about rice and maize. To solve the question about metal(loid) background and transferability in the system of karstic soils and crops with underground fruits, we designedly collected 246 paired soil–peanut seed samples in a world-famous karstic region in Southwestern China covering an area of 98,700 km². The concentrations of eight regulatory metal(loid)s (Cd, As, Cr, Cu, Hg, Ni, Pb, and Zn) in soil samples exceeded current standards to different degrees, demonstrating a typical high background. However, the transferability of metal(loid)s from soils to peanut seeds is quite low, resulting in a low exceedance rate of metal(loid)s (Cd, 12.2% and Pb, 1.2%) in seeds (“seed metal(loid)s”), in accordance with the results that metal(loid)s in soils mostly distributed in the inert/residual fractions. Based on the distinct response characteristics of peanut seed metal(loid)s to soil status from rice/maize grain metals, a model was further developed for effectively predicting the concentration of Cd in peanut seeds. Collectively, this study provides a basis for the assessment of soil environmental quality and safety zoning of upland field in karst areas.

To evaluate the influence of surface coatings on nano-fertilizers uptake and their phytotoxicity to crops and its health risk to Chinese adults, trisodium citrate (TC) and polyethylene glycol (PEG) coatings were prepared on the surface of copper oxide nanoparticles (CuO NPs), respectively, with 100 and 500 mg/L of bare CuO NPs, TC-CuO NPs, and PEG-CuO NPs were exposed to soil-grown Ipomoea aquatica Forssk. Combined bio-transmission electron microscopy and micro-CT observed cellular migration of coated CuO NPs in symplastic and apoplastic pathways, as well as nanoparticles transported through vascular tissues to the above-ground parts. Since TC-CuO NPs had less inhibition on vascular phylogeny of I. aquatica roots which was determined by RT-qPCR, their migration in plants was more efficient, thus exhibiting greater phytotoxicity to shoots. Meanwhile, coatings significantly reduced the phytotoxicity of CuO NPs by stimulating plant antioxidant defense. The risk of CuO nano-fertilizers on human dietary safety was evaluated, the HQ > 1 in the 500 mg/L CuO NPs treatment indicated a potential health risk to Chinese adults, which was reduced by the coatings. This work explored for the first time the mechanism of coating effects on nanoparticles migration efficiency and phytotoxicity at the molecular level and demonstrated that the migration of nanoparticles between tissues could have an impact on phytotoxicity. It implied that coating can be tailored to target nanoparticles to specific regions of the plant. In addition, this study highlights the potential health risks associated with the consumption of I. aquatica fertilized with CuO NPs and provides valuable insights into the environmental applications of nano-fertilizers.

Although biochar supports were widely adopted to fabricate the biochar (BC) supported layered double hydroxides (LDHs) composites (LDH-BC) for efficient environmental remediation, few studies focus on the important role of biochar support in alleviating the stacking of LDHs and enhancing LDH-BC's performance. Through the analysis of the material structure-performance relationship, the “support effect” of fine biochar prepared by ball milling was carefully explored. Compared with the original LDHs on LDH-BC, the LDHs on ball milled biochar (LDH-BMBC) had smaller particle size (from 1123 nm to 586 nm), crystallite size (from 20.5 nm to 6.56 nm), more abundant O-containing functional groups, and larger surface area (370 m² g⁻¹) and porous structure. The Langmuir model revealed that the maximum theoretical phosphate adsorption capacity of LDH-BMBC (56.2 mg P g⁻¹) was significantly higher than that of LDH-BC (27.6 mg P g⁻¹). The leaching experiment proved that the addition of LDH-BMBC in calcareous soil could significantly reduce the release of soil total phosphate (46.1%) and molybdate reactive phosphate (40.4%), even though pristine BC and BMBC significantly enhanced the soil phosphate leaching. This work fabricated high-performance and eco-friendly LDH-BMBC for phosphate adsorption in solution and phosphate retention in soil and also provide valuable insights into fine biochar support effect on LDHs exfoliation, extending the practical use of the engineered ball milled biochars in environment remediation.

The presence of microplastics in oceans and coastlines has increased during recent years due anthropogenic activities and represents a serious environmental problem. The establishment and assembly of microbial communities in these microplastics, specifically located near aquaculture activities, is not well understood. In this study, we analyzed unique and core members of bacterial communities attached to microplastics collected from three coastal environments of the South Pacific, which represent low, medium and high anthropogenic activity derived from the aquaculture industry. Microplastics were analyzed with Fourier-transform infrared spectroscopy, scanning electron microscopy, and next-generation sequencing to assess the prevailing microplastics types, and to characterize microbial communities attached to them. We identified four main types of microplastics (polypropylene, polyethylene, nylon and polystyrene) and 3102 Operational Taxonomic Units (OTUs) at the sampled sites, which were dominated by the phylum Cyanobacteria, Bacteroidetes and Proteobacteria (mainly Alpha and Gammaproteobacteria). Similarity index analysis showed that bacterial communities in microplastics differed from those found in the surrounding seawaters, and also that they varied among locations, suggesting a role of the environment and level of anthropogenic activities on the plastisphere taxa. Despite this difference, 222 bacterial OTUs were shared among the three sites representing between 34 and 51% of OTUs of each sampled site, and thus constituted a core microbiome of microplastics. Comparison of the core microbiome with bacterial communities of the surrounding seawater suggested that the plastisphere constituted a selective habitat for diverse microbial communities. Computational predictions also provided evidence of significantly enriched functions in the core microbiome. Co-occurrence networks revealed that putative ecological interactions among microplastics OTUs was dominated by positive correlations. To the best of our knowledge, this is the first study that evaluated the composition of microbial communities found in microplastics from the Patagonia region of the Southern Pacific Ocean.

In recent decades, nanotechnology has rapidly developed. Therefore, there is growing concern about the potential environmental risks of nanoparticles (NPs). Caenorhabditis elegans (C. elegans) has been used as a powerful tool for studying the potential ecotoxicological impacts of nanomaterials from the whole animal level to single cell level, especially in the area of reproduction. In this review, we discuss the reproductive toxicity of common nanomaterials in C. elegans, such as metal-based nanomaterial (silver nanoparticles (NPs), gold NPs, zinc oxide NPs, copper oxide NPs), carbon-based nanomaterial (graphene oxide, multi-walled carbon nanotubes, fullerene nanoparticles), polymeric NPs, silica NPs, quantum dots, and the potential mechanisms involved. This insights into the toxic effects of existing nanomaterials on the human reproductive system. In addition, we summarize how the physicochemical properties (e.g., size, charge, surface modification, shape) of nanomaterials influence their reproductive toxicity. Overall, using C. elegans as a platform to develop rapid detection techniques and prediction methods for nanomaterial reproductive toxicity is expected to reduce the gap between biosafety evaluation of nanomaterials and their application.

In the current investigation, we presented the success of the modified hydrothermal method for synthesizing the iron-oxide nanoparticles (Fe₂O₃-NPs) efficiently. These NPs were further characterized by using different techniques such as X-ray diffraction (XRD), scanning electron microscope (SEM) micrographs, energy-dispersive X-ray spectroscopy (EDAX)/Mapping pattern, Raman Spectroscopy Pattern, ultra violet (UV) and Photoluminescence (PL). All these analyses revealed highly pure nature of Fe₂O₃-NPs with no internal defects, and suggested its application for plant growth improvement. Therefore, we further investigated the separate as well as combined effects of the Fe₂O₃-NPs and citric acid (CA) in the alleviation of arsenic (As) toxicity in the soybean (Glycine max L.), by evaluating the different plant growth and metabolic attributes. Results of our study revealed that As-induced growth inhibition, reduction of photosynthesis, water use efficiency (WUE), and reactive oxygen species (ROS) accumulation whereas application of the Fe₂O₃-NPs and CA significantly reversed all these adverse effects in soybean plants. Moreover, the As-stress induced malondialdehyde (MDA) and hydrogen peroxide (H₂O₂) production were partially reversed by the Fe₂O₃-NPs and CA in the As-stressed plants by 16% and 10% (MDA) and 29% and 12% (H₂O₂). This might have resulted due to the Fe₂O₃-NPs and CA induced activities of the antioxidant defense in plants. Overall, the Fe₂O₃-NPs and CA supplementation separately and in combination positively regulated the As tolerance in soybean; however, the effect of the combined application on the As tolerance was more profound relative to the individual application. These results suggested the synergetic effect of the Fe₂O₃-NPs and CA on the As-tolerance in soybean. However, in-depth mechanism underlying the defense crosstalk between the Fe₂O₃-NPs and CA needs to be further explored.