Thiamethoxam Research Articles

The partitioning and distribution of neonicotinoid insecticides in human blood

The burden of neonicotinoid insecticides (neonics) in humans has attracted widespread attention in recent years due to the potential adverse effects. Nonetheless, information on the partitioning behavior and distribution in human blood is still limited. Herein, we obtained 115 adult whole blood and plasma specimens for analysis of eight neonics to better understand neonics’ partitioning and distribution in human blood. At least one neonic was detected in 49.6% of the red blood cells and 55.7% of the plasma. In red blood cells, the highest detection rate and concentration was thiamethoxam (THI) with 19.1% and 3832 ng/L, respectively. Imidacloprid had the highest detection rate with 26.1% in the plasma. The mass fraction (Fp) of neonics detected indicates that thiacloprid, imidacloprid, and dinotefuran are mostly resided in plasma upon entering into human blood, while thiamethoxam is mostly present in red blood cells. The distribution of clothianidin and acetamiprid between plasma and red blood cells is similar. The mass fraction (Fp) values for THI were significantly different compared to other neonics, and the effect of age and gender on THI partitioning concluded that there may not be significant variability in the distribution of THI in the sampled population. Overall, this study was the first to investigate neonics residuals in red blood cells and provided fundamental information on the partitioning and distribution of neonics in human blood.

Protective effect of vitamin C against thiamethoxam-induced toxicity in male rats.

Thiamethoxam (THM) is a neonicotinoid insecticide used to control different insect pests on fruits, vegetables, and field crops. The misuse and continuous exposure to THM cause many harmful effects on health and the reproductive system. This work aims to investigate the efficiency of vitamin C (vit C) in reducing or eliminating the harmful effects of THM on the testes, liver, and kidney of male rats. Forty-eight sexually mature male Wister albino rats (weight: 170-190 g; age: 10-11 weeks) were randomly allocated into six groups (8 males/group). The control group was orally given distilled water, vit C group was orally treated with 200 mg/kg b.wt of vit C, group 1/10 of THM LD50 orally treated with 156.3 mg/kg b.wt of THM, group 1/20 of THM LD50 orally treated with 78.15 mg/kg b.wt of THM, group 1/10 of THM LD50 + vit C orally treated with 156.3 mg/kg b.wt of THM + 200 mg/kg b.wt of vit C, and group 1/20 of THM LD50 + vit C orally treated with 78.15 mg/kg b.wt of THM + 200 mg/kg b.wt of vit C. All groups were treated for five days per week for a whole period of 58 days. Blood samples were collected at the end of the experiment, and serum was extracted for liver and kidney functions and antioxidant measurements. Reproductive organs (testis, epididymis, and seminal vesicles) were collected and weighed at the end of the experiment. The results showed that groups exposed to 1/10 and 1/20 of THM LD50 significantly (p < 0.05) decreased the body weight, the reproductive organ weights (testis, epididymis, and seminal vesicles), spermatid count, sperm (count and motility), and testosterone concentration with an increase in abnormalities. In addition, the groups exposed to THM showed a decrease in protein concentration, albumin, and globulin, and caused an increase in glucose concentration. The activities of alkaline phosphatase (ALP), alanine transaminase (ALT), aspartate transaminase (AST), creatinine, urea, and malondialdehyde (MDA) were increased while caused decrease in total antioxidant capacity (TAC) due to exposure to THM. The co-administration of vit C with HM modulated the harmful effects of the insecticide on testicular, liver, and kidney parameters, which confirmed in histopathological examination of testis. Groups orally treated with vit C showed a significant increase in spermatogenesis, spermatid numbers, and the weight of seminal vesicles. This study showed the importance of vit C in reducing toxic effects from exposure to THM. Accordingly, the intake of vit C by individuals who regularly handle this insecticide will be beneficial in reducing the adverse effects that may occur in the liver and kidney.

What does not kill it makes it stronger! The tolerance of the F1 larvae of Chironomus xanthus to a neonicotinoid insecticide formulation

Thiamethoxam (TMX) is a systemic neonicotinoid that acts as a partial agonist of the nicotinic acetylcholine receptors (nAChRs). However, target species have shown resistance to formulations based on such neonicotinoids, which can also be expected for non-target insects. This research aimed to study the effects of a formulation based on TMX [Cruiser® 350 FS (CRZ)] on the life traits of Chironomus xanthus filial generation (F1) and compare it with the parental generation (P). Environmentally relevant concentrations of CRZ significantly decreased larvae growth P generation , also slowing and decreasing their emergence. Larvae of the F1 generation were less sensitive than their parents, suggesting that the progeny were able to thrive and perform basic physiological functions better than the parental generation. Our results highlight that insect resistance to neonicotinoids may be associated with the better performance of the filial generation, which is related to the change in affinities of the active ingredient for the sub-units constituting the nAChRs subtypes of F1 organisms, inherited from P organisms that were able to survive and reproduce. Moreover, further studies using biochemical and omics tools should be performed to disentangle the specific changes occurring at the nAChRs throughout insect development.

Eco(toxicological) Assessment of the Neonicotinoid Formulation Actara® Using Planarian Girardia tigrina as Model Organism

Neonicotinoid pesticides are one of the most commercialized groups worldwide. Their application in agriculture aims to control pests through a systemic mode of action which is not specific to target species. Our study aimed to evaluate the effects of the insecticide Actara® [active ingredient thiamethoxam (TMX)] on a non-target species, Girardia tigrina. Therefore, acute and sublethal endpoints, such as mortality, feeding activity, locomotion and behavioral biomarkers were assessed. Actara® exerted low toxicity towards the planarian Girardia tigrina, showing a 96 h LC50 value of 77.6 mg TMX·L−1 (95% C.I: 74.1–81.2 mg TMX·L−1; R2 = 0.85). At the sublethal level, Actara® exerted no effect on regeneration of photoreceptors and auricles of planarians after 24 and 48 h post-exposure (NOEC &gt; 7.8 mg TMX·L−1). The feeding rate of planarians was significantly increased by Actara®, but only at the highest tested concentration (LOEC = 7.8 mg TMX·L−1). Planarians showed to be less sensitive to the active ingredient TMX compared to other freshwater species. This might be explained by the presence of a high proportion of sub-types of acetylcholine receptors in planarians, exhibiting low binding affinity sites for TMX, an acetylcholine partial agonist. The comparison between effects induced by Actara® with the ones caused by other formulations, in planarians, might support our understanding of how other unknown ingredients can modify the uptake, and bioavailability of such substances, as well as the detoxification capacity of planarians, all of which influences toxicity.

A Time-course Transcriptional Kinetics of Genes in Behavior, Cortisol Synthesis and Neurodevelopment in Zebrafish Larvae Exposed to Imidacloprid and Thiamethoxam.

Agricultural use of neonicotinoid insecticides, neuroactive nitroguanidine compounds, has been detected everywhere in the global, posing significant hazard to nontarget organisms. This work studied the developmental neurotoxicity of zebrafish larvae exposed to imidacloprid (IMI) and thiamethoxam (THM), ranging from 0.05µg L- 1 to 50µg L- 1 for 35 days. Transcriptions of genes belonging to the behavior, neurodevelopment and cortisol synthesis in zebrafish larvae were monitored. The qPCR data demonstrated that with exposure time increased, the transcription of behavior related genes was down-regulated in both IMI and THM groups, such as macf1, cdh6 and syt10. Additionally, IMI and THM significantly up-regulated the transcriptions of actha, and down-regulated il1rapl1b and pi4k2a at 35 dpf. Importantly, IMI markedly enhanced the transcripiton of gfap, shha, nkx2.2a and nestin in a time dependent manner. This work provided the foundation for understanding zebrafish larvae's neurotoxicity induced by IMI and THM.

Surrogate species in pesticide risk assessments: Toxicological data of three stingless bees species

Discussions about environmental risk reassessment of pesticides have grown in the last decades, especially in tropical and subtropical regions since the diversity of bee species in these places is quite different. Stingless bees are highly affected by pesticides, and toxicity information is necessary to include them in the regulatory process of countries that hosts a diversity of these species. Therefore, the present study aimed to evaluate the Median Lethal Concentration (LC50), estimate the Median Lethal Dose (LD50) and compared the sensitivity of three species of stingless bees exposed to the commercial formulation of the neonicotinoid thiamethoxam (TMX). The LD50 was estimated based on the LC50 determined in the present study (LC50 = 0.329 ng a.i./μL for Tetragonisca angustula; 0.624 ng a.i./μL for Scaptotrigona postica, and 0.215 ng a.i./μL for Melipona scutellaris). Considering these data, toxicity endpoints were used to fit species sensitive distribution curves (SSD) and determine the sensitivity ratio. The results showed that all the stingless bees tested are more sensitive to TMX than the Apis mellifera, the model organism used in ecotoxicological tests. Regarding the oral LC50, the most susceptible and most tolerant species were M. scutellaris > T. angustula > S. postica > A. mellifera. Following the same evaluated pattern, for the LD50 (considering the weight of the bees - ng a.i./g bee), we have: M. scutellaris > S. postica > T. angustula > A. mellifera, and without the weight considered (ng a.i./bee): T. angustula > M. scutellaris > S. postica > A. mellifera. The different sensitivities among stingless bee species highlight the importance of inserting more than one surrogate species with a variety of sizes in research and protocol development. Additionally, the research suggests the need to investigate patterns regarding the influence of body mass on pesticide sensitivity among stingless bee species.

Magnetic biochar pyrolyzed from municipal sludge for Fenton-like degradation of thiamethoxam: Characteristics and mechanism

Pesticide pollution is an arduous challenge encountered in the field of industrial wastewater treatment. As a Fenton-like metal catalyst, multifunctional biochar has attracted more and more attention in the dissolution of insoluble organic chemical pollutants. In this study, the magnetic municipal sludge biochars(MSDBC)were synthesized by one-step pyrolysis of sludge from sewage treatment plant. The biochars prepared at different temperatures have great differences in surface functional groups and composition of iron phase. MSDBC prepared at 400 °C has a better catalytic oxidation capacity, while MSDBC prepared at 800 °C has a stronger adsorption capacity. The reason is that the morphology and iron phase composition distribution of biochar are different. More pore structures were formed on the surface of biochar prepared at 800 °C, which not only has better adsorption performance, but also makes the impregnated Fe3+ enter the interior of biochar and transform during pyrolysis. However, the iron phase of MSDBC prepared at 400 °C is mostly located on the surface and the content of Fe2+ is higher. Notably, iron compounds embedded in the magnetic biochar have been proved to be the main catalysts for activating hydrogen peroxide (H2O2) to produce hydroxyl radicals (·OH). Radical quenching experiment and electron paramagnetic resonance (EPR) detection confirmed the production of ·OH and its important role in the oxidative degradation of thiamethoxam (THX). In the THX degradation, MSDBC/H2O2 Fenton-like system showed excellent effect at neutral pH environment. Finally, the innovative use of MSDBC/H2O2 Fenton-like technology in the degradation of complex actual wastewater showed good practicability and stability. This research provides a new idea for the treatment of pesticide wastewater.

A nano-delivery system expands the insecticidal target of thiamethoxam to include a devastating pest, the fall armyworm.

Nano-delivery systems have been applied to deliver various synthetic/botanical pesticides to increase the efficiency of pesticide use and reduce the volumes of pesticides applied. Previous studies have supported the hypothesis that the nanocarriers can help expand the insecticidal target of pesticides to include non-target pests. However, the potential mechanism underlying this interesting phenomenon remains unclear. Herein, a widely applied star polycation (SPc) nanocarrier was synthesized to construct a thiamethoxam (TMX) nano-delivery system. The SPc-based delivery system could promote the translocation of exogenous substances across the membrane of Sf9 cells, increase the cytotoxicity of TMX against Sf9 cells by nearly 20%, and expand the insecticidal target of TMX to include Spodoptera frugiperda (the fall armyworm), with a 27.5% mortality increase at a concentration of 0.25mg/mL. Moreover, the RNA-seq analysis demonstrated that the SPc could upregulate various transport-related genes, such as Rab, SORT1, CYTH, and PIKfyve, for the enhanced cellular uptake of TMX. Furthermore, enhanced cell death in larvae treated with the TMX-SPc complex was observed through changes in the expression levels of death-related genes, such as Casp7, BIRC5, MSK1, and PGAM5. The SPc-based nano-delivery system improved the cellular uptake of TMX and expanded its insecticidal target by adjusting the expression levels of death-related genes. The current study mainly identified the transport and cell death genes related to nanocarrier-based insecticidal target expansion, which is beneficial for understanding the bioactivity enhancement of the nano-delivery system.

Joint toxic effects of thiamethoxam and flusilazole on the adult worker honey bees (Apis mellifera L.)

Insect pollinators are routinely exposed to a complex mixture of many pesticides. However, traditional environmental risk assessment is only carried out based on ecotoxicological data of single substances. In this context, we aimed to explore the potential effects when worker honey bees (Apis mellifera L.) were simultaneously challenged by thiamethoxam (TMX) and flusilazole (FSZ). Results displayed that TMX possessed higher toxicity to A. mellifera (96-h LC50 value of 0.11 mg a. i. L−1) than FSZ (96-h LC50 value of 738 mg a. i. L−1). Furthermore, the mixture of TMX and FSZ exhibited an acute synergistic impact on the pollinators. Meanwhile, the activities of SOD, caspase 3, caspase 9, and PPO, as well as the expressions of six genes (abaecin, dorsal-2, defensin-2, vtg, caspase-1, and CYP6AS14) associated with oxidative stress, immune response, lifespan, cell apoptosis, and detoxification metabolism were noteworthily varied in the individual and mixture challenges than at the baseline level. These data revealed that it is imminently essential to investigate the combined toxicity of pesticides since the toxicity evaluation from individual compounds toward honey bees may underestimate the toxicity in realistic conditions. Overall, the present results could help understand the potential contribution of pesticide mixtures to the decline of bee populations.

Toxicity of the neonicotinoid insecticides thiamethoxam and imidacloprid to tadpoles of three species of South American amphibians and effects of thiamethoxam on the metamorphosis of Rhinella arenarum

ABSTRACT The present study examined the acute and chronic toxicity of the neonicotinoid insecticides imidacloprid (IMI) and thiamethoxam (TIA) on the neotropical amphibian species Rhinella arenarum, Rhinella fernandezae and Scinax granulatus. The median lethal concentration after 96 hr exposure (96 hr-LC50) ranged between 11.28 and >71.2 mg/L amongst all species and development stages tested, indicating that these pesticides are not likely to produce acute toxicity in the wild. The subchronic toxicity was also low, with 21 day-LC50 values ranging between 27.15 and >71.2 mg/L. However, tadpoles of Rhinella arenarum exposed to thiamethoxam from stage 27 until completion of metamorphosis presented a significantly lower metamorphic success rate together with a smaller size at metamorphosis, starting from the lowest concentration tested. Although a number of studies previously examined the effects of neonicotinoids on amphibian tadpoles, these investigations focused on the time to metamorphosis and reported a variety of results including retardation, acceleration or lack of effect. Here, data demonstrated that thiamethoxam predominantly impacts metamorphosis through reduction of the transformation success and body weight, rather than by affecting the timings of metamorphosis. By closely monitoring progression of tadpoles through the different stages, impairment of metamorphosis was demonstrated to occur during the transition from stage 39 to 42, suggesting an effect on the thyroid system. An asymmetry in the length of the arms was also observed in metamorphs treated with thiamethoxam. Overall, these results indicate that thiamethoxam, and conceivably other neonicotinoids, have the potential to significantly impair metamorphosis of amphibians and diminish their performance and survival in the wild.

Biodegradation and Metabolic Pathway of the Neonicotinoid Insecticide Thiamethoxam by Labrys portucalensis F11.

Thiamethoxam (TMX) is an effective neonicotinoid insecticide. However, its widespread use is detrimental to non-targeted organisms and water systems. This study investigates the biodegradation of this insecticide by Labrys portucalensis F11. After 30 days of incubation in mineral salt medium, L. portucalensis F11 was able to remove 41%, 35% and 100% of a supplied amount of TMX (10.8 mg L-1) provided as the sole carbon and nitrogen source, the sole carbon and sulfur source and as the sole carbon source, respectively. Periodic feeding with sodium acetate as the supplementary carbon source resulted in faster degradation of TMX (10.8 mg L-1); more than 90% was removed in 3 days. The detection and identification of biodegradation intermediates was performed by UPLC-QTOF/MS/MS. The chemical structure of 12 metabolites is proposed. Nitro reduction, oxadiazine ring cleavage and dechlorination are the main degradation pathways proposed. After biodegradation, toxicity was removed as indicated using Aliivibrio fischeri and by assessing the synthesis of an inducible β-galactosidase by an E. coli mutant (Toxi-Chromo test). L. portucalensis F11 was able to degrade TMX under different conditions and could be effective in bioremediation strategies.

A prompt electrochemical monitoring platform for sensitive and selective determination of thiamethoxam using Fe2O3@g-C3N4@MSB composite modified glassy carbon electrode

The current study reported the synthesis of Fe2O3 @g-C3N4 @melamine Schiff base via a simple and effective methodology. The prepared composite was well characterized by diverse characterization techniques X-ray diffraction (XRD), Fourier transformation infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), Brunauer, Emmett and Teller (BET), Field emission scanning electron microscopy (FESEM) with energy dispersive spectrometry (EDS) mapping, High-resolution transmission electron microscopy (HRTEM) and UV Visible spectrophotometer, which indicated the formation of desired pure composite material. Further, the prepared Fe2O3 @g-C3N4 @melamine Schiff base modified GCE was applied for the detection of thiamethoxam (TMX), a class of neonicotinoid pesticide. Additionally, the influence of numerous parameters such as the amount of electrocatalyst loaded, pH of the solution, accumulation temperature, and accumulation time was also studied to achieve efficient detection. Furthermore, the cyclic voltammetry (CV) and linear sweep voltammetry (LSV) revealed that the composite acts as an excellent sensor for the electrochemical determination of TMX and attained a very low limit of detection (0.137 µM / 39 ppb) with a broad linear range of 0.01–200.00 µM. Further, to evaluate the stability of the designed sensor; the prepared Fe2O3 @g-C3N4 @melamine Schiff base was also coated on the screen-printed electrode and the electrochemical experiment was performed by it for a period of 30 days. It was depicted that the proposed sensor afforded satisfactory stability, reproducibility as well as repeatability for TMX detection. Moreover, the current work also offers a promising approach for the electrochemical detection of TMX in real samples like potato, rice, and river water.

Effect of thiamethoxam on the behavioral profile alteration and toxicity of adult zebrafish at environmentally relevant concentrations

Thiamethoxam (THM) is a commercial neonicotinoid insecticide with broad-spectrum insecticidal activity. It has been widely detected in the aquatic environment, but its behavioral toxicity on aquatic organisms received limited attention. In this study, adult zebrafish were exposed to THM at three levels (0.1, 10, and 1000 μg/L) for 45 days to investigate its effect on their ecological behavior, histopathology, bioaccumulation, and stress response. The bioconcentration factor in zebrafish brain was significantly higher (p < 0.05) at low concentration of THM (0.1 μg/L) than in other treatment groups. In terms of individual behavior, the locomotor activity, aggregation, and social activity of fish were enhanced after THM exposure, but the memory of the food zone was disturbed and abnormal swimming behavior was observed. THM exposure caused brain tissue necrosis, erythrocyte infiltration, cloudy swelling, and other pathological changes in brain tissue and affected the concentrations of acetylcholinesterase and cortisol related to neurotoxicity. The condition factor and organ coefficients (brain, heart, and intestine) of zebrafish were markedly impacted by THM treatment at 0.1 and 1000 μg/L, respectively. This finding showed that THM was more harmful to fish behavior than lethality, reproduction, and growth, and a behavioral study can be a useful tool for ecological risk assessment.

Enhanced removal of Thiamethoxam from wastewater using waste-derived nanoparticles: Adsorption performance and mechanisms

Thiamethoxam (TMX) is a highly toxic systemic neonicotinoid pesticide and its entry into water bodies can greatly endanger human health and aquatic ecosystems. Hence, developing low-cost, ecofriendly and efficient adsorbents is urgently needed for removal of TMX from contaminated water. In this study, the nanostructured alum water treatment residuals (nWTR) were produced, characterized and evaluated, for the first time, for TMX removal from wastewater through sorption and mechanism studies. The impact of pH, sorbent/TMX solution ratio, exposure time, initial TMX concentration, and temperature on the TMX removal process were examined. The maximum adsorption capacity of TMX by nWTR was enhanced 2.6 times higher than that of bulk WTR due to enlarged specific surface area and pore volume. The adsorption equilibrium and kinetics data best followed Langmuir and first order models respectively. The thermodynamic study showed that the adsorption reaction of TMX onto nWTR was a spontaneous and endothermic process. The suggested mechanisms of TMX sorption by nWTR are hydrogen bonding, Al and Fe complexes formation and electrostatic interlinkage. Furthermore, the reusability study showed that nWTR sorbent can be effectively applied for up to 3 consecutive cycles for the remediation of TMX contaminated wastewater. The study demonstrates the potential use of nWTRs as cost effective, stable, reusable and promising adsorbent for TMX removal from wastewater. • Nanoscale water treatment residual (nWTR) was used for thiamethoxam (TMX) removal. • Adsorption capacity of nWTR for TMX was 2.6 times higher than that of bulk WTR. • The highest percentage removal of TMX (82%) was achieved at pH ∼ 7. • nWTR adsorbent maintained its high adsorption ability up to 3 consecutive cycles. • The mechanisms of TMX adsorption by nWTR were comprehensively elucidated.

Combined remediation effects of biochar and organic fertilizer on immobilization and dissipation of neonicotinoids in soils.

Neonicotinoid (NEO) pesticides have become a potential risk to ecological safety and human health after application. The combined use of biochar and organic fertilizer (OF) is a promising approach to reduce pesticide adverse effects and improve soil fertility in agricultural soils. However, the combined remediation effects of biochar and OF on immobilization and dissipation of NEOs in soils have not previously been systematically investigated. In this study, biochars derived from peanut shell prepared at low/high pyrolysis temperatures (PS400 and PS900) were combined with composted chicken manure (CCM) as an example for OF to remediate contaminated soils toward six typical NEOs, nitenpyram (NIT), thiamethoxam (THIA), clothianidin (CLO), imidacloprid (IMI), acetamiprid (ACE), thiacloprid (THI). Results shown that both biochars and CCM were effective in improving soil sorption capacity and immobilization efficiency. The Freundlich affinity parameters (Kf) of NEOs in soils increased 7.2-12.0 times after the combined remediation of biochar and CCM, and the Kf of six NEOs had negative correlation with their lipophilicity (p<0.05), which followed by THI>ACE ≈ IMI>CLO>THIA>NIT. Meanwhile, NEOs-abiotic degradation was accelerated by biochar, CCM and their combined addition by adjusting soil pH and stimulating hydrolysis action. Biotic degradation was dominant in NEOs dissipation processes in amended soils, and the contribution ratios of biotic degradation (CRbio) were in the range of 25.4-99.0%. The combined use of biochar and CCM selectively stimulated the relative abundance of NEOs-degraders, which simplified abiotic degradation of -NO2-containing NEOs (viz., NIT, THIA, CLO, and IMI), but inhibited -C≡N-containing NEOs (viz., ACE and THI). The combined remediation provided a strategy for immobilizing NEOs and facilitating dissipation of -NO2-containing NEOs in soils. The results in this study provide valuable information for policymakers and decision-makers to choose appropriate soil remediation approaches with respect to the NEO types.

An ultrasensitive label-free electrochemical aptasensing platform for thiamethoxam detection based on ZIF-67 derived Co-N doped porous carbon

Herein, a new electrochemical aptasensor was developed for the highly selective and sensitive detection of thiamethoxam (TMX). Co-N doped porous carbon (CoNC) was first modified on the glassy carbon electrode (GCE) as a conductive substrate. Then, nickel hexacyanoferrate nanoparticles (NiHCFNPs) were drop-coated on CoNC as signal probes to generate measurable redox peaks. Benefiting from the superior structural features and catalytic activity, CoNC not only facilitated the immobilization of NiHCFNPs, but also exhibited good catalytic activity for the redox of NiHCFNPs, thus clearly amplifying the sensing signal. Subsequently, gold nanoparticles (AuNPs) were deposited on NiHCFNPs/CoNC/GCE to anchor the aptamer of TMX. When TMX was captured onto the sensor via specific affinity of the aptamer, the formed TMX-Apt complex impeded electron transfer, resulting in a decrease in the peak current. Thus, TMX can be easily detected by measuring the change in peak current. The label-free aptasensor displays high sensitivity to TMX with a quite low LOD of 3.65 × 10-3 μg/L. The acceptable recoveries of environmental water and potato samples varied from 94.05 % to 105.20 %, demonstrating the proposed aptasensor will be a promising tool for the highly sensitive, specific and reliable detection of TMX in both environmental and food matrices.

Upcycling contaminated biomass into metal-supported heterogeneous catalyst for electro-Fenton degradation of thiamethoxam: Preparation, mechanisms, and implications

The safe disposal and resource utilization of heavy metal contaminated biomass has long posed a huge challenge. The direct preparation of heavy metal-contaminated straw into a biomass-derived multi-metal loading heterogeneous Fenton catalyst (BHFC) through pyrolysis for thiamethoxam (THX) degradation is a win–win strategy to address this problem. In this method, Fe, Mn, Cu, and Zn in contaminated biomass collected from mineral areas are released as active metals and loaded in the form of metal oxides on biomass pyrolysis biochar with a mesoporous structure. The presence of multiple metals accelerated the mutual redox, increased oxygen mobility, synergistically promoted the generation of hydroxyl radicals, and reached 100% THX degradation rate and 90% total organic carbon removal within 20 min using the optimum BHFC-600. The BHFC derived from biomass contaminated with different heavy metal contents showed differences in catalytic performance. The THX degradation rate of BHFC prepared from higher metal level biomass increased by 1.2-fold compared to the low level. Possible pathways and mechanisms of THX degradation was investigated using different methods, including density functional theory calculations. The degradation of THX can be mainly attributed to h+, OH, and O2– attacking the region with a high Fukui index. This study presents a promising strategy for preparing sustainable environmentally functional materials and provides new feasible ideas for the safe treatment of contaminated biomass.

Spatiotemporal distribution and fates of neonicotinoid insecticides during the urban water cycle in the lower reaches of the Yangtze River, China

Neonicotinoid insecticides (NNIs) are the most popular insecticides worldwide, yet their spatiotemporal distribution and fates during the urban water cycle remain limited on a large watershed scale. Thus, we investigated ten kinds of NNIs in surface water from the lower reaches of the Yangtze River and hubs of the urban water cycle in all seasons. In brief, eight out of ten NNIs were detected, and thiamethoxam (THM), imidacloprid (IMI), and dinotefuran (DNT) were the most abundant NNIs in surface water, with concentrations of 0.29–48.15 ng/L, 1.69–20.57 ng/L, and 0.98–25.32 ng/L, respectively. The average concentrations of total NNIs in summer were 1.96–4.41 folds higher than those in other seasons. NNIs in the effluents of municipal wastewater treatment plants (WWTPs) were lower than those in surface water, while the average concentrations of total NNIs in the effluents of industrial WWTPs were 1.56–6.86 folds higher than those in surface water, indicating that insecticide production is an important source for NNIs in surface water. DNT was the most recalcitrant NNI in WWTPs, with an average removal efficiency of 49.89%, while in drinking water treatment plants (DWTPs), the removal efficiencies of most NNIs were limited, except for clothianidin (CLO) (90%). Risk assessment showed that NNIs posed medium or high risks to aquatic life, and DNT contributed 26.86–51.48% to the cumulative risks of detected NNIs. This study investigates the spatiotemporal distribution and risks of NNIs and provides information for the supervision of NNIs in the Yangtze River basin, China.

Introduction of acid mine drainage in the direct production of 5-hydroxymethylfurfural from raw biomass and expanding the use of biomass conversion residue

Direct production of 5-hydroxymethylfurfural (HMF) through biomass always needs the addition of exogenous catalysts and causes extra costs. Herein, acid mine drainage (AMD), one of the traditional wastewaters, was introduced as a natural catalyst to produce HMF directly from lignocellulosic biomass. Key factors in the biomass conversion were optimized and investigated by the response surface methodology (RSM), and the HMF yield reached 13.51 wt% under optimal conditions. The metal elements and the acidic environment in AMD activated the Fenton reaction to effectively destroy the lignocellulose structure and synergistically promote the formation of HMF. Furthermore, the biomass substrate in the biomass conversion was indirectly modified by the AMD during this process. The biomass conversion residue could be prepared by pyrolysis to obtain a functional metal-loaded carbon material with good adsorption of thiamethoxam (THX), which provides a sustainable solution for the disposal of biomass conversion residue.

Soil organic matter can delay—but not eliminate—leaching of neonicotinoid insecticides

Soil organic matter (SOM) retains and attenuates many contaminants; however, its interactions with neonicotinoid insecticides under field conditions remain poorly understood. The goal of this study was to determine if SOM influences the persistence or leaching of two neonicotinoid insecticides: thiamethoxam (TMX) and its transformation-product clothianidin (CLO). Thiamethoxam-coated soybean [Glycine max(L.) Merr.] was planted into a clay soil containing different soil organic carbon (SOC) concentrations. Leachate and soil samples were collected for 10 wk after planting and were analyzed for insecticide concentrations using liquid chromatography-tandem mass spectrometry. Single and multiple linear regressions were performed between SOC, leaching volumes, and measured insecticide concentrations, focusing on rainfall events near the beginning, middle, and end of the study. Correlations were also tested between SOC and cumulative mass of leached insecticides. Neither SOC nor per-event leachate volumes explained variability in TMX leaching or residual CLO concentrations in soils; however, by the conclusion of the study residual thiamethoxam concentrations in soil were negatively correlated with cumulative volume of leached water. Initially, the concentration and total mass of leached CLO were significantly and negatively correlated with SOC content; however, this effect faded with time. Leachate dynamics also affected CLO transport, with positive correlations between leachate volume and CLO concentration during the latter events. This analysis demonstrates that SOM can reduce peak loading of neonicotinoids but may not alter cumulative leaching over the entire growing season.