Dihydroxyl modified UiO-66 as dispersive solid-phase extraction sorbent coupled with ultra-high performance liquid chromatography tandem mass spectrometry for detection of neonicotinoid insecticides.

The extensive usage of neonicotinoid insecticides (NIs) has raised many concerns about their potential harm to environment and human health. Thus, it is of great importance to develop an efficient and reliable method to determine NIs in food samples. In this work, three Zr4+-based metal-organic frameworks functionalized with various numbers of hydroxyl groups were fabricated with a facile one-pot solvothermal method. Among them, dihydroxy modified UiO-66 (UiO-66-(OH)2) exhibited best adsorption performance towards five target NIs. Then, a sensitive and efficient method for detection of NIs from vegetable and fruit samples was established based on dispersive solid phase extraction (dSPE) with UiO-66-(OH)2 as adsorbent coupled with ultra-high performance liquid chromatography tandem mass spectrometry (UHPLC-MS/MS). Key parameters affecting the dSPE procedure including amounts of adsorbent, adsorption time, eluent solvents and desorption time were investigated. Under the optimal conditions, rapid adsorption of NIs within five minutes was achieved due to the high affinity of UiO-66-(OH)2 towards NIs. The developed method exhibited high sensitivity with limits of detection (LODs) varied from 0.003 to 0.03 ng/mL and wide linearity range over 3-4 orders of magnitude from 0.01 to 500 ng/mL. Furthermore, the established method was applied for determining trace NIs from complex matrices with recoveries ranging from 74.6 to 99.6 % and 77.0-106.8 % for pear and tomato samples, respectively. The results indicate the potential of UiO-66-(OH)2 for efficient enrichment of trace NIs from complex matrices.

Highly Efficient Removal of Neonicotinoid Insecticides by Thioether-Based (Multivariate) Metal-Organic Frameworks.

Circumventing the impact of agrochemicals on aquatic environments has become a necessity for health and ecological reasons. Herein, we report the use of a family of five eco-friendly water-stable isoreticular metal-organic frameworks (MOFs), prepared from amino acids, as adsorbents for the removal of neonicotinoid insecticides (thiamethoxam, clothianidin, imidacloprid, acetamiprid, and thiacloprid) from water. Among them, the three MOFs containing thioether-based residues show remarkable removal efficiency. In particular, the novel multivariate MOF {SrIICuII6[(S,S)-methox]1.5[(S,S)-Mecysmox]1.50(OH)2(H2O)}·36H2O (5), featuring narrow functional channels decorated with both -CH2SCH3 and -CH2CH2SCH3 thioalkyl chains-from l-methionine and l-methylcysteine amino acid-derived ligands, respectively-stands out and exhibits the higher removal efficiency, being capable to capture 100% of acetamiprid and thiacloprid in a single capture step under dynamic solid-phase extraction conditions-less than 30 s. Such unusual combination of outstanding efficiency, high stability in environmental conditions, and low-cost straightforward synthesis in 5 places this material among the most attractive adsorbents reported for the removal of this type of contaminants.

Magnetic molecularly imprinted polymer nanoparticles for the extraction and clean-up of thiamethoxam and thiacloprid in light and dark honey.

In this work, new selective and sensitive dual-template molecularly imprinted polymer nanoparticles (MIPs) were synthesized and characterized. Sorbent MIPs were investigated for simultaneous extraction and clean-up of thiamethoxam and thiacloprid from light and dark honey samples. In this study, ultra-high-performance liquid chromatography-tandem mass spectrometry triple-quadrupole (UHPLC-MS/MS) (QQQ) was used to detect and quantify the pesticides. The kinetic model with adsorption kinetics of sorbent was investigated. The optimal adsorption conditions were 80 mg of polymer MIPs, a 30-min extraction time, and a pH of 7. The detection limit (LOD) and the quantification limit (LOQ) varied from 0.045 to 0.070 µg kg-1 and from 0.07 to 0.10 µg kg-1, respectively. The intra-day and inter-day precision (RSD, %) ranged from 1.3 to 2.0% and from 8.2 to 12.0%, respectively. The recovery of thiamethoxam and thiacloprid ranged from 96.8 to 106.5% and 95.3 to 104.4%, respectively, in light and dark honey samples.

Zeolitic imidazolate framework-8 decorated with gold nanoparticles for solid-phase extraction of neonicotinoids in agricultural samples.

A composite built with aminated zeolitic imidazolate framework and gold nanoparticles (AuNPs) for solid-phase extraction (SPE) of neonicotinoids in agricultural samples is presented. The composite was prepared through the assembly of AuNPs onto the surface of metal-organic framework based on the strong interaction between the amino group and AuNP. These metallic surfaces provided additional interactions based on the affinity of amino and cyano groups present in the target compounds. The composite was characterized by scanning electron microscopy, powder X-ray diffraction, Fourier-transform infrared spectroscopy, and surface area measurements. Regarding the SPE protocol, several parameters that can influence the extraction performance were optimized, such as sample volume or composition of elution solvent, among others. After elution, the analytes were determined via HPLC with diode-array detection. Under the selected conditions, satisfactory recoveries of five pesticides (thiamethoxan, clothianidin, imidacloprid, acetamiprid, and thiacloprid) were obtained (between 80 and 110%) in real samples, whereas the limits of detection ranged from 0.019 to 0.041 µg L-1 in aqueous samples and 0.3 to 0.8 µg g-1 in solid samples.

A QuEChERS-HPLC-MS/MS Method with Matrix Matching Calibration Strategy for Determination of Imidacloprid and Its Metabolites in Procambarus clarkii (Crayfish) Tissues.

We developed a method for determination of imidacloprid and its metabolites 5-hydroxy imidacloprid, olefin imidacloprid, imidacloprid urea and 6-chloronicotinic acid in Procambarus clarkii (crayfish) tissues using quick, easy, cheap, effective, rugged, and safe (QuEChERS) and high-performance liquid chromatography-triple quadrupole mass spectrometry. Samples (plasma, cephalothorax, hepatopancrea, gill, intestine, and muscle) were extracted with acetonitrile containing 0.1% acetic acid and cleaned up using a neutral alumina column containing a primary secondary amine. The prepared samples were separated using reverse phase chromatography and scanned in the positive and negative ion multiple reaction-monitoring modes. Under the optimum experimental conditions, spiked recoveries for these compounds in P. clarkii samples ranged from 80.6 to 112.7% with relative standard deviations of 4.2 to 12.6%. The limits of detection were 0.02-0.5 µg·L-1, the limits of quantification were 0.05-2.0 µg·L-1 and the method of quantification was 0.05-2.0 µg·kg-1. The method is rapid, simple, sensitive and suitable for rapid determination and analysis of imidacloprid and its metabolites in P. clarkii tissues.

Overview of Analytical Methods for the Determination of Neonicotinoid Pesticides in Honeybee Products and Honeybee.

Neonicotinoid pesticides are widely applied for controlling pests in a variety of agriculture crops. Due to the systemic distribution in plants, neonicotinoid pesticides have been found in nectar and pollen, which are the main source of food for the important pollinator honeybee. The risk of neonicotinoid residues in honeybee products and honeybee has caused great attention since their impacts on the environment, ecology, and food safety issues. These concerns require the accurate and sensitive determination of neonicotinoids and their metabolites in the honeybee products and honeybee. Since the trace residue level of neonicotinoid and the complexity of the samples, analysis of neonicotinoid targets in these important matrices is still a great challenge. The present review provides general overview of analytical methods for the determination of neonicotinoid pesticides and their metabolites in honeybee products and honeybee.

Chitosan functionalized AgNPs for efficient removal of Imidacloprid pesticide through a pressure-free design.

Wide dissemination of pesticides for protecting plants against pests has resulted in high production of un-infected crops but higher environmental pollution. High percentages of pesticides are released to the environment and finally use water as the final destination. The current study is concerning by removal of Imidacloprid pesticide from water using pressure-free passage through polymeric membrane integrated design. Both of chitosan and chitosan functionalized silver nanoparticles (AgNPs @chitosan) membranes were prepared, characterized and applied as adsorbent matrix for Imidacloprid. SEM, TEM and PSA analysis revealed the biosynthesis of AgNPs in the range of 25-50 nm. However, SEM and FTIR analysis revealed the proper formation of chitosan membrane and its proper functionalization with silver nanoparticles. Both of chitosan and AgNPs @chitosan membranes succeeded to remove 40 and 85% of Imidacloprid at slightly acidic pH, respectively. Moreover, the amount of removed Imidacloprid was proportional with the amount of its initial concentration indicating the successful removal of Imidacloprid by AgNPs @chitosan membrane even at higher pesticide concentrations. The obtained results indicate the promising use of AgNPs @chitosan membranes for removal of Imidacloprid pesticide from contaminated water depending on the pressure-free design that lacks external energy support.

Porous Activated Carbon from Lignocellulosic Agricultural Waste for the Removal of Acetampirid Pesticide from Aqueous Solutions.

A facile eco-friendly approach for acetampirid pesticide removal is presented. The method is based on the use of micro- and mesoporous activated carbon (TPAC) as a natural adsorbent. TPAC was synthesized via chemical treatment of tangerine peels with phosphoric acid. The prepared activated carbon was characterized before and after the adsorption process using Fourier- transform infrared (FTIR), X-ray diffraction (XRD), particle size and surface area. The effects of various parameters on the adsorption of acetampirid including adsorbent dose (0.02-0.2 g), pH 2-8, initial adsorbate concentration (10-100 mg/L), contact time (10-300 min) and temperature (25-50 °C) were studied. Batch adsorption features were evaluated using Langmuir and Freundlich isotherms. The adsorption process followed the Langmuir isotherm model with a maximum adsorption capacity of 35.7 mg/g and an equilibration time within 240 min. The adsorption kinetics of acetamiprid was fitted to the pseudo-second-order kinetics model. From the thermodynamics perspective, the adsorption was found to be exothermic and spontaneous in nature. TPAC was successfully regenerated and reused for three consecutive cycles. The results of the presented study show that TPAC may be used as an effective eco-friendly, low cost and highly efficient adsorbent for the removal of acetamiprid pesticides from aqueous solutions.

Dummy template surface molecularly imprinted polymers based on silica gel for removing imidacloprid and acetamiprid in tea polyphenols.

Dummy template surface molecularly imprinted polymers based on silica gel were prepared through the surface molecular imprinting technique. Nonpoisonous nicotinamide, which is a structural analogue of imidacloprid and acetamidine, was chosen as the dummy template molecule. The obtained polymers were characterized using scanning electron microscopy, Fourier transform infrared spectroscopy, and X-ray diffraction. The results showed that the polymers exhibited high adsorption capacity and selectivity for imidacloprid and acetamiprid. The maximum adsorption capacities of the polymers toward imidacloprid and acetamiprid were 42.05 and 22.99 mg/g, and the adsorption could reach binding equilibrium within 150 min. The polymers were successfully applied as column-filling materials to extract imidacloprid and acetamiprid from tea polyphenols with a relatively high removal rate (92.36 and 95.20%). The polymers also showed great stability and reusability during the application. The obtained polymers possessed good application prospects for removing imidacloprid and acetamiprid in tea polyphenol production processes.

A signal on-off ratiometric electrochemical sensor coupled with a molecular imprinted polymer for selective and stable determination of imidacloprid.

This work presents a signal on-off ratiometric electrochemical sensor coupled with a molecular imprinted polymer (MIP) for imidacloprid (IMI) determination. The ratiometric strategy corrects the detection results by setting 6-(Ferrocenyl)hexanethiol (FcHT) as an internal reference. The MIP membrane, as a molecular recognition receptor, has a three-dimensional structure and is complementary in the shape and chemical functionality to the template. The combination of a ratiometric strategy and MIP improves the sensitivity and selectivity of the sensors. The experimental parameters, such as monomer/template ratio, electropolymerization cycle and adsorption time, are optimized to improve the IMI sensing performance of the as-fabricated electrode. Under optimal electrochemical conditions, the proposed sensor is used to detect IMI in laboratory and real samples. In a range as wide as 5 × 10-7-1 × 10-4 mol L-1, a linear relationship is well established, and the value of the correlation coefficient is 0.9984. The limit of detection (LOD, S/N = 3) is well defined as 4.7 × 10-8 mol L-1. The recovery rates range from 97.4% to 103.5% while testing real samples. The fabricated electrode shows superior anti-interference ability for IMI determination in the presence of analogs at a higher level.

A functionalized magnetic covalent organic framework for sensitive determination of trace neonicotinoid residues in vegetable samples.

A functionalized magnetic covalent organic framework containing the nitro groups (Fe3O4@COF-(NO2)2) with core-shell structure was synthesized for magnetic solid phase extraction (MSPE) of six neonicotinoid insecticides residue in vegetable samples. The structure of Fe3O4@COF-(NO2)2 was investigated by various characterization techniques. The Fe3O4@COF-(NO2)2 exhibits the excellent thermal and chemical stability, high surface area (254.72 m2 g-1), total pore volume (0.19 cm3 g-1), high magnetic responsivity (27.7 emu g-1), which can be used as an ideal adsorbent for rapid isolation and enrichment of target analytes. A sensitive method was developed by using Fe3O4@COF-(NO2)2-based MSPE coupled with HPLC with UV detection. It offered good linearity within the range of 0.1-30 ng mL-1, low limits of detection (S/N = 3) of 0.02-0.05 ng mL-1. Furthermore, high enrichment factors of 170-250 for six neonicotinoid insecticides were obtained. The applicability of Fe3O4@COF-(NO2)2 is demonstrated for measuring trace neonicotinoid residues in vegetable samples with satisfactory recoveries, which ranged from 77.5 to 110.2%. The results indicated that the Fe3O4@COF-(NO2)2 microspheres offer great potential for efficient extraction of neonicotinoid insecticides from complex samples.

Health risk assessment of neonicotinoid insecticide residues in pistachio using a QuEChERS-based method in combination with HPLC-UV.

There is an increasing need to address the potential risks arising from combined exposures to multiple residues from pesticides in the diet. Pesticide residue-related pollution is a problem that arises because of the increased use of pesticides in agriculture to meet the growing demands of food production. In this study, pesticide residue data were obtained based on an optimized extraction method. For this purpose, we established a method based on quick, easy, cheap, effective, rugged, and safe (QuEChERS) extraction for simultaneous determination of imidacloprid (IMI) and acetamiprid (ACT) in pistachio nuts. The parameters influencing the QuEChERS method were the sample-to-water ratio and adsorbent amounts. As a result, both were optimized to improve the recovery of the analytes as well as the clean-up efficiency of the pistachio matrix. Our results indicated that a freeze-out step and use of primary and secondary amines as an adsorbent led to much cleaner chromatograms with lower baseline drift, without using graphitized carbon black and C18 -based adsorbent, which reduced both cost and time of analysis. Following extraction, the pesticide residues were separated and quantified by reverse-phase HPLC. For validation purposes, recovery studies were carried out using a concentration range from 20 to 2500 µg/L at nine levels. The suitable linearity, precision, and accuracy were obtained with HPLC-UV with recoveries of 70.37%-89.80% for IMI and 81.05%-113.57% for ACT, with relative standard deviations <12%. The validated method was successfully applied to the analysis of pistachio samples collected from a field trial to estimate maximum residue limits. There was no significant health risk for consumers via pistachio consumption.

Simultaneous removal of neonicotinoid insecticides by a microbial degrading consortium: Detoxification at reactor scale.

Neonicotinoid insecticides show high persistence in the environment, and standard biological approaches such as biopurification systems have shown mostly inefficient removal of such compounds. In this work, soil pre-exposed to imidacloprid was used to obtain presumptive imidacloprid-degrading consortia. Cometabolic enrichment yielded a microbial consortium composed of eight bacterial and one yeast strains, capable of degrading not only this compound, but also thiamethoxam and acetamiprid, as demonstrated in cross-degradation assays. The biological removal process was scaled-up to batch stirred tank bioreactors (STBR); this configuration was able to simultaneously remove mixtures of imidacloprid + thiamethoxam or imidacloprid + thiamethoxam + acetamiprid, reaching elimination of 95.8% and 94.4% of total neonicotinoids, respectively. Removal rates in the bioreactors followed the pattern imidacloprid > acetamiprid > thiamethoxam, including >99% elimination of imidacloprid in 6 d and 17 d (binary and ternary mixtures, respectively). A comprehensive evaluation of the detoxification in the STBR was performed using different biomarkers: seed germination (Lactuca sativa), bioluminescence inhibition (Vibrio fischeri), and acute oral tests in honeybees. Overall, ecotoxicological tests revealed partial detoxification of the matrix, with clearer detoxification patterns in the binary mixture. This biological approach represents a promising option for the removal of neonicotinoids from agricultural wastewater; however, optimization of the process should be performed before application in farms.

A nitrile-mediated aptasensor for optical anti-interference detection of acetamiprid in apple juice by surface-enhanced Raman scattering.

Currently, the detection of pesticide is critical for food safety assurance, but it is still challenging due to the presence of biological interferents from complex food matrix. In this study, we developed an optical anti-interference surface-enhanced Raman scattering (SERS) aptasensor system for trace detection of acetamiprid. 4-(Mercaptomethyl) benzonitrile (MMBN) containing CN bond was used as Raman tag to provide a sharp peak (2227 cm-1) in the Raman-silent spectral window (1800-2800 cm-1) where no Raman signal existed for most of molecules. Gold nanoparticles (AuNPs) bonded with polyadenine (polyA)-mediated aptamer and Raman tag (MMBN-AuNPs-aptamer) was synthesized as Raman probe, while the complementary DNA (cDNA) conjugated with AgNPs-decorated silicon wafer (AgNPs@Si) was used as SERS substrate. As acetamiprid molecule could specifically combine with aptamer, preventing the formation of MMBN-AuNPs-aptamer-cDNA-AgNPs@Si (expressed as "Au-AgNPs@Si") hybrid through DNA sequence linking, Raman signal intensities of MMBN in Au-AgNPs@Si decreased when the concentration of acetamiprid increased. Under the optimum assay condition, the proposed method displayed a linear response for acetamiprid detection in the range of 25-250 nM with a low detection limit of 6.8 nM. Finally, the developed aptasensor was successfully used to determine acetamiprid content in apple juice. Accordingly, this novel anti-interference SERS aptasensor could be a promising acetamiprid sensor for food safety assurance.

Determination of 107 Pesticide Residues in Wolfberry with Acetate-buffered Salt Extraction and Sin-QuEChERS Nano Column Purification Coupled with Ultra Performance Liquid Chromatography Tandem Mass Spectrometry.

A multi-residue method for the determination of 107 pesticide residues in wolfberry has been developed and validated. Similar pretreatment approaches were compared, and the linearity, matrix effect, analysis limits, precision, stability and accuracy were validated, which verifies the satisfactory performance of this new method. The LODs and LOQs were in the range of 0.14-1.91 µg/kg and 0.46-6.37 µg/kg, respectively. The recovery of analytes at three fortification levels (10 µg/kg, 50 µg/kg, 100 µg/kg) ranged from 63.3-123.0%, 72.0-118.6% and 67.0-118.3%, respectively, with relative standard deviations (RSDs) below 15.0%. The proposed method was applied to the analysis of fifty wolfberry samples collected from supermarkets, pharmacies and farmers' markets in different cities of Shandong Province. One hundred percent of the samples analyzed included at least one pesticide, and a total of 26 pesticide residues was detected in fifty samples, which mainly were insecticides and bactericide. Several pesticides with higher detection rates were 96% for acetamiprid, 82% for imidacloprid, 54% for thiophanate-methyl, 50% for blasticidin-S, 42% for carbendazim, 42% for tebuconazole and 36% for difenoconazole in wolfberry samples. This study proved the adaptability of the developed method to the detection of multiple pesticide residues in wolfberry and provided basis for the research on the risks to wolfberry health.

Matrix-Induced Sugaring-Out: A Simple and Rapid Sample Preparation Method for the Determination of Neonicotinoid Pesticides in Honey.

In the present work, we developed a simple and rapid sample preparation method for the determination of neonicotinoid pesticides in honey based on the matrix-induced sugaring-out. Since there is a high concentration of sugars in the honey matrix, the honey samples were mixed directly with acetonitrile (ACN)-water mixture to trigger the phase separation. Analytes were extracted into the upper ACN phase without additional phase separation agents and injected into the HPLC system for the analysis. Parameters of this matrix-induced sugaring-out method were systematically investigated. The optimal protocol involves 2 g honey mixed with 4 mL ACN-water mixture (v/v, 60:40). In addition, this simple sample preparation method was compared with two other ACN-water-based homogenous liquid-liquid extraction methods, including salting-out assisted liquid-liquid extraction and subzero-temperature assisted liquid-liquid extraction. The present method was fully validated, the obtained limits of detection (LODs) and limits of quantification (LOQs) were from 21 to 27 and 70 to 90 µg/kg, respectively. Average recoveries at three spiked levels were in the range of 91.49% to 97.73%. Precision expressed as relative standard deviations (RSDs) in the inter-day and intra-day analysis were all lower than 5%. Finally, the developed method was applied for the analysis of eight honey samples, results showed that none of the target neonicotinoid residues were detected.

Evaluation of pressurized liquid extraction for the determination of neonicotinoid pesticides in green onion.

A pressurized liquid extraction (PLE) method was presented for the determination of six neonicotinoid pesticides, acetamiprid, clothianidin, dinotefuran, imidacloprid, thiacloprid, and thiamethoxam in green onion. The critical parameters of PLE, e.g. extraction solvent, temperature, pressure, number of cycles, and static extraction time, were optimized by test on the spiked green onion with six neonicotinoids and the incurred green onion applied with four commercial neonicotinoid insecticide formulations (acetamiprid, dinotefuran, imidacloprid, and thiamethoxam). As a result, the recoveries of six neonicotinoids obtained by one cycle PLE with acetonitrile at 140 °C and 50 bar for 10 min were 94.7-99.5%. These results were acceptable according to the validation guideline for testing method of agricultural chemicals in food by Ministry of Health, Labour, and Welfare in Japan. PLE was also validated by the test on the incurred green onion. The analytical values of four neonicotinoids obtained by PLE were good agreement with those obtained by solid-liquid extraction with homogenizer, which is employed for Japanese official method for the analysis of pesticide residues in food (the ratios of analytical values obtained by PLE to those obtained by solid-liquid extraction were 99.7-101.2%). These results indicate that PLE is applicable for the determination of neonicotinoids in green onion.

A higher efficiency removal of neonicotinoid insecticides by modified cellulose-based complex particle.

Cellulose as an eco-friendly material is extensive in the nature. In this study, modified cellulose-based complex particle (MCCP) was produced through hydrothermal carbonization with methacrylic acid in the stirring and sand bath circumstance. The activated modified carbon-based porous particle (AMCCP) was prepared by treating with potassium hydroxide at high temperature, showing higher efficiency in removing neonicotinoids than MCCP. The AMCCP was fully characterized via scanning electron microscopy, X-ray photoelectron spectroscopy and Brunauer-Emmett-Teller analysis. The Brunauer-Emmett-Teller analysis showed the prepared AMCCP has smaller aggregated particles with higher surface area than MCCP. The adsorption kinetic and the adsorption isotherm of AMCCP were studied, revealing that the pseudo-second-order kinetic model and the Langmuir model correlated with the experimental data better. The maximum adsorption capacity of AMCCP is 142.36 mg/g for acetamiprid. The adsorption process is spontaneous, favorable, and endothermic in nature. After five regeneration time, the adsorption efficiency of the AMCCP is still over 95%.

Determinations of dinotefuran and metabolite levels before and after household coffee processing in coffee beans using solid-phase extraction coupled with liquid chromatography-tandem mass spectrometry.

BACKGROUND: Coffee is one of the most popular beverages in the world. However, as daily consumables, coffee beans may contain pesticide residues that are capable of causing adverse health effects. Thus, we investigated residue dynamics in coffee beans using supervised field trials under Good Agricultural Practice conditions and determined the effects of household coffee processing on the coffee-bean pesticide residues dinotefuran and its metabolites 1-methyl-3-(tetrahydro-3-furylmethyl) urea (UF) and 1-methyl-3-(tetrahydro-3-furylmethyl) guanidine (DN). RESULTS: The recovery rate of dinotefuran and its metabolites UF and DN was in the range 73.5%-106.3%, with a relative SD < 10%. The limits of detection and limits of quantification for dinotefuran, UF and DN were all 0.003 and 0.01 mg kg-1 , respectively. Dissipation experiments were conducted over 2015 and 2016 and showed a mean half-life of 40.8 days. Coffee processing procedures were performed as described for traditional household coffee processing in Ethiopia. Dinotefuran contents were reduced by 44.4%-86.7% with washing of coffee beans and the roasting process reduced these contents by 62.2%-100%. DN residues were not detected in roasted coffee beans before day 21 or in brewed coffee before day 35 and UF residues were not detected in brewed coffee before day 35. Kruskal-Wallis analyses indicated large variations in the stability of pesticide residues between processing methods (P ≤ 0.05). Reductions of pesticide concentrations with washing were also significantly lower than those following roasting (P = 0.0001) and brewing processes (P = 0.002). Moreover, processing factors were less than one for all processing stages, indicating reductions of pesticides contents for all processing stages. CONCLUSION: The cumulative effects of the three processing methods are of paramount importance with respect to an evaluation of the risks associated with the ingestion of pesticide residues, particularly those in coffee beans. © 2018 Society of Chemical Industry.

Kinetics and isotherm modeling of azoxystrobin and imidacloprid retention in biomixtures.

The paper reports the kinetics and adsorption isotherm modeling for imidacloprid (IMIDA) and azoxystrobin (AZOXY) in rice straw (RS)/corn cob (CC) and peat (P)/compost (C) based biomixtures. The pseudo-first-order (PFO), pseudo-second-order (PSO), Elovich and intraparticle diffusion models were used to describe the kinetics. The adsorption data were subjected to the Langmuir and the Freundlich isotherms. Results (r2Adj values) suggested that the modified Elovich model was the best suited to explain the kinetics of IMIDA sorption while different models explained AZOXY sorption kinetics in different biomixtures (PFO in RS + C and RS + P; PSO in CC + P and Elovich in CC + C). Biomixtures varied in their capacity to adsorb both pesticides and the adsorption coefficient (Kd) values were 116.8-369.24 (AZOXY) and 24.2-293.4 (IMIDA). The Freundlich isotherm better explained the sorption of both pesticides. Comparison analysis of linear and nonlinear method for estimating the Freundlich adsorption constants was made. In general, r2Adj values were higher for the nonlinear fit (AZOXY = 0.938-0.982; IMIDA = 0.91-0.970) than the linear fit (AZOXY = 0.886-0.993; IMIDA = 0.870-0.974) suggesting that the nonlinear Freundlich equation better explained the sorption. The rice straw-based biomixtures performed better in adsorbing both the pesticides and can be used in bio-purification systems.