Recent advances and prospects of neonicotinoid insecticides removal from aquatic environments using biochar: Adsorption and degradation mechanisms.

In recent years, neonicotinoid insecticides (NNIs), representing a new era of pest control, have increasingly replaced traditional classes such as organophosphorus compounds, carbamates, and pyrethroids due to their precise targeting and broad-spectrum efficacy. However, the high water solubility of NNIs has led to their pervasion in aquatic ecosystems, raising concerns about potential risks to non-target organisms and human health. Therefore, there is an urgent need for research on remediating NNI contamination in aquatic environments. This study demonstrates that biochar, characterized by its extensive surface area, intricate pore structure, and high degree of aromaticity holds significant promise for removing NNIs from water. The highest reported adsorption capacity of biochar for NNIs stands at 738.0 mg·g-1 with degradation efficiencies reaching up to 100.0 %. This review unveils that the interaction mechanisms between biochar and NNIs primarily involve π-π interactions, electrostatic interactions, pore filling, and hydrogen bonding. Additionally, biochar facilitates various degradation pathways including Fenton reactions, photocatalytic, persulfate oxidations, and biodegradation predominantly through radical (such as SO4-, OH, and O2-) as well as non-radical (such as 1O2 and electrons transfer) processes. This study emphasizes the dynamics of interaction between biochar surfaces and NNIs during adsorption and degradation aiming to elucidate mechanistic pathways involved as well as assess the overall efficacy of biochar in NNI removal. By comparing the identification of degradation products and degradation pathways, the necessity of advanced oxidation process is confirmed. This review highlights the significance of harnessing biochar's potential for mitigating NNI pollution through future application-oriented research and development endeavors, while simultaneously ensuring environmental integrity and promoting sustainable practices.

Remediation of polycyclic aromatic hydrocarbons polluted soil by biochar loaded humic acid activating persulfate: performance, process and mechanisms.

The remediation for polycyclic aromatic hydrocarbons contaminated soil with cost-effective method has received significant public concern, a composite material, therefore, been fabricated by loading humic acid into biochar in this study to activate persulfate for naphthalene, pyrene and benzo(a)pyrene remediation. Experimental results proved the hypothesis that biochar loaded humic acid combined both advantages of individual materials in polycyclic aromatic hydrocarbons adsorption and persulfate activation, achieved synergistic performance in naphthalene, pyrene and benzo(a)pyrene removal from aqueous solution with efficiency reached at 98.2%, 99.3% and 90.1%, respectively. In addition, degradation played a crucial role in polycyclic aromatic hydrocarbons remediation, converting polycyclic aromatic hydrocarbons into less toxic intermediates through radicals of ·SO4-, ·OH, ·O2-, and 1O2 generated from persulfate activation process. Despite pH fluctuation and interfering ions inhibited remediation efficiency in some extent, the excellent performances of composite material in two field soil samples (76.7% and 91.9%) highlighted its potential in large-scale remediation.

Effect of soil organic matter-mediated electron transfer on heavy metal remediation: Current status and perspectives.

Soil contamination by heavy metals poses major risks to human health and the environment. Given the current status of heavy metal pollution, many remediation techniques have been tested at laboratory and contaminated sites. The effects of soil organic matter-mediated electron transfer on heavy metal remediation have not been adequately studied, and the key mechanisms underlying this process have not yet been elucidated. In this review, microbial extracellular electron transfer pathways, organic matter electron transfer for heavy metal reduction, and the factors affecting these processes were discussed to enhance our understanding of heavy metal pollution. It was found that microbial extracellular electrons delivered by electron shuttles have the longest distance among the three electron transfer pathways, and the application of exogenous electron shuttles lays the foundation for efficient and persistent remediation of heavy metals. The organic matter-mediated electron transfer process, wherein organic matter acts as an electron shuttle, promotes the conversion of high valence state metal ions, such as Cr(VI), Hg(II), and U(VI), into less toxic and morphologically stable forms, which inhibits their mobility and bioavailability. Soil type, organic matter structural and content, heavy metal concentrations, and environmental factors (e.g., pH, redox potential, oxygen conditions, and temperature) all influence organic matter-mediated electron transfer processes and bioremediation of heavy metals. Organic matter can more effectively mediate electron transfer for heavy metal remediation under anaerobic conditions, as well as when the heavy metal content is low and the redox potential is suitable under fluvo-aquic/paddy soil conditions. Organic matter with high aromaticity, quinone groups, and phenol groups has a stronger electron transfer ability. This review provides new insights into the control and management of soil contamination and heavy metal remediation technologies.

Electrochemical trifluoroalkylation/annulation for the synthesis of CF3-functionalized tetrahydroquinolines and dihydroquinolinones.

Tuning the electronic structure of protecting groups on the nitrogen atom of substrates has emerged as an effective strategy to achieve the tandem trifluoromethylation/C(sp2)-H annulation using Langlois' reagent as the CF3 source for the electrochemical synthesis of functionalized tetrahydroquinolines and dihydroquinolinones.

Immobilized sulfate reducing bacteria (SRB) enhanced passivation performance of biochar for Zn.

The low survival rate in harsh environments has been hindering the transformation of microbial remediation technology for heavy metal-contaminated soil from laboratory to field application. Therefore, biochar was selected as the carrier in this study to immobilize the heavy metal tolerant sulfate-reducing bacteria of SRB14-2-3 for the passivation of Zn-contaminated soil. The results showed that the immobilized bacteria of IBWS14-2-3 exhibited the highest passivation performance, as the total content of bioavailable Zn fractions (exchangeable + carbonates) in soil with initial Zn concentration of 350, 750 and 1500 mg·kg-1 decreased by almost 34.2 %, 30.0 % and 22.2 % compared to the control group, respectively. In addition, the introducing of SRB14-2-3 into biochar has successfully alleviated the possible adverse effects on soil caused by the application of large amounts of biochar, while the protection of biochar against immobilized bacteria significantly improved the reproduction of SRB14-2-3, since the number of SRB14-2-3 increased by 82,278, 42 and 5 times in three different level contaminated soil. Furthermore, the new passivation mechanism for heavy metals brought by SRB14-2-3 is expected to make up for the deficiency of biochar in long-term application. And more attention should be paid on the performance of immobilized bacteria under field practical application in the future research.

Effect of combined aging treatment on biochar adsorption and speciation distribution for Cd(II).

As a passivation material for heavy metals in-situ remediation, biochar (BC) has often been expected to maintain long-term adsorption performance for target pollutants. There is still lack of consensus about the impact of aging processes on biochar properties, particularly with respect to its long-term sorption performance. In this study, the changes to immobilization mechanisms as well as the speciation distribution of Cd(II) triggered by combined aging simulation (dry-wet, freeze-thaw cycle and oxidation treatment) on BC prepared under three levels of pyrolysis temperatures (300, 500 and 700 °C) were investigated. The results showed significant inhibition of aging on adsorption performance with the adsorptive capacity of BC300, BC500 and BC700 for Cd(II) decreased by 31.12 %, 50.63 % and 14.94 %, respectively. However, sequential extraction results indicated little influence of the aging process on the relative fractionation of Cd(II) speciation. The distribution of readily bioavailable, potentially bioavailable and non-bioavailable fractions of Cd(II) on BC showed only minimal changes post-aging. Overall, there was less Cd(II) sorption following aging, but the fractional availability (in relative terms) remained the same. Compared with 300 and 700 °C, the biochar prepared under 500 °C accounted the highest fraction of non-bioavailable Cd(II) (67.23 % of BC500, 59.17 % of Aged-500), and thus showed most promising for Cd(II) immobilization. This study has important practical significance for the long-term application of biochar in real environment.

A Novel Adsorbent of Attapulgite & Carbon Composites Derived from Spent Bleaching Earth for Synergistic Removal of Copper and Tetracycline in Water.

Simultaneously eliminating tetracycline (TC) and copper (Cu-II) from wastewater was investigated by applying a novel adsorbent fabricated by transforming spent bleaching earth (SBE) into attapulgite & carbon composites (A&Cs). Pyrolysis temperature for A&Cs preparation exhibited a positive effect on Cu(II) adsorption, while the AC500 possessed the greatest performance for TC remediation. Interestingly, a synergistic effect instead of competitive adsorption occurred between Cu(II) and TC under the combined binary system, as both TC and Cu(II) adsorption amount on A&C500 increased more than that in the single system, which could be mainly attributed to the bridge actions between the TC and Cu(II). In addition, hydrogen bonding, á´¨-á´¨ EDA interaction, pore-filling and complexation exerted significant roles in the adsorption process of TC and Cu(II). In general, this study offered a new perspective on the regeneration of livestock and poultry industry wastewater polluted with antibiotics and heavy metals.

A review of spatiotemporal patterns of neonicotinoid insecticides in water, sediment, and soil across China.

Neonicotinoid insecticides (NNIs) have been widely used to control insect pests, while their environmental residues and associated hazardous impacts on human and ecosystem health have attracted increasing attention worldwide. In this study, we examined the current levels and associated spatial and temporal patterns of NNIs in multiple environmental media across China. Concentrations of NNIs in surface water, sediment, and soil were in the range of 9.94-755 ng·L-1, 0.07-8.30 ng·g-1 DW, and 0.009-356 ng·g-1 DW, respectively. The high levels of NNIs in surface water, such as in Yangtze River (755 ng·L-1), North River (539 ng·L-1), Nandu River (519 ng·L-1), and Minjiang River (514 ng·L-1), were dominated by imidacloprid, thiamethoxam, and acetamiprid due to their extensive use. The levels of NNIs in sediments were relatively low, and the highest concentration (8.30 ng·g-1 DW) was observed in Dongguan ditch. Sediment-water exchange calculated from fugacity fraction indicated that NNIs in sediment can be released back into the water due to their high solubility and low KOW. Soils from agricultural zones contained the largest residual NNIs, with imidacloprid concentrations in cultivated soil reaching 119 ng·g-1 DW. The calculated leaching potential showed that clothianidin has the highest migration potential to deep soil or groundwater. The monitored data of NNIs presented a decreasing trend from 2016 to 2018, which might be caused by the implementation of relevant control policies for NNI applications. The high levels of NNIs mainly occurred in southern China due to frequent agricultural activities and warm and humid meteorological conditions. The results from this study improve our understanding of the pollution levels and environmental behavior of NNIs in different environmental media across China and provide new knowledge that is needed for making future control policies for NNIs production and application.

Effects of pyrolysis temperature and aging treatment on the adsorption of Cd2+ and Zn2+ by coffee grounds biochar.

As an in-situ immobilization material for heavy metals, biochar can exist in the environment for thousands of years, while whether the natural aging would affect its heavy metals adsorption performance still remains unclear. Therefore, the coffee grounds biochar (CGB) was prepared under different pyrolysis temperatures (300, 500 and 700 °C) in this study, and the simulated artificial aging treatment was carried out to investigate the effects of pyrolysis temperature and aging treatment on Cd2+ and Zn2+ (both separate and combined conditions) adsorption performance of CGB. The result revealed that Fresh-CGB adsorption performance increased with increasing pyrolysis temperature, while the relationship was not so clear with Aged-CGB where adsorption performance peaked at medium pyrolysis temperature (500 °C) but reduced again as pyrolysis temperature increased to 700 °C. The changes of Aged-CGB adsorption performance for Cd2+ and Zn2+ represented the long-term performance of naturally aging biochar in environment, and a mid-range pyrolysis temperature would seem most appropriate for long-term application of biochar. The X-ray Diffraction (XRD) result revealed that the degree of graphitization of CGB increased with increasing pyrolysis temperature, which represents a stronger environmental stability as the weight loss of CGB300, CGB500 and CGB700 after aging treatment was 2.38%, 0.66%, and 0%, respectively. The EDS and FTIR results suggested that ion-exchange and complexation between CGB/Aged-CGB with Cd2+/Zn2+ played a dominant role in adsorption processes. In addition, the selectivity for Cd2+ was significantly improved after the aging treatment. This is desirable given the stronger toxicity of Cd2+ relative to Zn2+. In general, this study provides new insights into the practical application of biochar from the perspective of long-term effects.

Occurrence, variations, and risk assessment of neonicotinoid insecticides in Harbin section of the Songhua River, northeast China.

Neonicotinoid insecticides (NNIs) have been intensively used and exploited, resulting in their presence and accumulation in multiple environmental media. We herein investigated the current levels of eight major NNIs in the Harbin section of the Songhua River in northeast China, providing the first systematic report on NNIs in this region. At least four NNIs in water and three in sediment were detected, with total concentrations ranging from 30.8 to 135 ng L-1 and from 0.61 to 14.7 ng g-1 dw, respectively. Larger spatial variations in surface water NNIs concentrations were observed in tributary than mainstream (p < 0.05) due to the intensive human activities (e.g., horticulture, urban landscaping, and household pet flea control) and the discharge of wastewater from many treatment plants. There was a significant positive correlation (p < 0.05) between the concentrations of residual imidacloprid (IMI), clothianidin (CLO), and Σ4NNIs in the sediment and total organic carbon (TOC). Due to its high solubility and low octanol-water partition coefficient (K ow), the sediment-water exchange behavior shows that NNIs in sediments can re-enter into the water body. Human exposure risk was assessed using the relative potency factor (RPF), which showed that infants have the highest exposure risk (estimated daily intake (ΣIMIeq EDI): 31.9 ng kg-1 bw·d-1). The concentration thresholds of NNIs for aquatic organisms in the Harbin section of the Songhua River were determined using the species sensitivity distribution (SSD) approach, resulting in a value of 355 ng L-1 for acute hazardous concentration for 5% of species (HC5) and 165 ng L-1 for chronic HC5. Aquatic organisms at low trophic levels were more vulnerable to potential harm from NNIs.