Multifunctional 2D hemin-bridged MOF for the efficient removal and dual-mode detection of organophosphorus pesticides.

The high-residual and bioaccumulation property of organophosphorus pesticides (OPs) creates enormous risks towards the ecological environment and human health, promoting the research for smart adsorbents and detection methods. Herein, 2D hemin-bridged MOF nanozyme (2D-ZHM) was fabricated and applied to the efficient removal and ultrasensitive dual-mode aptasensing of OPs. On the one hand, the prepared 2D-ZHM contained Zr-OH groups with high affinity for phosphate groups, endowing it with selective recognition and high adsorption capacity for OPs (285.7 mg g-1 for glyphosate). On the other hand, the enhanced peroxidase-mimicking biocatalytic property of 2D-ZHM allowed rapid H2O2-directed transformation of 3,3',5,5'-tetramethylbenzidine to oxidic product, producing detectable colorimetric or photothermal signals. Using aptamers of specific recognition capacity, the rapid quantification of two typical OPs, glyphosate and omethoate, was realized with remarkable sensitivity and selectivity. The limit of detections (LODs) of glyphosate were 0.004 nM and 0.02 nM for colorimetric and photothermal methods, respectively, and the LODs of omethoate were 0.005 nM and 0.04 nM for colorimetric and photothermal methods, respectively. The constructed dual-mode aptasensing platform exhibited outstanding performance for monitoring OPs in water and fruit samples. This work provides a novel pathway to develop MOF-based artificial peroxidase and integrated platform for pollutant removal and multi-mode aptasensing.

Upconversion fluorescence nanosensor based on enzymatic inhibited and copper-triggered o-phenylenediamine oxidation for the detection of dimethoate pesticides.

Pesticide residues in agricultural products pose a significant threat to human health. Herein, a sensitive fluorescence method employing upconversion nanoparticles was developed for detecting organophosphorus pesticides (OPs) based on the principle of enzyme inhibition and copper-triggered o-phenylenediamine (OPD) oxidation. Copper ions (Cu2+) oxidized the colorless OPD to a yellow 2,3-diaminophenazine (oxOPD). The yellow solution oxOPD quenched the fluorescence of upconversion nanoparticles due to the fluorescence resonance energy transfer. The high affinity of Cu2+ for thiocholine reduced the level of oxOPD, resulting in almost no fluorescence quenching. The addition of dimethoate led to the inhibition of acetylcholinesterase activity and thus prevented the formation of thiocholine. Subsequently, Cu2+ oxidized OPD to form oxOPD, which attenuated the fluorescence signal of the system. The detection system has a good linear range of 0.01 ng/mL to 50 ng/mL with a detection limit of 0.008 ng/mL, providing promising applications for rapid detection of dimethoate.

Synthesis and antiviral effect of phosphamide modified vidarabine for treating HSV 1 infections.

Vidarabine (ARA) was one of the earliest marine-related compounds to be used clinically for antiviral therapy, however, its fast metabolism is the main defect of this drug. To overcome this, we designed and synthesized a group of phosphamide-modified ARA compounds using ProTide technology. With a phosphamide modification, these compounds could become the substrate of specific phospholipase enzymes expressed in the liver. Among all 16 synthesized compounds, most showed stronger activity against herpes simplex virus type 1 (HSV-1) than ARA (EC50 of approximately 10 µM). The top three compounds were compound 2 (EC50 = 0.52 ± 0.04 µM), compound 6 (EC50 = 1.05 ± 0.09 µM) and compound 15 (EC50 = 1.18 ± 0.08 µM) (about 2 times higher than Sp type compound 2). This study provides evidence for use of the phosphamide modification, which could give ARA higher activity and liver cell targeting.

Glove performance in a warming climate: The role of glove material and climate on permeation resistance to organophosphate insecticides.

Hands and forearms are the principal sites of dermal exposure to organophosphate insecticides, which makes glove use one of the most important components of an exposure control strategy. However, the selection of suitable gloves depends on issues such as task, type, and concentration of organophosphate as well as cost. In addition, chemical protection performance of gloves may be temperature dependent, which is of increasing concern in a warming climate. Two recommended reusable glove materials (polyvinylchloride and nitrile butadiene rubber) and one single-use glove (nitrile/neoprene) were tested for permeation resistance to actual formulations of organophosphate insecticides with active ingredients dimethoate and malathion. Chemical resistance parameters were measured using American society for testing and materials permeation test cells and compared across glove, organophosphate type, and temperature. The three gloves demonstrated comparable and adequate chemical resistance (less than one µg cm-2 min-1 for up to 8 hr exposure; 25-60 °C) for dilute forms of dimethoate and malathion, used during spraying activities. However, the single-use nitrile/neoprene glove is not designed to fully cover the elbow which limits its suitability. In permeation tests that reflect "worst case" exposure scenario to concentrated (neat) organophosphate formulations, as in mixing/loading tasks, a significant variation in chemical resistance between gloves was observed. While polyvinylchloride offered the maximum resistance, physical degradation of nitrile butadiene rubber after 3 hr of continuous exposure makes it unsuitable for handling neat dimethoate. The single-use nitrile/neoprene glove material had considerably poorer permeation resistance (up to 155-fold greater permeation and 6-fold shorter breakthrough) against neat formulations. Overall, elevated temperature (>40 °C) was shown to result in significantly greater (P < 0.05) cumulative permeation of neat formulation insecticides. This work demonstrates the variation in glove performance and potential for greater exposure risk particularly when mixing concentrated pesticides at elevated temperature conditions such as an occluded human skin or hot greenhouses. Training and guidance on testing, selection, use, and storage of gloves should consider in-use exposure scenarios and temperature-induced reduction in chemical protective performance.

Reduction of Pesticide Toxicity Under Field-Relevant Conditions? The Interaction of Titanium Dioxide Nanoparticles, Ultraviolet, and Natural Organic Matter.

In surface waters, the illumination of photoactive engineered nanomaterials (ENMs) with ultraviolet (UV) light triggers the formation of reactive intermediates, consequently altering the ecotoxicological potential of co-occurring organic micropollutants including pesticides due to catalytic degradation. Simultaneously, omnipresent natural organic matter (NOM) adsorbs onto ENM surfaces, altering the ENM surface properties. Also, NOM absorbs light, reducing the photo(cata)lytic transformation of pesticides. Interactions between these environmental factors impact 1) directly the ecotoxicity of photoactive ENMs, and 2) indirectly the degradation of pesticides. We assessed the impact of field-relevant UV radiation (up to 2.6 W UVA/m²), NOM (4 mg TOC/L), and photoactive ENM (nTiO2, 50 µg/L) on the acute toxicity of 6 pesticides in Daphnia magna. We selected azoxystrobin, dimethoate, malathion, parathion, permethrin, and pirimicarb because of their varying photo- and hydrolytic stabilities. Increasing UVA alone partially reduced pesticide toxicity, seemingly due to enhanced degradation. Even at 50 µg/L, nano-sized titanium dioxide (nTiO2) reduced but also increased pesticide toxicity (depending on the applied pesticide), which is attributable to 1) more efficient degradation and potentially 2) photocatalytically induced formation of toxic by-products. Natural organic matter 1) partially reduced pesticide toxicity, not evidently accompanied by enhanced pesticide degradation, but also 2) inhibited pesticide degradation, effectively increasing the pesticide toxicity. Predicting the ecotoxicological potential of pesticides based on their interaction with UV light or interaction with NOM was hardly possible, which was even more difficult in the presence of nTiO2. Environ Toxicol Chem 2020;39:2237-2246. © 2020 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC.

A simple spectroscopic method to determine dimethoate in water samples by complex formation.

A simple and rapid method for the determination of dimethoate in water was developed based on the monitoring of the complex formation between bis 5-phenyldipyrrinate of nickel (II) and the herbicide dimethoate. The method showed a short response time (10 s), high selectivity (very low interference from other sulfate and salts), high sensitivity (limit of detection (LOD) 0.45 µM, limit of quantitation (LOQ) of 1.39 µM), and a Kd of 2.4 µM. Stoichiometry experiments showed that complex formation occurred with a 1:1 relation. The method was applied to different environmental water samples such as lagoon, stream, urban, and groundwater samples. The results indicated that independently from the water source, the method exhibited high precision (0.25-2.47% variation coefficient) and accuracy (84.42-115.68% recovery). In addition, the method was also tested using an effluent from a wastewater treatment plant from Mexico; however, the results indicated that the presence of organic matter had a pronounced effect on the detection.

Comparative Toxicity of Two Different Dimethoate Formulations in the Common Toad (Rhinella arenarum) Tadpoles.

Dimethoate (D) are among the most commonly used organophosphates insecticides in the world. To evaluate the toxicity of two D formulations were selected as test organisms tadpoles of Rhinella arenarum. This toad species has an extensive neotropical distribution and is easy to handle and acclimate to laboratory conditions. The tadpoles were exposed in an acute assay for 48 h to D soluble concentrates (DSC) and emulsifiable concentrates (DEC). The 48 h-LC50 (95% confidence limits) value of DSC was 57.46 mg L-1 (40.52-81.43) and to DEC was 12.76 mg L-1 (10.39-15.68). These differences in toxicity were statistically significant (p < 0.05). In both formulations, acetylcholinesterase), carboxylesterase, and glutathione-S-transferases enzyme activities varied significantly respect to those of control group (p < 0.05). The DEC formulation was the most toxic. These results would allow the assessment and characterization of potential ecological risks following the application of those formulations.

Fluorescent hydrogel test kit coordination with smartphone: Robust performance for on-site dimethoate analysis.

Precise monitoring of pesticide with portable device was challenging because it required high sensitivity, short response time, strong stability and excellent selectivity. Herein, we newly constructed a stimuli-responsive hydrogel (SRHg)-based portable kit by embedding copper nanoparticles (CuNPs) in agarose hydrogel. In this work, dimethoate as inhibitor of urease restrained the generation of ammonia, which reduced in-situ etching of CuNPs, resulting in the fluorescence color response of test kit under ultraviolet illumination. Interestingly, by means of smartphone-based nanocolorimetry, the photo image of portable kit could be translated into digital information using ImageJ software, achieving a direct quantitative tool for dimethoate identification. The simplicity of SRHg-based portable kit combined with smartphone-based color recognition not only improved the analysis sensitivity (detection limit of 1.0 µg L-1), accuracy and stability, but also simplified operation process and shortened sample-to-answer analysis time (55 min), demonstrating that the methodology met the needs of daily testing and provided a new sight for on-site monitoring of food safety and human health.

NIR Hyperspectral Imaging Technology Combined with Multivariate Methods to Study the Residues of Different Concentrations of Omethoate on Wheat Grain Surface.

In this study, a hyperspectral imaging system of 866.4-1701.0 nm was selected and combined with multivariate methods to identify wheat kernels with different concentrations of omethoate on the surface. In order to obtain the optimal model combination, three preprocessing methods (standard normal variate (SNV), Savitzky-Golay first derivative (SG1), and multivariate scatter correction (MSC)), three feature extraction algorithms (successive projections algorithm (SPA), random frog (RF), and neighborhood component analysis (NCA)), and three classifier models (decision tree (DT), k-nearest neighbor (KNN), and support vector machine (SVM)) were applied to make a comparison. Firstly, based on the full wavelengths modeling analysis, it was found that the spectral data after MSC processing performed best in the three classifier models. Secondly, three feature extraction algorithms were used to extract the feature wavelength of MSC processed data and based on feature wavelengths modeling analysis. As a result, the MSC-NCA-SVM model performed best and was selected as the best model. Finally, in order to verify the reliability of the selected model, the hyperspectral image was substituted into the MSC-NCA-SVM model and the object-wise method was used to visualize the image classification. The overall classification accuracy of the four types of wheat kernels reached 98.75%, which indicates that the selected model is reliable.

Sand as a solid support in ultrasound-assisted MSPD: A simple, green and low-cost method for multiresidue pesticide determination in fruits and vegetables.

Sand was studied as a solid support in ultrasound-assisted matrix solid-phase dispersion (UA-MSPD) for the extraction of different pesticide classes, including organophosphates, carbamates, triazoles and pyrethroids from fruits and vegetables, with determination by GC-MS and LC-MS/MS. The performance of sand was compared with that of different types of classic solid supports and alternative natural materials from renewable sources. The best results were obtained using 0.5 g sample, 1 g sand as a solid support, 20 mg activated charcoal and 5 mL ethyl acetate as elution solvent. Recoveries ranged from 55 to 140% with an RSD ≤ 20%. LOQs varied from 0.005 to 0.5 mg kg-1 for all analytes. Thiamethoxam, captan, chlorpyrifos, dimethoate and pyrimethanil were found in strawberry samples at concentrations from 0.01 to 0.06 mg kg-1. Acephate and tebuconazole were found in a tomato sample at concentrations of 0.45 and 0.30 mg kg-1, respectively. The method developed was efficient, simple, cheap, robust, and environmentally friendly.

Identification and Dissipation of Omethoate and Its Main Metabolite DMP in Wheat Determined by UPLC-QTOF/MS.

A study was carried out to evaluate the dissipation kinetics of field-applied omethoate during wheat storage. Both the identification and metabolic dynamics of omethoate metabolites were analyzed using UPLC-QTOF/MS. The presence of the metabolite dimethyl phosphate (DMP) was confirmed in wheat samples with applied omethoate. This might be because the group attached to the P atom of omethoate is replaced by a hydroxyl group through hydrolysis, thus leading to the formation of the specific metabolite DMP during wheat storage. Although the initial concentrations of DMP in different doses were considerably lower than those of omethoate, the half-life values of DMP were 11.87-31.50 days, which were close to the half-life of the parent omethoate (11.85-30.94 days). This indicates that potential health risks might be caused by dietary exposure to DMP and omethoate. Therefore, more importance should be given to the risk assessment for omethoate and its metabolite DMP in wheat.

KOH modified Thevetia peruviana shell activated carbon for sorption of dimethoate from aqueous solution.

Modified Thevetia peruviana shell activated carbon for sorption of dimethoate from aqueous solution derived with potassium hydroxide (KOH) was studied at different concentrations for its potential application in water treatment. The batch sorption was investigated using dimethoate solution of 10-100 mg/L concentrations. Proximate analysis was determined and changes on the surfaces and structure of the TPS were characterized after chemical activation with KOH using XRD, FTIR, SEM-EDAX, pHpzc, BET. The quantum chemical calculation for dimethoate yielded molecule associated energies of -9.8421 (HOMO) and -2.3879 (LUMO) and a total energy of -53,376.2. The kinetic of the sorption was modeled which indicated the sorption equilibrium time as 90 min and pseudo-first order kinetics model showing R2 = 0.994 provided a better description of the process. Analysis of sorption equilibrium revealed that the data fitted well to Freundlich sorption isotherm model (R2 = 0.966), indicating multi-layer sorption of dimethoate on the surface of sorbent. The sorption of dimethoate onto KOHTPS shows 92.60% removal efficiency.

Ultra-thin bimetallic alloy nanowires with porous architecture/monolayer MoS2 nanosheet as a highly sensitive platform for the electrochemical assay of hazardous omethoate pollutant.

A novel electrochemical biosensor was designed for sensitive detection of organophosphate pesticides based on three-dimensional porous bimetallic alloy architecture with ultrathin nanowires (PdCo NWs, PdCu NWs, PdNi NWs) and monolayer MoS2 nanosheet (m-MoS2). The bimetallic alloy NWs/m-MoS2 nanomaterials were used as a sensing platform for electrochemical analysis of omethoate, a representative organophosphate pesticide, via acetylcholinesterase inhibition pathway. We demonstrated that all three bimetallic alloy NWs enhanced electrochemical responses of enzymatic biosensor, benefited from bimetallic synergistic action and porous structure. In particular, PdNi NWs outperformed other two bimetallic alloy. Moreover, PdNi NWs/m-MoS2 as an electronic transducer is superior to the corresponding biosensor in the absence of monolayer MoS2 nanosheet, which arise from synergistic signal amplification effect between different components. Under optimized conditions, the developed biosensor on the basis of PdNi NWs/m-MoS2 shows outstanding performance for the electrochemical assay of omethoate, such as a wide linear range (10-13 M∼10-7 M), a low detection limit of 0.05 pM at a signal-to-noise ratio of 3, high sensitivity and long-time stability. The results demonstrate that bimetallic alloy NWs/m-MoS2 nanocomposites could be excellent transducers to promote electron transfer for the electrochemical reactions, holding great potentials in the construction of current and future biosensing devices.

Photocatalytic degradation of dimethoate in Bok choy using cerium-doped nano titanium dioxide.

Dimethoate, a systemic insecticide, has been used extensively in vegetable production. Insecticide residues in treated vegetables, however, pose a potential risk to consumers. Photocatalytic degradation is a new alternative to managing pesticide residues. In this study, the degradation of dimethoate in Bok choy was investigated under the field conditions using cerium-doped nano titanium dioxide (TiO2/Ce) hydrosol as a photocatalyst. The results show that TiO2/Ce hydrosol can accelerate the degradation of dimethoate in Bok choy. Specifically, the application of TiO2/Ce hydrosol significantly increased the reactive oxygen species (ROS) contents in the treated Bok choy, which speeds up the degradation of dimethoate. Ultra-performance liquid chromatography coupled with mass spectrometry (UPLC-MS) analysis detected three major degradation products, including omethoate, O,O,S-trimethyl thiophosphorothioate, and 1,2-Bis (acetyl-N-methyl-) methane disulfide. Two potential photodegradation pathways have been proposed based on the intermediate products. To understand the relationship between photodegradation and the molecular structure of target insecticides, we investigated the bond length, Mulliken atomic charge and frontier electron density of dimethoate using ab initio quantum analysis. These results suggest the P = S, P-S and S-C of dimethoate are the initiation sites for the photocatalytic reaction in Bok choy, which is consistent with our empirical data.

Phosphamide-containing diphenylpyrimidine analogues (PA-DPPYs) as potent focal adhesion kinase (FAK) inhibitors with enhanced activity against pancreatic cancer cell lines.

A family of phosphamide-containing diphenylpyrimidine analogues (PA-DPPYs) were synthesized as potent focal adhesion kinase (FAK) inhibitors. The PA-DPPY derivatives could significantly inhibit the FAK enzymatic activity at concentrations lower than 10.69 nM. Among them, compounds 7a and 7e were two of the most active FAK inhibitors, possessing IC50 values of 4.25 nM and 4.65 nM, respectively. In particular, compound 7e also displayed strong activity against AsPC cell line, with an IC50 of 1.66 µM, but show low activity against the normal HPDE6-C7 cells (IC50 > 20 µM), indicating its low cell cytotoxicity. Additionally, flow cytometry analysis showed that after treatment with 7e (8 µM, 72 h), both AsPC and Panc cells growth were almost totally inhibited, with a cell viability rate of 16.8% and 18.1%, respectively. Overall, compound 7e may be served as a valuable FAK inhibitor for the treatment of pancreatic cancer.

Liquid-phase membrane extraction of targeted pesticides from manufacturing wastewaters in a hollow fibre contactor with feed-stream recycle.

A two-phase membrane extraction in a hollow fibre contactor with feed-stream recycle was applied to remove selected pesticides (tebufenozide, linuron, imidacloprid, acetamiprid and dimethoate) from their mixed aqueous solutions. The contactor consisted of 50 polypropylene hollow fibres impregnated with 5% tri-n-octylphosphine oxide in di-n-hexyl ether. For low-polar pesticides with log P ≥ 2 (tebufenozide and linuron), the maximum removal efficiency increased linearly from 85% to 96% with increasing the feed flow rate. The maximum removal efficiencies of more polar pesticides were significantly higher under feed recirculation (86%) than in a continuous single-pass operation (30%). It was found from the Wilson's plot that the mass transfer resistance of the liquid membrane can be neglected for low-polar pesticides. The pesticide removals from commercial formulations were similar to those from pure pesticide solutions, indicating that built-in adjuvants did not affect the extraction process.

Synergistic toxicity of zno nanoparticles and dimethoate in mice: Enhancing their biodistribution by synergistic binding of serum albumin and dimethoate to zno nanoparticles.

The extensive applications of ZnO nanoparticles (nano ZnO) and dimethoate (DM) have increased the risk of humans' co-exposure to nano ZnO and DM. Here, we report the synergistic effect of nano ZnO and DM on their biodistribution and subacute toxicity in mice. Nano ZnO and DM had a synergistic toxicity in mice. In contrast, bulk ZnO and DM did not cause an obvious synergistic toxicity in mice. Although nano ZnO was low toxic to mice, coexposure to nano ZnO and DM significantly enhanced DM-induced oxidative damage in the liver. Coadministration of nano ZnO with DM significantly increased Zn accumulation by 30.9 ± 1.9% and DM accumulation by 45.6 ± 2.2% in the liver, respectively. The increased accumulations of DM and Zn in the liver reduced its cholinesterase activity from 5.65 ± 0.32 to 4.37 ± 0.49 U/mg protein and induced hepatic oxidative stress. Nano ZnO had 3-fold or 2.4-fold higher binding capability for serum albumin or DM, respectively, than bulk ZnO. In addition, serum albumin significantly increased the binding capability of nano ZnO for DM by approximately four times via the interaction of serum albumin and DM. The uptake of serum albumin- and DM-bound nano ZnO by the macrophages significantly increased DM accumulation in mice. Serum albumins play an important role in the synergistic toxicity of nano ZnO and DM. © 2016 Wiley Periodicals, Inc. Environ Toxicol 32: 1202-1212, 2017.

A novel amidohydrolase (DmhA) from Sphingomonas sp. that can hydrolyze the organophosphorus pesticide dimethoate to dimethoate carboxylic acid and methylamine.

OBJECTIVES: To characterize a novel dimethoate amidohydrolase from Sphingomonas sp. DC-6. RESULTS: A gene, dmhA, encoding the dimethoate amidohydrolase responsible for transforming dimethoate to dimethoate carboxylic acid and methylamine, was cloned from Sphingomonas sp. DC-6. Sequence analysis and molecular modeling indicate that DmhA shares 31-57 % amino acid sequence identities with other functionally confirmed amidohydrolase. DmhA was expressed in Escherichia coli BL21 (DE3) and purified by Ni-NTA affinity chromatography. The purified DmhA could hydrolyze 4-acetaminophenol, dimethoate and propanil. DmhA activity was optimal at 30 °C and pH 7.5. Hg(2+), Zn(2+), Cu(2+), Cd(2+), Tween 80, Triton X-100 or SDS strongly inhibited its activity. The K m and k cat values of DmhA for dimethoate are 0.02 mM and 1.2 s(-1), respectively. CONCLUSIONS: DmhA was confirmed to be a novel dimethoate amidohydrolase which could eliminate the toxicity of dimethoate, providing a novel gene resource for the development of pesticide-degrading enzyme preparation and mechanistic study of dimethoate hydrolysis.

Environmental Fate and Toxicology of Dimethoate.

The insecticide dimethoate, an organophosphate, was first introduced in 1962 for broad spectrum control of a wide range of insects including mites, flies, aphids, and plant hoppers. It inhibits AChE activity, resulting in nerve damage, which may lead to death. It is considered highly toxic to insects although dimethoate resistance has been observed. Dimethoate has both a low vapor pressure (0.247 mPa) and Henry's law constant (l.42x10(-6) Pa m3/mol), thus volatilization is not a major route of dissipation from either water or moist soils. Photolysis is considered a minor dissipation pathway. However, studies have shown that in the presence of a catalyst, the rate of photolysis does increase. The insecticide has high water solubility (39,800 mg/L) and under alkaline conditions, hydrolysis predominates representing a major degradation pathway. It has a low soil sorption capacity (Koc=20) which varies by soil type and organic matter content. Dimethoate is degraded by microbes under anaerobic conditions and bacterial species have been identified that are capable of using dimethoate as a carbon source. Although many intermediate by-products have been identified by abiotic and biotic processes, the major degradation product is omethoate. Dimethoate has been found to adversely impact many organisms. In plants, photosynthesis and growth are highly impacted, whereas birds exhibit inhibition in brain enzyme activity, thus sublethal effects are apparent. Furthermore, aquatic organisms are expected to be highly impacted via direct exposure, often displaying changes in swimming behavior. Toxicity results include inhibition in growth and more importantly, inhibition of acetylcholinesterase activity.

Comparative evaluation of the efficiency of low-cost adsorbents and ligninolytic fungi to remove a combination of xenoestrogens and pesticides from a landfill leachate and abate its phytotoxicity.

In this study, two widely available low-cost adsorbents, almond shells and a green compost, and two ligninolytic fungi, Pleurotus ostreatus and Stereum hirsutum, were used to remove organic contaminants from a landfill leachate (LLe) and abate its phytotoxicity. The methodology adopted was based on the occurrence of two simultaneous processes, such as adsorption and bioremoval. The leachate was artificially contaminated with a mixture of the xenoestrogens bisphenol A (BPA), ethynilestadiol (EE2) and 4-n-nonylphenol (NP), the herbicide linuron and the insecticide dimethoate at concentrations of 10, 1, 1, 10 and 10 mg L(-1), respectively. Three adsorption substrates were prepared: potato dextrose agar alone or the same incorporating each adsorbent. The substrates were either not inoculated or inoculated with each fungus, separately, before to be superimposed on LLe. After 2 months, the residual amount of each contaminant, the electrical conductivity, the pH and the content of total phenols were measured in treated LLe. Germination assays using lettuce, ryegrass and radish were performed to evaluate LLe phytotoxicity. The combination substrate+P. ostreatus showed the best results with average removals of 88, 96, 99, 58 and 46% for BPA, EE2, NP, linuron and dimethoate, respectively. The same treatment considerably reduced the phenol content in LLe compared to no treatment. The combination substrate+S. hirsutum produced average removals of 39, 71, 100, 61 and 32% for BPA, EE2, NP, linuron and dimethoate, respectively. Also uninoculated substrates showed relevant adsorption capacities towards the five contaminants. Most treatments significantly reduced LLe phytotoxicity, especially on lettuce. The best results were obtained with the treatment compost+S. hirsutum, which produced root and shoot lengths and seedling biomass of lettuce, respectively, 2.3, 3.3, and 1.9 times those measured in untreated LLe. In general, germination results were negatively correlated with LLe properties like the residual amount of the contaminants, the electrical conductivity and the pH. These results show that the methodology adopted in the study, i.e., combined adsorption/biodegradation, is suitable not only to remove xenobiotic contaminants from the leachate but also to reduce considerably its inhibition on seed germination.