Sensitive Coatings Based on Molecular-Imprinted Polymers for Triazine Pesticides' Detection.

Triazine pesticide (atrazine and its derivatives) detection sensors have been developed to thoroughly check for the presence of these chemicals and ultimately prevent their exposure to humans. Sensitive coatings were designed by utilizing molecular imprinting technology, which aims to create artificial receptors for the detection of chlorotriazine pesticides with gravimetric transducers. Initially, imprinted polymers were developed, using acrylate and methacrylate monomers containing hydrophilic and hydrophobic side chains, specifically for atrazine, which shares a basic heterocyclic triazine structure with its structural analogs. By adjusting the ratio of the acid to the cross-linker and introducing acrylate ester as a copolymer, optimal non-covalent interactions were achieved with the hydrophobic core of triazine molecules and their amino groups. A maximum sensor response of 546 Hz (frequency shift/layer height equal to 87.36) was observed for a sensitive coating composed of 46% methacrylic acid and 54% ethylene glycol dimethacrylate, with a demonstrated layer height of 250 nm (6.25 kHz). The molecularly imprinted copolymer demonstrated fully reversible sensor responses, not only for atrazine but also for its metabolites, like des-ethyl atrazine, and structural analogs, such as propazine and terbuthylazine. The efficiency of modified molecularly imprinted polymers for targeted analytes was tested by combining them with a universally applicable quartz crystal microbalance transducer. The stable selectivity pattern of the developed sensor provides an excellent basis for a pattern recognition procedure.

The effect of pre-treatments on atrazine removal from source water by microbubble ozonation.

Ozone-based advanced oxidation processes (AOPs) have emerged a promising avenue for water treatment, offering effective removal of micropollutants. Recent research underscores the potential of ozone microbubbles to enhance ozone mass transfer during water treatment, particularly when combined with pre-treatment steps. This study aimed to evaluate the efficacy of three different combined processes (chlorine/KMnO4/PAC pre-treatment followed by ozonation) in removing atrazine, a common micropollutant from natural source water. Results revealed that all combined processes achieved higher atrazine removal rates compared to individual pre-treatment or ozonation methods. Notably, the highest atrazine removal rates were observed under alkaline pH conditions, with treatment outcomes influenced by oxidant dose and pH levels. Among the combined processes, chlorine pre-treatment followed by ozonation emerged as the most effective approach, achieving a removal rate of 59.7% that exceeded the sum of individual treatments. However, this treatment efficacy was affected by water quality parameters, particularly the presence of organic matter and elevated ammonia nitrogen concentration (> 0.5 mg/L). This study highlights the potential for utilizing ozone micro/nanobubbles to enhance ozone mass transfer and offers valuable insights for optimizing the combined application of pre-treatment and ozonation strategies for efficient atrazine removal from natural water sources.

Acid-modified hydrochar for higher biodegradation rate of atrazine in various conditions by Paenarthrobacter sp. KN0901: Higher cell viability and bacterial number.

Microbial remediation is a viable and eco-friendly approach for decontaminating pollution. However, its effectiveness can be limited by the microorganisms' survival and growth in changing environments. Hydrochar materials have been utilized in this study to increase the growth and atrazine degradation capabilities of Paenarthrobacter sp. KN0901, a strain capable of atrazine biodegradation. Acid-modified hydrochars exhibited a higher carbonation rate, specific surface area, and number of defect sites compared to raw hydrochar. Following three days of incubation at 15 °C, the atrazine degradation rate increased from 90.7 % to 98.2 % when utilizing H3PO4-modified hydrochar (PHC). Additionally, the addition of PHC resulted in an increase in both bacterial concentration and cell viability of strain KN0901, by 1.6 and 1.4 times, respectively. Under various conditions, including temperatures of 4 ºC and 35 ºC, as well as pH levels of 5 and 9, and dd·H2O media, PHC exhibited a significant enhancement in atrazine degradation and cell viability of strain KN0901. Furthermore, PHC demonstrated the ability to sustain high proliferation and viability of strain KN0901 over five cycles, indicating its remarkable stability and biocompatibility. This study offers a new perspective on the development and application of bioremediation approaches in restoring atrazine-polluted environments, even under challenging conditions.

Mechanistic insights into sulfadimethoxine degradation via microbially driven Fenton reactions.

Biodegradation, while cost-effective, is hindered by the requirement for specialized microorganisms and co-contaminants. Innovative biological technologies like the microbially driven Fenton reaction, hold promise for enhancing degradation efficiency. However, the intricate biochemical processes and essential steps for effective degradation in such systems have remained unclear. In this study, we harnessed the potential of the microbially driven Fenton reaction by employing Shewanella oneidensis MR-1 (MR-1). Our approach showcased remarkable efficacy in degrading a range of contaminants, including sulfadimethoxine (SDM), 4,4'-dibromodiphenyl ether (BDE-15) and atrazine (ATZ). Using SDM as a model contaminant of emergent contaminants (ECs), we unveiled that biodegradation relied on the generation of hydroxyl radicals (•OH) and involvement of oxidoreductases. Transcriptomic analysis shed light on the pivotal components of extracellular electron transfer (EET) during both anaerobic and aerobic periods. The presence of reactive oxidizing species induced cellular damage and impeded DNA repair, thereby affecting the Mtr pathway of EET. Moreover, the formation of vivianite hindered SDM degradation, underscoring the necessity of maintaining iron ions in the solution to ensure sustainable and efficient degradation. Overall, this study offers valuable insights into microbial technique for ECs degradation, providing a comprehensive understanding of degradation mechanisms during aerobic/anaerobic cycling.

A Tunable Threshold Colorimetric DNA Logic Gate for Intuitive Assessment of Chemical Contaminant Exceedance.

Current molecular logic gates are predominantly focused on the qualitative assessment of target presence, which has certain limitations in scenarios requiring quantitative assessment, such as chemical contaminant monitoring. To bridge this gap, we have developed a novel DNA logic gate featuring a tunable threshold, specifically tailored to the limits of contaminants. At the core of this logic gate is a DNA-gold nanoparticle (AuNP) hybrid film that incorporates aptamer sequences to selectively bind to acetamiprid (ACE) and atrazine (ATR). Upon interaction with these contaminants, the film degrades, releasing AuNPs that, in the presence of Hg2+, catalyze the oxidation of TMB, resulting in a visible blue coloration on test paper. This aptamer-enabled process effectively establishes an OR logic gate, with ACE and ATR as inputs and the appearance of blue color as the output. A key innovation of our system is its tunable input threshold. By adjusting the concentration of Hg2+, we can fine-tune the color mutation points to match the input threshold to predefined limits, such as Maximum Residue Limits (MRLs). This alignment allows semiquantitative assessment of contaminant levels, providing intuitive visual feedback of contaminant exceedance. Validation experiments with spiked samples confirm its accuracy and reliability by closely matching HPLC results. Therefore, our colorimetric DNA logic gate is emerging as a promising tool for easy and semiquantitative monitoring of chemical contaminants across diverse applications.

Buffer-free ozone-ferrate(VI) systems for enhanced oxidation of electron-deficient contaminants: Synergistic enhancement effects, systematic toxicity assessment, and practical applications.

The combination of ozone (O3) and ferrate (Fe(VI)) oxidation technology demonstrates substantial potential for practical applications, though it has been underreported, resulting in gaps in comprehensive activity assessments and thorough exploration of its mechanisms. This study reveals that the previous use of a borate buffer solution obscured certain synergistic reactions between O3 and Fe(VI), causing a reduction of activity by ∼40 % when oxidizing the electron-deficient pollutant atrazine. Consequently, we reassessed the activity and mechanisms using a buffer-salt-free O3/Fe(VI) system. Our findings showed that the hydroxyl radical (·OH) served as the predominant active species, responsible for an impressive 95.9 % of the oxidation activity against electron-deficient pollutants. Additional experiments demonstrated that the rapid production of neglected and really important superoxide radicals (·O2-) could facilitate the decomposition of O3 to generate ·OH and accelerate the reduction of Fe(VI) to Fe(V), reactivating O3 to produce ·OH anew. Intriguingly, as the reaction progressed, the initially depleted Fe(VI) was partially regenerated, stabilizing at over 50 %, highlighting the significant potential of this combined system. Moreover, this combined system could achieve a high mineralization efficiency of 80.4 % in treating actual coking wastewater, complemented by extensive toxicity assessments using Escherichia coli, wheat seeds, and zebrafish embryos, showcasing its robust application potential. This study revisits and amends previous research on the O3/Fe(VI) system, providing new insights into its activity and synergistic mechanisms. Such a combined technology has potential for the treatment of difficult-to-degrade industrial wastewater.

Rational design of waste anode graphite-derived carbon catalyst to activate peroxymonosulfate for atrazine degradation.

As the rapidly growing number of waste lithium-ion batteries (LIBs), the recycling and reutilization of anode graphite is of increasing interest. Converting waste anode graphite into functional materials may be a sensible option. Herein, a series of carbonaceous catalysts (TG) were successfully prepared using spent anode graphite calcined at various temperatures and applied for activating peroxymonosulfate (PMS) to degrade atrazine (ATZ). The catalyst obtained at 800 °C (TG-800) showed the optimum performance for ATZ removal (99.2% in 6 min). Various experimental conditions were explored to achieve the optimum efficiency of the system. In the TG-800/PMS system, free radicals (e.g., SO4·-, HO·), singlet oxygen (1O2), together with a direct electron transfer pathway all participated in ATZ degradation, and the ketonic (CO) group was proved as the leading catalytic site for PMS activation. The potential degradation routes of ATZ have also been presented. According to the toxicity assessment experiments, the toxicity of the intermediate products decreased. The reusability and universal applicability of the TG-800 were also confirmed. This research not only provides an efficient PMS activator for pollutant degradation, but also offers a meaningful reference for the recovery of waste anode graphite to develop environmentally functional materials.

Migration mechanism of atrazine in the simulated lake icing process at different freezing temperatures based on density function theory.

Atrazine causes concern due to its resistant to biodegradation and could be accumulated in aquatic organisms, causing pollution in lakes. This study measured the concentration of atrazine in ice and the water under ice through a simulated icing experiment and calculated the distribution coefficient K to characterize its migration ability in the freezing process. Furthermore, density functional theory (DFT) calculations were employed to expatiate the migration law of atrazine during icing process. According to the results, it could release more energy into the environment when atrazine staying in water phase (-15.077 kcal/mol) than staying in ice phase (-14.388 kcal/mol), therefore it was beneficial for the migration of atrazine from ice to water. This explains that during the freezing process, the concentration of atrazine in the ice was lower than that in the water. Thermodynamic calculations indicated that when the temperature decreases from 268 to 248 K, the internal energy contribution of the compound of atrazine and ice molecule (water cluster) decreases at the same vibrational frequency, resulting in an increase in the free energy difference of the compound from -167.946 to -165.390 kcal/mol. This demonstrated the diminished migratory capacity of atrazine. This study revealed the environmental behavior of atrazine during lake freezing, which was beneficial for the management of atrazine and other pollutants during freezing and environmental protection.

Unveiling carcinogenic pollutant levels in environmental water samples through facile fabrication of gold nanoparticles on sulfur-doped graphitic carbon nitride.

Extensive utilization of pesticides and herbicides to boost agricultural production increased the environmental health risks, which can be mitigate with the aid of highly sensitive detection systems. In this study, an electrochemical sensor for monitoring the carcinogenic pesticides in the environmental samples has been developed based on sulfur-doped graphitic-carbon nitride-gold nanoparticles (SCN-AuNPs) nanohybrid. Thermal polycondensation of melamine with thiourea followed by solvent exfoliation via ultrasonication leads to SCN formation and electroless deposition of AuNPs on SCN leads to SCN-AuNPs nanohybrid synthesis. The chemical composition, S-doping, and the morphology of the nanohybrid were confirmed by various microscopic and spectroscopic tools. The as-synthesized nanohybrid was fabricated with glassy carbon (GC) electrode for determining the carcinogenic hydrazine (HZ) and atrazine (ATZ) in field water samples. The present sensor exhibited superior electrocatalytic activity than GC/SCN and GC/AuNPs electrodes due to the synergism between SCN and AuNPs and the amperometric studies showed the good linear range of detection of 20 nM-0.5 mM and 500 nM-0.5 mM with the limit of detection of 0.22 and 69 nM (S/N = 3) and excellent sensitivity of 1173.5 and 13.96 µA mM-1 cm-2 towards HZ and ATZ, respectively. Ultimately, the present sensor is exploited in environmental samples for monitoring HZ and ATZ and the obtained results are validated with high-performance liquid chromatography (HPLC) technique. The excellent recovery percentage and close agreement with the results of HPLC analysis proved the practicability of the present sensor. In addition, the as-prepared materials were utilized for the photocatalytic degradation of ATZ and the SCN-AuNPs nanohybrid exhibited higher photocatalytic activity with the removal efficiency of 93.6% at 90 min. Finally, the degradation mechanism was investigated and discussed.

The effectiveness and feasibility of ball-milled powdered activated carbon (BPAC) for removal of organic pesticides in conventional drinking water treatment process.

In the conventional drinking water treatment process (CDWTP), powdered activated carbon (PAC) is commonly used for removing organic pesticides, or other organic contaminants. However, the hydraulic retention time (HRT) in CDWTP is insufficient for fulfilling PAC adsorption equilibrium to realize its full capacity. This study examined the adsorption kinetics, adsorption thermal dynamics, and removal efficiency for six organic pesticides using the ball-milled PAC (BPAC) with varying particle sizes in CDWTP. Based on the experiments with the pesticides of atrazine, diazinon, dimethoate, fenitrothion, isoproturon and thiometon, the results indicated that as the particle size reduced from around 38 µm for the commercial PAC to 1 µm for the BPAC, the adsorption rates for hydrophobic pesticides increased up to twentyfold. Diffusional adsorption from the bulk solution to the external PAC surface is the most likely predominant mechanism. This could allow a sufficient pesticides' adsorption within the limited HRT and to achieve a great depth removal of these toxic compounds. However, the addition of BPAC with a diameter of 1 µm was observed to significantly increase residual particles in treated water after the conventional treatment process. With a further systematic evaluation of both adsorption rate and particle penetration, a particle size of around 6 µm BPAC was considered a practical compromise between the adsorption rate and particle penetration for real application. Results from five surface waters of different water quality indicated that, compared to commercial PAC, application of 6 µm BPAC could achieve up to a 75% reduction in adsorbent dosage while maintaining around the same pesticide removal efficiencies. Additionally, thermodynamic analyses suggest that adsorption of these pesticides could be enthalpically or entropically driven depending on the degree of pesticide hydrophobicity.

Fabrication of lignosulfonate-derived porous carbon via pH-tunable self-assembly strategy for efficient atrazine removal.

Herein, a straightforward protocol was developed for the one-pot synthesis of N-doped lignosulfonate-derived carbons (NLDCs) with a tunable porous structure using natural amino acids-templated self-assembly strategy. Specifically, histidine was employed as a template reagent, leading to the preparation of 10-NLDC-21 with remarkable characteristics, including the large specific surface area (SBET = 1844.5 m2/g), pore volume (Vmes = 1.22 cm3/g) and efficient adsorption for atrazine (ATZ) removal. The adsorption behavior of ATZ by NLDCs followed the Langmuir and pseudo-second-order models, suggesting a monolayer chemisorption nature of ATZ adsorption with the maximum adsorption capacity reached up to 265.77 mg/g. Furthermore, NLDCs exhibited excellent environmental adaptability and recycling performance. The robust affinity could be attributed to multi-interactions including pore filling, electrostatic attraction, hydrogen bonding and π-π stacking between the adsorbents and ATZ molecules. This approach offers a practical method for exploring innovative bio-carbon materials for sewage treatment.

Biodegradation of atrazine and nicosulfuron by Streptomyces nigra LM01: Performance, degradative pathway, and possible genes involved.

Microbial herbicide degradation is an efficient bioremediation method. In this study, a strain of Streptomyces nigra, LM01, which efficiently degrades atrazine and nicosulfuron, was isolated from a corn field using a direct isolation method. The degradation effects of the identified strain on two herbicides were investigated and optimized using an artificial neural network. The maximum degradation rates of S. nigra LM01 were 58.09 % and 42.97 % for atrazine and nicosulfuron, respectively. The degradation rate of atrazine in the soil reached 67.94 % when the concentration was 108 CFU/g after 5 d and was less effective than that of nicosulfuron. Whole genome sequencing of strain LM01 helped elucidate the possible degradation pathways of atrazine and nicosulfuron. The protein sequences of strain LM01 were aligned with the sequences of the degraded proteins of the two herbicides by using the National Center for Biotechnology Information platform. The sequence (GE005358, GE001556, GE004212, GE005218, GE004846, GE002487) with the highest query cover was retained and docked with the small-molecule ligands of the herbicides. The results revealed a binding energy of - 6.23 kcal/mol between GE005358 and the atrazine ligand and - 6.66 kcal/mol between GE002487 and the nicosulfuron ligand.

Modulation of Electron Transfer Branches by Atrazine and Triazine Herbicides in Photosynthetic Reaction Centers.

Quinone analogue molecules, functioning as herbicides, bind to the secondary quinone site, QB, in type-II photosynthetic reaction centers, including those from purple bacteria (PbRC). Here, we investigated the impact of herbicide binding on electron transfer branches, using herbicide-bound PbRC crystal structures and employing the linear Poisson-Boltzmann equation. In contrast to urea and phenolic herbicides [Fufezan, C. Biochemistry 2005, 44, 12780-12789], binding of atrazine and triazine did not cause significant changes in the redox-potential (Em) values of the primary quinone (QA) in these crystal structures. However, a slight Em difference at the bacteriopheophytin in the electron transfer inactive branch (HM) was observed between the S(-)- and R(+)-triazine-bound PbRC structures. This discrepancy is linked to variations in the protonation pattern of the tightly coupled Glu-L212 and Glu-H177 pairs, crucial components of the proton uptake pathway in native PbRC. These findings suggest the existence of a QB-mediated link between the electron transfer inactive HM and the proton uptake pathway in PbRCs.

LaCoO3/SBA-15 as a high surface area catalyst to activate peroxymonosulfate for degrading atrazine in water.

An efficient perovskite-based heterogeneous catalyst is highly desired to activate peroxymonosulfate (PMS) for removing organic pollutants in water. A high surface area PMS-activator was fabricated by loading LaCoO3 on SBA-15 to degrade atrazine (ATR) in water. The LaCoO3/SBA-15 depicted better textural properties and higher catalytic activity than LaCoO3. In 6.0 min, atrazine (ATZ) degradation in the selected LaCoO3/SBA-15/PMS system, LaCoO3, adsorption by LaCoO3/SBA-15, sole PMS processes reached approximately 100%, 55.15%, 12.80%, and 16.65 % respectively. Furthermore, 0.04 mg L-1 Co was leached from LaCoO3/SBA-15 during PMS activation by LaCoO3/SBA-15. The LaCoO3/SBA-15 showed stable catalytic activity after reuse. The use of radical scavengers and electron paramagnetic resonance spectroscopy (EPR) demonstrated that ROS such as 1O2, O2•-, •OH, and SO4•- were generated by PMS activated by LaCoO3/SBA-15 owing to redox reactions [Co2+/Co3+, and O2-/O2]. EPR, XPS, ATR-FTIR, EIS, LSV, and chronoamperometric measurements were used to explain the catalytic mechanism for PMS activation. Excellent atrazine degradation was due to high surface area, porous nature, diffusion-friendly structure, and ROS. Our investigation proposes that perovskites with different A and B metals and modified perovskites can be loaded on high surface area materials to activate PMS into ROS.

Design of a multi-electrode dielectric barrier discharge reactor and experimental study on the degradation of atrazine in water.

Atrazine (ATZ) is widely used in agriculture as a triazine herbicide, and its long-term use can cause serious environmental pollution. This paper independently designed a multi-electrode reactor, explored the output power and energy utilization efficiency of the dielectric barrier discharge reactor, and used the dielectric barrier discharge reactor to treat ATZ solution. The results showed that the degradation efficiency of ATZ was 96.39% at 30 min at an initial ATZ concentration of 14 mg/L, an input voltage of 34 kV, an input current of 1.38 mA, an aeration rate of 100 L/h, and a treatment water volume of 150 mL. The degradation of ATZ was significantly increased by the addition of persulfate (PS), Fe2+, and H2O2. After adding radical quenchers (EtOH, p-BQ, and FFA), the degradation efficiency of ATZ decreased, indicating that free radicals (•OH, •O2-, and 1O2) played a key role in the degradation process of ATZ.

Prediction of atrazine degradation in soil based on XGBoost model.

We established the optimal model by using the automatic machine learning method to predict the degradation efficiency of herbicide atrazine in soil, which could be used to assess the residual risk of atrazine in soil. We collected 494 pairs of data from 49 published articles, and selected seven factors as input features, including soil pH, organic matter content, saturated hydraulic conductivity, soil moisture, initial concentration of atrazine, incubation time, and inoculation dose. Using the first-order reaction rate constant of atrazine in soil as the output feature, we established six models to predict the degradation efficiency of atrazine in soil, and conducted comprehensive analysis of model performance through linear regression and related evaluation indicators. The results showed that the XGBoost model had the best performance in predicting the first-order reaction rate constant (k). Based on the prediction model, the feature importance ranking of each factor was in an order of soil moisture > incubation time > pH > organic matter > initial concentration of atrazine > saturated hydraulic conductivity > inoculation dose. We used SHAP to explain the potential relationship between each feature and the degradation ability of atrazine in soil, as well as the relative contribution of each feature. Results of SHAP showed that time had a negative contribution and saturated hydraulic conductivity had a positive contribution. High values of soil moisture, initial concentration of atrazine, pH, inoculation dose and organic matter content were generally distributed on both sides of SHAP=0, indicating their complex contributions to the degradation of atrazine in soil. The XGBoost model method combined with the SHAP method had high accuracy in predicting the performance and interpretability of the k model. By using machine learning method to fully explore the value of historical experimental data and predict the degradation efficiency of atrazine using environmental parameters, it is of great significance to set the threshold for atrazine application, reduce the residual and diffusion risks of atrazine in soil, and ensure the safety of soil environment.

Nitrogen fertiliser-domesticated microbes change the persistence and metabolic profile of atrazine in soil.

Pesticides and fertilisers are frequently used and may co-exist on farmlands. The overfertilisation of soil may have a profound influence on pesticide residues, but the mechanism remains unclear. The effects of chemical fertilisers on the environmental behaviour of atrazine and their underlying mechanisms were investigated. The present outcomes indicated that the degradation of atrazine was inhibited and the half-life was prolonged 6.0 and 7.6 times by urea and compound fertilisers (NPK) at 1.0 mg/g (nitrogen content), respectively. This result, which was confirmed in both sterilised and transfected soils, was attributed to the inhibitory effect of nitrogen fertilisers on soil microorganisms. The abundance of soil bacteria was inhibited by nitrogen fertilisers, and five families of potential atrazine degraders (Micrococcaceae, Rhizobiaceae, Bryobacteraceae, Chitinophagaceae, and Sphingomonadaceae) were strongly and positively (R > 0.8, sig < 0.05) related to the decreased functional genes (atzA and trzN), which inhibited hydroxylation metabolism and ultimately increased the half-life of atrazine. In addition, nitrogen fertilisers decreased the sorption and vertical migration behaviour of atrazine in sandy loam might increase the in-situ residual and ecological risk. Our findings verified the weakened atrazine degradation with nitrogen fertilisers, providing new insights into the potential risks and mechanisms of atrazine in the context of overfertilisation.

Degradation of Atrazine by an Anaerobic Microbial Consortium Enriched from Soil of an Herbicide-Manufacturing Plant.

Atrazine is an important herbicide that has been widely used for weed control in recent decades. However, with the extensive use of atrazine, its residue seriously pollutes the environment. Therefore, the microbial degradation and detoxification of atrazine have received extensive attention. To date, the aerobic degradation pathway of atrazine has been well studied; however, little is known about its anaerobic degradation in the environment. In this study, an anaerobic microbial consortium capable of efficiently degrading atrazine was enriched from soil collected from an herbicide-manufacturing plant. Six metabolites including hydroxyatrazine, deethylatrazine, N-isopropylammelide, deisopropylatrazine, cyanuric acid, and the novel metabolite 4-ethylamino-6-isopropylamino-1,3,5-triazine (EIPAT) were identified, and two putative anaerobic degradation pathways of atrazine were proposed: a hydrolytic dechlorination pathway is similar to that seen in aerobic degradation, and a novel pathway initiated by reductive dechlorination. During enrichment, Denitratisoma, Thiobacillus, Rhodocyclaceae_unclassified, Azospirillum, and Anaerolinea abundances significantly increased, dominating the enriched consortium, indicating that they may be involved in atrazine degradation. These findings provide valuable evidence for elucidating the anaerobic catabolism of atrazine and facilitating anaerobic remediation of residual atrazine pollution.

Occurrence, distribution and ecological risk assessment of herbicide residues in cropland soils from the Mollisols region of Northeast China.

The first systematic and comprehensive investigation of herbicide residues was conducted by identifying their spatial distribution, influencing factors and ecological risk in cropland soils from the Mollisols region covering 109 million hm2 in Northeast China. Fifty-six herbicides were detected with total herbicide concentrations ranging from 1.01 to 1558.13 µg/kg (mean: 227.45). Atrazine, its degradates deethyl atrazine (DEA) and deisopropyl atrazine (DIA), trifluralin and butachlor were the most frequently detected herbicides, while DEA, clomazone, nicosulfuron, fomesafen, and mefenacet exhibited the highest concentrations. Despite being less frequently reported in Chinese soils, fomesafen, nicosulfuron, clomazone, and mefenacet were found widely present. Although most of the compounds posed a minimal or low ecological risk, atrazine, nicosulfuron and DEA exhibited medium to high potential risks. The key factors identified to regulate the fate of herbicides were soil chemical properties, amount of herbicides application, and the crop type. The soybean soils showed highest herbicide residues, while the soil mineral contents likely adsorbed more herbicides. This study provides a valuable large-scale dataset of herbicide residues across the entire Mollisols region of China along with fine-scale characterization of the ecological risks. Mitigation and management measures are needed to reduce the herbicide inputs and residues in the region.

Biodegradation of atrazine with biochar-mediated functional bacterial biofilm: Construction, characterization and mechanisms.

The abuse and residue of herbicides in the black soil area had seriously affected the soil structure, function and crop growth, posing severe threats to agricultural soil environment and public health. Given the limitation of routine microbial remediation, innovative and eco-friendly functional bacterial biofilm which could adapt under adverse conditions was developed on the biochar to investigate its enhanced bioremediation and metabolic characteristics of typical herbicide atrazine. Results revealed that the atrazine degrading strain Acinetobacter lwoffii had competitive advantage in soil indigenous microorganisms and formed dense biofilms on the biochar which was beneficial to cell viability maintenance and aggregations. Metatranscriptomics and RT-qPCR analysis demonstrated that the biochar-mediated biofilm improved the frequency of intercellular communications through quorum sensing and two-component signal regulation systems, and enhanced the atrazine biodegradation efficiency through horizontal gene transfer in co-metabolism mode, providing important scientific basis for the biological remediation of farmland soil non-point source pollution.