Pesticide dissipation curves in peach, pear and tomato crops in Uruguay

Dissipation curves of azoxystrobin and of the neonicotinoids acetamiprid and thiacloprid in peach; azinphos-methyl and carbaryl in pear and azoxystrobin, chlorfenapyr and chlorpyrifos in high-tunnel tomato crops were studied in the Southern region of Uruguay. An analytical methodology based on solid phase extraction (SPE) and detection by High Performance Liquid Chromatography with Diode Array Detector (HPLC/DAD) was used for acetamiprid and thiacloprid. Coupled SPE and detection by Gas Chromatography with Mass Selective Detector (GC/MSD) was used for the detection of azinphos-methyl, azoxystrobin, carbaryl, chlorfenapyr and chlorpyrifos residues. Curves were modeled mathematically with Solver program of Microsoft Excel. The best fit for acetamiprid and thiacloprid in peach was achieved with the exponential model (r(2)=0.961 and 0.944, respectively). In the case of peach fruits there is not a Maximum Residue Limit (MRL) for acetamiprid in the Codex Alimentarius, while 0.5 mg/kg is the value rated for thiacloprid. The MRLs accepted by the European Union (EU) are 0.1 mg/kg for acetamiprid and 0.3 mg/kg for thiacloprid. According to the curves determined in these experiments, thiacloprid residues 10 to 12 days after application (daa) were below the MRLs established by both sources. In the case of acetamiprid, 25 daa would be required, according to the exponential mathematical model, to get residues levels below the MRL values established by the EU. For azinphos methyl in pear, the residues detected were mathematically fitted to an exponential model (r(2)=0.999). According to it, residue levels under the MRL established by the EU (0.05 mg/kg) are gotten in our conditions in 20 daa. In plastic tunnel tomato chlorfenapyr residues were not detected from 16 daa, having the dissipation curve an exponential trend. In the same condition, there was not a decay of the azoxystrobin concentration during a 24-day trial, being it around 0.40 ± 0.05 mg/kg.     

Quantitative analysis of acetamiprid and imidacloprid residues in tomato fruits under greenhouse conditions

Abstract

A selective liquid chromatographic analytical method was studied for determination of two neonicotinoids, acetamiprid and imidacloprid, in tomato fruits under greenhouse conditions in Egypt. The fruits were extracted and cleaned up by QuEChERS method followed by HPLC determination. The method showed a good linearity with a determination coefficient (R²) of higher than 0.99 for the 0.0125–0.15 µg/mL concentration range. The method was validated using a blank tomato spiked at 5, 25 and 50 mg/kg and the recovery percentages were 83.71, 94.52 and 97.49% for acetamiprid and 88.59, 89.63 and 90.18% for imidacloprid, respectively. The rates of dissipation of both pesticides were studied and the preharvest intervals (PHIs) were calculated. Imidacloprid dissipated faster than acetamiprid and half-life periods were 1.30 and 2.07 days, respectively. Acetamiprid and imidacloprid residues were below the already established European maximum residue limits (EU MRLs) (0.5 mg/kg) 3 and 5 days after application, respectively.     

Assessing washing methods for reduction of pesticide residues in Capia pepper with LC-MS/MS

Abstract

The effects of washing treatments on removal rates of some pesticides residues (acetamiprid, chlorpyrifos and formetanate hydrochloride) on pepper were investigated. Method verification was conducted through spiking pepper samples at 0.1, 1.0 and 10.0 × MRL. QuEChERS method produced average recovery of 104.91% with relative standard deviation (RSD) of 13.41%. LOQ values of acetamiprid, chlorpyrifos and formetanate hydrochloride were estimated as 2, 10 and 5?µg/kg, respectively. Capia peppers grown in open fields were sprayed three times with pesticides. Peppers were harvested after 1st, 2nd and 3rd day of the treatments. Then the peppers were subjected to tap water, acetic acid and citric acid washing and ultrasonic cleaning treatments (for 2 and 5?min). Based on three different harvest times and two different washing durations, processing factors (PFs) and reduction rates were calculated for each washing treatment. The residues gradually decreased during washing treatments with increasing process duration. Similarly, a gradual reduction was noted with the progress of harvest times. This in turn corresponded to an increase in PF. Ultrasonic cleaning and citric acid (9%) washing were more effective than the others. Non-systemic pesticides (chlorpyrifos) were more readily removed than the systemic ones (acetamiprid). Similarly, highly soluble pesticides exhibited higher reduction.     

Residues and dissipation kinetic of abamectin,chlorfenapyr and pyridaben acaricides in green beans (Phaseolus vulgaris L.) under field conditions using QuEChERS method and HPLC

Abstract

The current study estimated the dissipation rates of abamectin, chlorfenapyr and pyridaben acaricides in pods of green beans (Phaseolus vulgaris L.) under field conditions in Egypt. Pesticides were extracted and cleaned-up by QuEChERS method and were analyzed by HPLC. The dissipation of these acaricides followed the first order kinetics model with half-life (t_1/2) values 1.00, 3.50 and 1.50?days for abamectin, chlorfenapyr and pyridaben, respectively. The lowest residues, at different time intervals of field application rate of each pesticide, were observed with abamectin followed by pyridaben and then chlorfenapyr. Pre-harvest intervals (PHIs) were 10.00, 13.50 and 6.00?days for abamectin, chlorfenapyr and pyridaben, respectively and were below the established European maximum residue limits (EU MRLs) 10–14, 14–21 and 7–10?days after application, respectively. If the fresh pods will be consumed after harvest, it is expected that the presence of these pesticides in the food will have a negative impact on human health. Therefore, the elimination of the residues of these harmful pesticides must be carried out.     

Validation of QuEChERS method for the determination of some pesticide residues in two apple varieties

This study was undertaken to validate the “quick, easy, cheap, effective, rugged and safe” (QuEChERS) method using Golden Delicious and Starking Delicious apple matrices spiked at 0.1 maximum residue limit (MRL), 1.0 MRL and 10 MRL levels of the four pesticides (chlorpyrifos, dimethoate, indoxacarb and imidacloprid). For the extraction and cleanup, original QuEChERS method was followed, then the samples were subjected to liquid chromatography-triple quadrupole mass spectrometry (LC-MS/MS) for chromatographic analyses. According to t test, matrix effect was not significant for chlorpyrifos in both sample matrices, but it was significant for dimethoate, indoxacarb and imidacloprid in both sample matrices. Thus, matrix-matched calibration (MC) was used to compensate matrix effect and quantifications were carried out by using MC. The overall recovery of the method was 90.15% with a relative standard deviation of 13.27% (n = 330). Estimated method detection limit of analytes blew the MRLs. Some other parameters of the method validation, such as recovery, precision, accuracy and linearity were found to be within the required ranges.     

Determination of neonicotinoids in Estonian honey by liquid chromatography–electrospray mass spectrometry

The aim of the study was to provide a comprehensive overview of neonicotinoid pesticide residues in honey samples for a single country and compare the results with the import data for neonicotinoid pesticides. The levels of four neonicotinoid pesticides, namely thiamethoxam, imidacloprid, acetamiprid, and thiacloprid, were determined in 294 honey samples harvested from 2005 to 2013 from more than 200 locations in Estonia. For the analyzed honey samples, 27% contained thiacloprid, and its levels in all cases were below the maximum residue level set by the European Union. The other neonicotinoids were not detected. The proportion of thiacloprid-positive samples for different years correlates well with the data on thiacloprid imports into Estonia, indicating that honey contamination with neonicotinoids can be estimated based on the import data.     

Minor crops for export: A case study of boscalid,pyraclostrobin, lufenuron and lambda-cyhalothrin residue levels on green beans and spring onions in Egypt

Dissipation rates of boscalid [2-chloro-N-(4′ -chlorobiphenyl-2-yl)nicotinamide], pyraclostrobin [methyl 2-[1-(4-chlorophenyl) pyrazol-3-yloxymethyl]-N-methoxycarbanilate], lufenuron [(RS)-1-[2,5-dichloro-4-(1,1,2,3,3,3-hexafluoropropoxy)phenyl]-3-(2,6-difluorobenzoyl)urea] and λ-cyhalothrin [(R)-cyano(3-phenoxyphenyl)methyl (1S,3S)-rel-3-[(1Z)-2-chloro-3,3,3-trifluoro-1-propenyl]-2,2-dimethylcyclopropanecarboxylate] in green beans and spring onions under Egyptian field conditions were studied. Field trials were carried out in 2008 in a Blue Nile farm, located at 70 kilometer (km) from Cairo (Egypt). The pesticides were sprayed at the recommended rate and samples were collected at pre-determined intervals. After treatment (T₀) the pesticide residues in green beans were 7 times lower than in spring onions. This is due to a different structure of vegetable plant in the two crops. In spring onions, half-life (t_1/2) of pyraclostrobin and lufenuron was 3.1 days and 9.8 days respectively. At day 14th (T₁₄) after treatment boscalid residues were below the Maximum Residue Limit (MRL) (0.34 versus 0.5 mg/kg), pyraclostrobin and λ -cyhalothrin residues were not detectable (ND), while lufenuron residues were above the MRL (0.06 versus 0.02 mg/kg). In green beans, at T₀, levels of boscalid, lufenuron and λ -cyhalothrin were below the MRL (0.28 versus 2 mg/kg; ND versus 0.02 mg/kg; 0.06 versus 0.2 mg/kg, respectively) while, after 7 days treatment (T₇) pyraclostrobin residues were above the MRL (0.03 versus 0.02 mg/kg). However, after 14 days the residue level could go below the MRL (0.02 mg/kg), as observed in spring onions.     

Determination of sixteen pesticides in peppers using high-performance liquid chromatography/mass spectrometry

A method for the detection and quantification of 16 pesticides: flufenoxuron, fenoxycarb, dimethomorph, acetamiprid, imidacloprid, lufenuron, thiacloprid, thiabendazole, thiophanate-methyl, spinosad, fenbutatin oxide, methoxyfenozide, oxamyl, clothianidin, thiamethoxam and carbendazim has been developed based on high-performance liquid chromatography-mass spectrometry. Pesticide residues were extracted from the samples according to the QuEChERS method which stands for quick, essay, cheap, effective, rugged and safe. Homogenised analytical portions (10 g ± 0.1) of samples of peppers were spiked at two levels (10 and 100 μg kg?1) with a small volume of an appropriate standard mixture solution containing each pesticide. Analyses were performed using electrospray ionization (ESI) and a MSD trap system. Chromatography separation was achieved using a ZORBAX SB-C18 3.5 μm particle size analytical column, 2.1 × 50 mm from Agilent, with gradient elution at a flow-rate of 0.4 mL/min with mobile phases: waters-0.1 % HCOOH-5 mM HCOONH? and MeOH-5 mM HCOONH?. The method has been validated based on the SANCO European Guidelines. Under the optimized conditions the recoveries (n = 7) were in the range 70-110 % with satisfactory precision (CV ≤ 20 %). A linear dynamic range was obtained over a range of concentrations from 10 to 100 μg kg?1 for each of the analytes, with correlation coefficients >0.997.     

Consumer health risk to pesticide residues in Salvia officinalis L. and its infusions

Salvia officinalis L. is a popular herb widely used in culinary, cosmetic, and medicinal preparations, and also as an ornamental plant. Sage crops are threatened by many diseases, such as gray mold, powdery mildew, and leaf spot, by weeds, and by pests, such as aphids. Use of crop protection products may lead to presence of pesticide residues in this herb. The aim of this work was to study presence of pesticide residues in the herb, S. officinalis L., available on the retail market in Poland, to verify their compliance with the maximum residue levels (MRLs) and to assess the chronic and acute risks associated with consumption of this herb and infusions prepared from contaminated sage plants. Ninety active substances of pesticides were analyzed, including all active substances registered in Poland for protection of the sage. Five active substances were found, one fungicide – boscalid and four insecticides: chlorpyrifos, pp′-DDT, dimethoate (residue levels above MRL) and indoxacarb. The chronic and acute exposure to pesticide residues consumed with sage did not exceed 0.02% of the acceptable daily intake (ADI) and 0.1% of the acute reference dose (ARfD), respectively.     

Limitations in the determination of maximum residue limits and highest residues of pesticides: Part I

The pesticide usages are controlled by comparing residue concentrations in treated commodities to legally permitted maximum levels (MRLs) determined based on supervised trials designed to reflect likely maximum residues occurring in practice following authorised use. The number of trials available may significantly affect the accuracy of estimated maximum residues. We conducted a study with synthetic lognormal distributions with mean of 1 and standard deviations of 0.8 and 1.0, which reflect the residue distributions observed in practice. The likely residues in samples were modelled by drawing random samples of size 3, 5, 10 and 25 from the synthetic populations. The results indicate that the estimations of highest residues (HR), used for calculation of short-term intake, and the MRLs, serving as legal limits, are very uncertain based on 3–5 trials indicated by the calculated HR_0.975/HR_0.025 and MRL_0.975/MRL_0.025 ratios of 12 and 9, and 13 and 10, respectively, which question the suitability of such trials for the intended purpose. As the 95% range of HR and MRL rapidly decreases with number of trials, ideally ≥15 but minimum 6–8 trials should be used for estimation of HR and MRL according to the current typical practice of Codex Alimentarius.     

Pesticide distribution in an agricultural environment in Argentina

An assessment of the off-site migration of pesticides from agricultural activity into the environment in the Neuquen River Valley was performed. The aim of this study was to evaluate the distribution of pesticides in several compartments of a small agricultural sub-catchment. Soil, surface water, shallow groundwater and drift deposition were analyzed for pesticide residues. Results showed the presence of some pesticide residues in soil, surface water and shallow groundwater compartments. The highest detection frequencies in water (surface and subsurface) were found for azinphos-methyl and chlorpyrifos (>70%). In terms of concentration, the highest levels were observed in shallow groundwater for azinphos methyl (22.5 μg/L) and carbaryl (45.7 μg/L). In the soil, even before the application period had started, accumulation of residues was present. These residues increased during the period studied. Spray drift during pesticide application was found to be a significant pathway for the migration of pesticide residues in surface water, while leaching and preferential flows were the main transport routes contributing to subsurface contamination.     

Estimation of residue levels and dietary risk assessment of cyproconazole and azoxystrobin in cucumber after field application in China

Residue field trials in cucumber were conducted for the safe use of a commercial formulation of cyproconazole·azoxystrobin 28% suspension concentrate (SC 294 g a.i. ha^?1, three applications at a 7-day interval) in the year 2018, in China. To determine the residues of cyproconazole and azoxystrobin in cucumber, a quick, easy, cheap, effective, rugged, and safe (QuEChERS) method was developed using high-performance liquid chromatography coupled with tandem mass spectrometry. This validated method was applied to analyze cucumber samples collected from 12 specified regions. At the 3-day interval to harvest, the highest residue (HR) of azoxystrobin was 0.150 mg kg^?1, which was lower than the maximum residue limit (MRL; 0.5 mg kg^?1) permitted in China, and the HR of cyproconazole was 0.084 mg kg^?1, for which no MRL value has been set in China. The chronic risk quotient values of cyproconazole and azoxystrobin for Chinese adults at a 3-day interval to harvest were 2.56% and 13.72%, respectively. The acute risk quotient values of cyproconazole in cucumber were specified as 5.52% for children (1–6 years old) and 2.83% for the adults (>?18 years old) in China. These results indicate that cyproconazole·azoxystrobin 28% SC sprayed on cucumber at the pre-harvest interval of 3 days has no significant potential risk for Chinese consumers.

     

Pesticide distribution in an agricultural environment in Argentina

An assessment of the off-site migration of pesticides from agricultural activity into the environment in the Neuquen River Valley was performed. The aim of this study was to evaluate the distribution of pesticides in several compartments of a small agricultural sub-catchment. Soil, surface water, shallow groundwater and drift deposition were analyzed for pesticide residues. Results showed the presence of some pesticide residues in soil, surface water and shallow groundwater compartments. The highest detection frequencies in water (surface and subsurface) were found for azinphos-methyl and chlorpyrifos (>70%). In terms of concentration, the highest levels were observed in shallow groundwater for azinphos methyl (22.5 μg/L) and carbaryl (45.7 μg/L). In the soil, even before the application period had started, accumulation of residues was present. These residues increased during the period studied. Spray drift during pesticide application was found to be a significant pathway for the migration of pesticide residues in surface water, while leaching and preferential flows were the main transport routes contributing to subsurface contamination.     

Evaluation of the field dissipation of fungicides and insecticides used on fruit bearing trees in northern Italy

The dissipation of the fungicides captan, cyprodinil, fludioxonil, dithianon, and tebuconazole and of the insecticides chlorpyrifos, fenitrothion, and malathion was studied, following a single treatment of different cultivars of pears, apples, and peaches. The study was conducted in northern Italy, over two successive growing seasons (2004 and 2005). The treatments were performed by the farmers involved, in line with their usual practice. At various time intervals from treatment to harvest, representative samples of fruit were collected and analyzed for pesticide residues. In some cases, concentrations lower than the maximum residue levels (MRLs) were found immediately after treatment. In all trials a rapid decline in pesticide concentrations was observed leading to residues at harvest greatly below the MRLs.     

Residues behavior of some fungicides applied on two greenhouse tomato varieties different in shape and weight

The degradation of 12 fungicides (azoxystrobin, cymoxanil, cyproconazole, cyprodinil, fenarimol, fludioxonil, iprovalicarb, mepanipyrim, penconazole, pyrimethanil, tolclofos-methyl, triadimenol), commonly used in pest management strategies on Sardinian greenhouse tomato crops was studied. A different residue behaviour was observed between the studied cultivar. On the smaller, a “cherry” type tomato, field data showed an initial residue mostly higher than the “beefsteak” tomato. In any case, except for penconazole, all pesticide residues were below their maximum residue levels (MRLs) reaching the pre-harvest interval (PHI). On both cultivar, triadimenol and cymoxanil residues completely disappeared reaching their PHI, while iprovalicarb, fenarimol, and fludioxonil disappeared in a time of 17 to 24 days. On the contrary, azoxystrobin, cyproconazole, cyprodinil, penconazole, tolclofos-methyl, mepanipyrim, and pyrimethanil showed a long persistence on both tested cultivar and may have residual problems due to an accumulation effect if repeated field treatments will be performed. The first group of molecules according to their rapid degradation could be used in low pesticide-input management in order to obtain tomatoes with low or no detectable residues.     

Residues behavior of some fungicides applied on two greenhouse tomato varieties different in shape and weight

The degradation of 12 fungicides (azoxystrobin, cymoxanil, cyproconazole, cyprodinil, fenarimol, fludioxonil, iprovalicarb, mepanipyrim, penconazole, pyrimethanil, tolclofos-methyl, triadimenol), commonly used in pest management strategies on Sardinian greenhouse tomato crops was studied. A different residue behaviour was observed between the studied cultivar. On the smaller, a "cherry" type tomato, field data showed an initial residue mostly higher than the "beefsteak" tomato. In any case, except for penconazole, all pesticide residues were below their maximum residue levels (MRLs) reaching the pre-harvest interval (PHI). On both cultivar, triadimenol and cymoxanil residues completely disappeared reaching their PHI, while iprovalicarb, fenarimol, and fludioxonil disappeared in a time of 17 to 24 days. On the contrary, azoxystrobin, cyproconazole, cyprodinil, penconazole, tolclofos-methyl, mepanipyrim, and pyrimethanil showed a long persistence on both tested cultivar and may have residual problems due to an accumulation effect if repeated field treatments will be performed. The first group of molecules according to their rapid degradation could be used in low pesticide-input management in order to obtain tomatoes with low or no detectable residues.     

Dissipation of fenoxycarb and pyriproxyfen in fresh and canned peach

The objective of this work was to determine the dissipation of fenoxycarb and pyriproxyfen in fresh and canned peaches in order to know the levels of residues that can reach consumers in real circumstances. Two field dissipation studies were carried out, one of them at the pre-harvest interval (PHI) with good agricultural practice (GAP) and the other one in a situation of critical agricultural practice (CAP). Two canning dissipation studies were carried out for samples from both agricultural situations in an industrial pilot plant and the dissipation was determined in each relevant step. An analytical methodology was used including acetone-dichloromethane extraction, purification and analysis by liquid chromatography and diode array detection (LC-DAD) with a limit of quantification (LOQ) of 0.05 mg/kg. It was validated under SANCO/10232/2006 Guidelines. These pesticides complied with the official maximum residue limits (MRLs) in peaches at the PHI with good agricultural practices. In hypothetical situation of a second application at the PHI, fenoxycarb and pyriproxyfen residues were above the MRLs in peaches. The canning study reduced the residues to no detectable levels in the cans for consumers.     

Dissipation of fenoxycarb and pyriproxyfen in fresh and canned peach

The objective of this work was to determine the dissipation of fenoxycarb and pyriproxyfen in fresh and canned peaches in order to know the levels of residues that can reach consumers in real circumstances. Two field dissipation studies were carried out, one of them at the pre-harvest interval (PHI) with good agricultural practice (GAP) and the other one in a situation of critical agricultural practice (CAP). Two canning dissipation studies were carried out for samples from both agricultural situations in an industrial pilot plant and the dissipation was determined in each relevant step. An analytical methodology was used including acetone-dichloromethane extraction, purification and analysis by liquid chromatography and diode array detection (LC-DAD) with a limit of quantification (LOQ) of 0.05 mg/kg. It was validated under SANCO/10232/2006 Guidelines. These pesticides complied with the official maximum residue limits (MRLs) in peaches at the PHI with good agricultural practices. In hypothetical situation of a second application at the PHI, fenoxycarb and pyriproxyfen residues were above the MRLs in peaches. The canning study reduced the residues to no detectable levels in the cans for consumers.     

Tank mixture additives approach to improve efficiency of bentazon against broadleaf weeds in peas

Efficiency of different tank-mixed additives with bentazon at half rate was investigated on (Malva parviflora) and other broad leaf weeds compared with bentazon at the full recommended rate without additives in peas in open field. All the tested additives enhanced the efficiency of bentazon at the half rate. Nonyl phenol and toximol S proved to be the most effective additives in comparison with the full rate treatment. The tested treatments did not show any significant effect on chlorophyll content and soil microorganisms. Bentazon residues were determined in certain treatments to investigate the effect of the tested additives on bentazon deposition. Samples were extracted using QuEChERS method and residues were determined using LC-MS/MS. Residues after 24 hours in the half rate treatment reached 4 times lower than the Maximum Residues Limit (MRL) (0.11 mg kg(-1)), compared to the full rate treatment (0.51 mg kg(-1)), that was slightly above the MRL.     

Solid-phase extraction for multi-residue analysis of pesticides in honey

A fast and simple multi-residue method for the analysis of 15 organophosphorus (OP), 17 organochlorine (OC), 8 pyrethroids (PYR), 12 N-methyl-carbamate (NMC) pesticide residues and bromopropylate in honey is presented. Ready–to–use EXtrelut®NT 20 column, eluted with dichloromethane, was used to extract the pesticide residues from the aqueous-acetone honey sample, obtaining a clean extract directly analyzable. Determination was carried out by gas chromatography (GC) coupled with flame photometric detector (FPD) for OP compounds and by GC coupled with mass spectrometry detector (MSD) for OC and PYR pesticides and bromopropylate. The NMC pesticides were analysed by liquid chromatography-double derivatization coupled with spectrofluorimetric detector (LC/DD/Fl). This method allows the determination of the 53 pesticide residues at low concentrations (0.0005–0.074 mg/kg) and can be used to assess the compliance with the Maximum Residues Levels (MRLs) set by the European Union. The performance of the method was evaluated and specificity, linearity, recovery, repeatability, reproducibility, limit of quantification (LOQ) and limit of detection (LOD) were determined. A good linearity (r²? 0.99) was found in the range 0.0005–0.074 mg/kg for the majority of the compounds studied. Most of the pesticides had recoveries in the range 70–103 % and values of relative standard deviation (RSD) < 20 for repeatability and reproducibility, showing good accuracy and precision of the method. Aldicarb partially degraded in aldicarb sulphoxide during the analytical procedure, giving anomalous values. The LOQ for all pesticides investigated was from 0.0005 to 0.025 mg/kg while the LOD ranged from 0.0002 to 0.008 mg/kg.