Degradation of the emerging brominated flame retardant tetrabromobisphenol S using organo-montmorillonite supported nanoscale zero-valent iron.

The widespread occurrence of emerging brominated flame retardant tetrabromobisphenol S (TBBPS) has become a major environmental concern. In this study, a nanoscale zero-valent iron (nZVI) impregnated organic montmorillonite composite (nZVI-OMT) was successfully prepared and utilized to degrade TBBPS in aqueous solution. The results show that the nZVI-OMT composite was very stable and reusable as the nZVI was well dispersed on the organic montmorillonite. Organic montmorillonite clay layers provide a strong support, facilitate well dispersion of the nZVI chains, and accelerate the overall TBBPS transformation with a degradation rate constant 5.5 times higher than that of the original nZVI. Four major intermediates, including tribromobisphenol S (tri-BBPS), dibromobisphenol S (di-BBPS), bromobisphenol S (BBPS), and bisphenol S (BPS), were detected by high-resolution mass spectrometry (HRMS), indicating sequential reductive debromination of TBBPS mediated by nZVI-OMT. The effective elimination of acute ecotoxicity predicted by toxicity analysis also suggests that the debromination process is a safe and viable option for the treatment of TBBPS. Our results have shown for the first time that TBBPS can be rapidly degraded by an nZVI-OMT composite, expanding the potential use of clay-supported nZVI composites as an environmentally friendly material for wastewater treatment and groundwater remediation.

Determination of chiral prothioconazole and its chiral metabolite in water, juice, tea, and vinegar using emulsive liquid-liquid microextraction combined with ultra-high performance liquid chromatography.

Emulsive liquid-liquid microextraction (ELLME), a simple, rapid, and environmentally friendly technique, was established to identify chiral prothioconazole and its chiral metabolite in water, juice, tea, and vinegar using ultra-high-performance liquid chromatography (UPLC). Environmentally friendly extractant was mixed with pure water to prepare a high-concentration emulsion, which was added to samples to complete the emulsification and extraction in 1 s. Afterward, an electrolyte solution was added to complete the demulsification without centrifugation. ELLME did not use dispersants compared to the familiar dispersive liquid-liquid microextraction (DLLME), thus reducing the use of toxic solvents and avoiding the effect of dispersants on the partition coefficient. The linear range was from 0.01 to 1 mg/L. The limit of detection was 0.003 mg/L. The extraction recoveries ranged from 82.4 % to 101.6 %, with relative standard deviations of 0.7-5.2 %. The ELLME method developed has the potential to serve as an alternative to DLLME.

Spatial-temporal distribution and potential risk of pesticides in ambient air in the North China Plain.

The intensive use of pesticides in the North China Plain (NCP) has resulted in widespread contamination of pesticides in the local atmosphere, posing risks to air quality and human health. However, the occurrence and distribution of atmospheric pesticides in the NCP as well as their risk assessment have not been well investigated. In this study, 300 monthly samples were collected using passive air samplers with polyurethane foam at ten rural sites with different crop systems in Quzhou county, the NCP, from June 2021 to May 2022. The pesticides were quantified using mass-spectrometric techniques. Our results revealed that chlorpyrifos, carbendazim, and atrazine were the most frequently found pesticides in the air samples, with detection frequencies of ≥ 87 % across the samples. The average concentrations of atmospheric pesticides during spring (7.47 pg m-3) and summer (16.05 pg m-3) were significantly higher than those during autumn (2.04 pg m-3) and winter (1.71 pg m-3), attributable to the intensified application of pesticides during the warmer seasons. Additionally, cash crop sites exhibited higher concentrations (10.26 pg m-3) of atmospheric pesticides compared to grain crop (5.59 pg m-3) and greenhouse sites (3.81 pg m-3), primarily due to more frequent pesticides spraying events in cash crop fields. These findings indicate a distinct spatial-temporal distribution pattern of atmospheric pesticides influenced by both seasons and crop systems. Furthermore, the model-based inhalation risk assessment indicates that inhalation exposure to atmospheric pesticides is unlikely to pose a significant public concern.

Subzero-temperature homogeneous liquid-liquid extraction for the stereoselective determination of chiral triadimefon and its metabolite in water, fruit juice, vinegar, and fermented liquor by HPLC.

A novel method based on homogeneous liquid-liquid extraction with deep eutectic solvents (DES) under subzero-temperature conditions in combination with high performance liquid chromatography (HPLC) for the determination of chiral fungicide triadimefon (TF) and its metabolite triadimenol (TN) in water, fruit juice, vinegar, and fermented liquor was developed in this study. The method involved using deep eutectic solvents (DES) under subzero-temperature conditions in combination with high performance liquid chromatography (HPLC). This novel technique, known as subzero-temperature homogeneous liquid-liquid extraction (STHLLE), offers several advantages, including high efficiency, time-saving, low-cost, and eco-friendliness. The enantiomers of chiral TF and TN were simultaneously separated and quantified using HPLC coupled with a Daicel Chiralpak OD-RH column. Various experimental parameters such as DES composition and volume, freezing condition, salt concentration, and pH were optimized to enhance the recoveries of the target analytes. Under the optimized conditions, spiked recoveries of six enantiomers (i.e., S-TF, R-TF, SR-TN, RS-TN, SS-TN, and RR-TN) in the water, fruit juice, vinegar, and fermented liquor samples were 82.2-100.1% with relative standard deviations of 0.4-10.1%. The current method demonstrated a detection range of 0.03-0.06 mg L-1 in the target analytes. This established technique exhibits potential for efficient and precise extraction and quantification of the enantiomers of TF and TN in water phase samples.

Enantioselective Behaviors of Chiral Pesticides and Enantiomeric Signatures in Foods and the Environment.

Unreasonable application of pesticides may result in residues in the environment and foods. Chiral pesticides consist of two or more enantiomers, which may exhibit different behaviors. This Review intends to provide progress on the enantioselective residues of chiral pesticides in foods. Among the main chiral analytical methods, high performance liquid chromatography (HPLC) is the most frequently utilized. Most chiral pesticides are utilized as racemates; however, due to enantioselective dissipation, bioaccumulation, biodegradation, and chiral conversion, enantiospecific residues have been found in the environment and foods. Some chiral pesticides exhibit strong enantioselectivity, highlighting the importance of evaluation on an enantiomeric level. However, the occurrence characteristics of chiral pesticides in foods and specific enzymes or transport proteins involved in enantioselectivity needs to be further investigated. This Review could help the production of some chiral pesticides to single-enantiomer formulations, thereby reducing pesticide consumption as well as increasing food production and finally reducing human health risks.

Efficient degradation of clothianidin and thiamethoxam in contaminated soil by peroxymonosulfate process.

The widespread use of neonicotinoids has led to their frequent detection in the environment and potential environmental risk in recent years. Clothianidin (CLO) and thiamethoxam (TMX), as the second generation of neonicotinoid insecticides, are usually used as seed agents with a high risk of residue in the soil. Efficient degradation of CLO and TMX in soil using peroxymonosulfate (PMS) process was investigated in the present study. The degradation efficiencies of CLO and TMX reached 91.4% and 98.6% in 60 min with the addition of 20 mM PMS at pH 5.5 and 25℃. High degradation efficiencies of CLO were achieved with a high PMS dosage and temperature or a low CLO concentration and initial pH. The degradation of CLO was reduced in the presence of high concentration of inorganic anions (Cl-, HCO3-). Soil organic matter might be one critical factor in the degradation of CLO and TMX. Radical scavenger experiments confirmed SO4•- and 1O2 were the dominant reactive species on the CLO and TMX degradation. Based on the detected degradation intermediates, the degradation pathways of CLO and TMX include dichlorination, hydroxylation, cleavage of C-N or C-C bond and further oxidation in the PMS-based soil. Overall, the PMS process is one effective and economical method for the remediation of the neonicotinoid contaminated soil.

Acid-washed zero-valent aluminum as a highly efficient persulfate activator for degradation of phenacetin.

Phenacetin (PNT) is one of the most frequently detected nonsteroidal anti-inflammatory drugs in the water ecosystems, which poses a potential risk to environmental aquatic organisms. Acid-washed zero-valent aluminum (ZVAl) as a highly efficient activator for persulfate (PS) process was investigated to degrade PNT from the aqueous solution. The results indicated that acid-washed pretreatment for ZVAl could efficiently increase the degradation efficiency of PNT in the PS treatment. The degradation efficiency of PNT (50 µM) was up to 90% in 4 hours with the addition of 0.2 g/L acid-washed ZVAl and 8 mM PS at pH 6.8 and 25 °C. The PNT degradation followed pseudo-first order kinetics in the present system. High activator dosage, PS concentration, and reaction temperature could enhance the PNT degradation. The presence of inorganic anions (i.e., NO3-, HCO3-) and humic acid (HA) showed inhibitory effects on the PNT degradation. The reuse results illustrated the acid-washed ZVAl material would have continuous and efficient activation performance for PS to degrade the PNT. Radical scavenger experiments and electron paramagnetic resonance indicated that both SO4•- and •OH were major reactive species during the PNT degradation. The possible degradation pathways of PNT mainly included the break of C-N and C-O bonds and further oxidation.

Synthetical effect of microplastics and chiral drug amphetamine on a primary food source algae Chlorella pyrenoids.

The biological effects and fate of the chiral illicit drug amphetamine in the presence and absence of microplastics on freshwater algae (Chlorella pyrenoids), including acute toxicity, growth inhibition, photosynthetic pigment content, oxidative stress, lipid peroxidation, and enantioselective fate were assessed. An agglomeration and the shading effects of microplastics in algae suspension were also determined. Microplastics were observed to increase the toxicity of amphetamine to algae and reduce algae cell growth. Exposed Chlorella pyrenoids exhibited a reduced algae cell counts in an agglomeration test, wherein algae cells decreased between 18% and 56% among treatment groups exposed to 5-50 mg L-1 of microplastics. The agglomeration test suggested that microplastics might significantly increase the adverse effect on algae. Furthermore, our experiments demonstrated enantioselective degradation of amphetamine in algae, and demonstrated that the S-enantiomer was preferably degraded by algae cells. Adding microplastics to the algae suspension significantly reduced the enantioselectivity, with an EF value of 0.41 compared with amphetamine-alone group (0.34) after 21 d exposure. These results demonstrated the first evidence of microplastics acting as a vehicle to enhance amphetamine toxicity to Chlorella pyrenoids, as well as provided new insights into the co-effect of microplastics and organic contaminants on food source.

Efficient degradation of imidacloprid in soil by thermally activated persulfate process: Performance, kinetics, and mechanisms.

Imidacloprid (IMI) as a first-generation commercial neonicotinoid has been frequently detected in the environment in recent years. In this study, the efficient degradation of IMI in soil by a thermally activated persulfate (PS) process was investigated. The degradation efficiencies of IMI were in the range of 82-97% with the PS dosage of 10 mM, when the initial concentrations of IMI were 5-50 mg/kg in the soil. Degradation of the IMI was fitted with a pseudo-first-order kinetic model under different reaction temperatures. Inhibition effects of the common inorganic anions on the IMI degradation in the system followed the order Cl- > HCO3- > H2PO4- > NO3-. Soil pH and soil organic matter were also main factors affecting the degradation of IMI. The degradation efficiencies (64-97%) of three other typical neonicotinoids (acetamiprid, clothianidin, and dinotefuran) indicated that the thermally activated persulfate process could be used for remediation of neonicotinoid-contaminated soil. Quenching experiments indicated that the major reactive species in IMI degradation were SO4•-, O2•-, and •OH. Six degradation intermediates of IMI were inferred in the soil, and degradation pathways of IMI included hydroxylation, denitrification, C-N bond break and further oxidation.

Herbicidal activity and differential metabolism of lactofen in rat and loach on an enantiomeric level.

Enantioselectivity of chiral compounds is receiving growing concern. Lactofen, a chiral herbicide widely used in field crops and vegetables to control broadleaf weeds, is still sold as racemate. In this work, the herbicidal activity and metabolism behavior of lactofen were investigated on an enantiomeric level. Two common broadleaf weeds (Eclipta prostrata L. and Portulaca oleracea L.) were used to evaluate the herbicidal activity of rac-/R- and S-lactofen, and their metabolism behavior in loach and rat liver microsomes was explored. Higher herbicidal activity of S-lactofen was observed, with the 20d-EC50 values being 1.9-3.4 times lower than R-lactofen. Both loach and rat liver microsomes had ability to metabolize rac-lactofen, with half-lives of 1.93 and 1.28 h, respectively. Enantioselective metabolism behaviors were observed in loach and rat liver microsomes and the direction of enantioselectivity were different. R-lactofen was preferentially metabolized in loach liver microsome, while S-lactofen was preferentially metabolized in rat liver microsome. No interconversion of R- and S-lactofen was found. Besides, the main metabolic pathways of R- and S-lactofen were found to be significantly different. R-lactofen was metabolized to R-desethyl lactofen in both loach and rat liver microsomes without further metabolism. However, S-lactofen was metabolized to both S-desethyl lactofen and acifluorfene in rat liver microsome, which was mainly metabolized to acifluorfene in loach liver microsome. This study indicated enantioselectivity and metabolites should be taken into consideration when overall evaluating the environmental behavior of lactofen.

Occurrence and dietary risk assessment of 37 pesticides in wheat fields in the suburbs of Beijing, China.

The co-occurrence of multiple pesticides in wheat fields adversely affects human health and the environment. Herein, 206 pairs of wheat and soil samples were collected from wheat fields in Beijing, China from 2018 to 2020. One or multiple pesticide residues were detected, and carbendazim (maximum: 38511.5 µg/kg) and tebuconazole (maximum: 45.4 µg/kg) had heavy occurrence in the wheat samples. Carbendazim, triazoles, and neonicotinoids were frequently detected in the soil samples. HCHs and DDTs were detected, with p,p'-DDE in 100.0% of the soil samples at a maximum concentration of 546.0 µg/kg in 2020. Concentrations of carbendazim, tebuconazole, hexaconazole, and cyhalothrin in the paired soil and wheat samples exhibited significant positive correlations. Pesticides that exceeded the maximum residue limits do not pose non-carcinogenic risks, with one exception. The results provide important references towards risk monitoring and control in wheat fields, as well as facilitating the scientific and reasonable use of these pesticides.

Graphitic carbon nitride-based materials in activating persulfate for aqueous organic pollutants degradation: A review on materials design and mechanisms.

With the increasingly serious water environment problem, the persulfate-based advanced oxidation process (PS-AOP) has attracted considerable attention in water pollution treatment. To date, graphitic carbon nitride (g-C3N4) has been greatly favored by researchers in activating PS for its capability and unique superiorities. Though g-C3N4-based PS-AOP exhibits huge development prospects in removing organic pollutants, the review about its research progress has not been reported. Herein, this paper reviews the modification of g-C3N4 on the basis of its applications and properties for PS activation systematically. The activation mechanisms of g-C3N4-based modified materials are analyzed in detail, and the main formation pathways of radicals and non-radicals and their interaction mechanism with pollutants are thoroughly summarized. Finally, the existing challenges and future development directions of the PS-AOP driven by g-C3N4-based materials are critically discussed. The key purpose is to provide a reference for promoting the further popularization of this novel and efficient cooperative AOP in water purification industries, as well as multidisciplinary inspirations for g-C3N4-involved fields.

Acetaminophen degradation by a synergistic peracetic acid/UVC-LED/Fe(II) advanced oxidation process: Kinetic assessment, process feasibility and mechanistic considerations.

Application of peracetic acid (PAA) in Advanced Oxidation Processes (AOPs) has seen an increase in the last few years. In this study, PAA/UVC-LED/transition metal was used to degrade acetaminophen (ACT) in an aqueous solution. Amongst tested transition metals (Fe, Cu, Co, Mn, Ag), Fe(II) demonstrated the highest efficiency. The effect of pH, PAA dosage, initial concentration of ACT and Fe(II) concentration was investigated on ACT removal. More than 95% removal efficiency was obtained in 30 min employing pH = 5.0, PAA 4 mM and 0.5 mM Fe(II) (kapp = 0.0993 min-1). Scavenging experiments highlighted the contribution of oxygen-centered radicals; however, the dominant mechanism is hydroxyl radical-induced, while the superoxide radicals had a negligible role. The effect of anions in water showed that carbonate, (dihydrogen) phosphate and nitrite ions had a strong inhibitory effect, while a neutral effect was observed by sulfate, nitrate and chloride ions. Seven intermediates of ACT oxidation were determined and the ACT degradation pathway by the PAA/UVC-LED/Fe(II) is presented. The efficacy of the PAA/UVC-LED/Fe(II) process was also verified for the degradation of other contaminants of emerging concern and disinfection of fecal indicator microorganisms in real matrix (secondary WW). In conclusion, the studied PAA/UVC-LED/Fe(II) process opens a new perspective as a promising application of advanced oxidation for the degradation of organic pollutants.

Co-occurrence of antiseptic triclocarban and chiral anti-inflammatory ibuprofen in environment: Association between biological effect in sediment and risk to human health.

Residues of antiseptics and drugs have been ubiquitously detected in aquatic water-sediment systems, and are thus considered emerging contaminants that threaten our global environment. To investigate the potential risk of ibuprofen and triclocarban in sediment, effects of enzyme activity on the enantioselective degradation in sediment were investigated. Enantioselective fate of rac-ibuprofen was observed in sediment with R-enantiomer exhibiting preferential degradation. Enzyme evidence showed that high levels of triclocarban could significantly inhibit activities of catalase and urease activities in sediment, as well as increase the half-life of ibuprofen (from 5.8 d to 10.1 d). Cytotoxicity data suggested that cell growth processes were significantly affected by ibuprofen and triclocarban co-exposure, which was consistent with apoptosis results. Additionally, the expression of several proteins (Cyto-c, Nrf2, p62, Keap1, NQO1, and Pink1) were markedly induced upon exposure to ibuprofen in the presence of triclocarban. In conclusion, these findings illustrated that co-occurrence of ibuprofen and triclocarban residues have synergistic adverse effects to the environment and synergistically threaten human health.

Occurrence, source and ecotoxicological risk assessment of pesticides in surface water of Wujin District (northwest of Taihu Lake), China.

This study investigated the occurrence and distribution of pesticides in surface water (lakes, major rivers and tributaries) and potential discharge sources (fish ponds, livestock and poultry farms, and sewage treatment plants) in Wujin District (northwest of Taihu Lake), Jiangsu province, China. An analytical liquid chromatography-tandem mass spectrometry method was developed for 38 pesticides, which was applied in the monitoring of 240 surface water samples and 76 potential discharge source samples. Eleven insecticides and five fungicides with temporal and spatial variation were detected in surface water. The total pesticide concentrations in surface water in different seasons were as follows: March > August > June > November. The two most polluting and widespread pesticides were carbendazim (maximum concentration 508 ng L-1, detection rate 100%) and imidacloprid (maximum concentration 438 ng L-1, detection rate 88%). Gehu Lake (S46) and Sanshangang River (S12) were seriously polluted water bodies. Seven insecticides and four fungicides were detected in the potential discharge sources; and their composition changed significantly with the seasons. The concentrations of detected organophosphorus pesticides and neonicotinoids (e.g. acetamiprid in March and dichlorvos in November) in a few non-agricultural planting sources were far greater than those detected in surface water, and hence a few fish ponds, livestock and poultry farms, and sewage treatment plants might be the potential discharge sources of pesticides in the surrounding surface water. The estimated input flux of the studied pesticides from upstream rivers to Taihu Lake was 141.95 kg a-1. Furthermore, more attention should be paid to the medium or high aquatic ecotoxicological risk presented by the levels of organophosphorus pesticides, carbamates, and benzimidazoles.

Dispersive solid-phase extraction combined with dispersive liquid-liquid microextraction for simultaneous determination of seven succinate dehydrogenase inhibitor fungicides in watermelon by ultra high performance liquid chromatography with tandem mass spectrometry.

In this study, a simple and accurate sample preparation method based on dispersive solid-phase extraction and dispersive liquid-liquid microextraction has been developed for the determination of seven novel succinate dehydrogenase inhibitor fungicides (isopyrazam, fluopyram, pydiflumetofen, boscalid, penthiopyrad, fluxapyroxad, and thifluzamide) in watermelon. The watermelon samples were extracted with acetonitrile, cleaned up by dispersive solid-phase extraction procedure using primary secondary amine, extracted and concentrated by the dispersive liquid-liquid microextraction procedure with 1,1,2,2-tetrachloroethane, and then analyzed by ultra high performance liquid chromatography with tandem mass spectrometry. The main experimental factors affecting the performance of dispersive solid-phase extraction and dispersive liquid-liquid microextraction procedure on extraction efficiency were investigated. The proposed method had a good linearity in the range of 0.1-100 µg/kg with correlation coefficients (r) of 0.9979-0.9999. The limit of quantification of seven fungicides was 0.1 µg/kg in the method. The fortified recoveries of seven succinate dehydrogenase inhibitor fungicides at three levels ranged from 72.0 to 111.6% with relative standard deviations of 3.4-14.1% (n = 5). The proposed method was successfully used for the rapid determination of seven succinate dehydrogenase inhibitor fungicides in watermelon.

MiR-511 mimic transfection inhibits the proliferation, invasion of osteosarcoma cells and reduces metastatic osteosarcoma tumor burden in nude mice via targeting MAPK1.

Osteosarcoma, a highly aggressive cancer, can rapidly metastasize to distant organs such as lung, liver, brain. Despite much progress in the therapeutic regime has been made, the prognosis of osteosarcoma remains poor. In present study, microRNA-511 (miR-511) is lowly expressed in osteosarcoma cells, including MG63, U-2 OS, Saos-2 cells, while mitogen activated protein kinase1 (MAPK1) is highly expressed in osteosarcoma cells. Interestingly, MAPK1 might be a target of miR-511. We found that overexpression of miR-511 by miR-511 mimic transfection may result to low expression of MAPK1. Further study showed that miR-511 mimic inhibits the development of osteosarcoma MG63 cell, including proliferation and invasion. Moreover, miR-511 mimic transfection reduces metastatic osteosarcoma tumor burden in nude mice. These activities are mediated by targeting MAPK1. Our study provides a new sight for the molecular pathogenesis of osteosarcoma.

Plants mediate precipitation-driven transport of a neonicotinoid pesticide.

Neonicotinoid insecticides provide crop protection via water solubility and systemicity, yet these chemical characteristics, combined with high toxicity to non-target invertebrates (e.g., honeybees), elicit concern of environmental transport. Neonicotinoids have been detected in soil and surface water throughout North America; however, no investigation has defined a direct connection to planted seed dressings. We quantified the physical transport of thiamethoxam (TMX), a neonicotinoid, under field conditions. We planted TMX-coated corn seeds and maintained plots with and without viable crops (n = 3 plots per treatment) to determine plant influence on pesticide transport. TMX concentrations were measured in soil and drainage throughout the growing season. Storm-generated runoff was the dominant transport mechanism (maximum TMX concentration 1.72 ±â€¯0.605 µg L-1; no viable plants), followed by shallow (<72 cm) lateral drainage (0.570 ±â€¯0.170 µg L-1; no viable plants), and deep (110 cm) drainage (0.170 ±â€¯0.265 µg L-1; viable plants). Soil samples confirmed vertical and lateral movement within 23 and 36 days of planting, respectively. Plants facilitated downward migration of TMX in soil but restricted TMX drainage. Altogether, these study results revealed that neonicotinoids can be transported from seed coatings both above and through the soil profile, which may enable migration into surrounding ecosystems.

Transport of a neonicotinoid pesticide, thiamethoxam, from artificial seed coatings.

Neonicotinoid insecticides coat the seeds of major crops worldwide; however, the high solubility of these compounds, combined with their toxicity to non-target organisms, makes it critical to decipher the processes by which they are transported through soils and into aquatic environments. Transport and distribution of a neonicotinoid (thiamethoxam, TMX) were investigated by growing TMX-coated corn seeds in coarse-textured and fine-textured soil columns (20 and 60cm lengths). To understand the influence of living plants, corn plants were terminated in half of the columns (no plant treatment) and allowed to grow to the V5 growth stage (33days of growth) in the other half (with plant treatment). TMX was analyzed in leachate 12 times over 33days and in bulk soil after 8, 19, and 33days of corn growth. All 20cm columns leached TMX at levels exceeding the United States Environmental Protection Agency benchmark for aquatic invertebrates (17.5µgL-1). TMX migrated from seeds to adjacent bulk soil by the eighth day and reached deeper soil sections in later growth stages (e.g., 30-45cm depth by Day 33). Fine-particle soils transported over two orders of magnitude more TMX than coarse-textured soils (e.g., 29.9µg vs 0.17µg, respectively), which was attributed to elevated evapotranspiration (ET) rates in the sandy soil driving a higher net retention of the pesticide and to structural flow occurring in the fine-textured soil. Living plants increased TMX concentrations at depth (i.e., 30-60cm) compared to the no plant treatment, suggesting that corn growth may drive preferential transport of TMX from coated seeds. Altogether, this study showed that neonicotinoid seed coatings can be mobilized through soil leachate in concentrations considered acutely toxic to aquatic life.

Co-transport of Pesticide Acetamiprid and Silica Nanoparticles in Biochar-Amended Sand Porous Media.

The role of biochar as a soil amendment on the transport of acetamiprid, a widely used neonicotinoid pesticide, is little known. We conducted saturated column experiments to examine cotransport of acetamiprid and silica nanoparticles (NPs) in pure and biochar-amended sands. Retention of acetamiprid was minor in the pure sand, whereas application of biochar in the sand significantly increased retention. Retention was greater at lower ionic strengths and near neutral pH values and was attributed to biodegradation and sorption through π-π interaction and pore filling. The convection-diffusion equation with inclusion of first-order sorption, desorption, and degradation well described the transport of acetamiprid in the biochar-amended sand. The simulation results show that the sorption rate did not change with pH. This is because the acetamiprid is nonionic and cannot be bonded with the biochar by protonation or deprotonation. The desorption rate was independent of variation of solution chemistry, indicating that desorption was a physical process (i.e., pore diffusion). Application of biochar in the sand had little influence on the transport of silica NPs in NaCl but caused complete attachment in CaCl. Energy dispersive X-ray spectroscopy suggested that the enhanced attachment was due to cation bridging between silica NPs and functional groups in biochar by the Ca. The co-presence of acetamiprid and silica NPs in the solutions enhanced transport of acetamiprid and NPs in the biochar-amended sand by competing for the binding sites on the biochar surfaces.