Pesticide residue dynamics in passion fruits: Comparing field trial and modelling results

We evaluated the exposure to pesticides from the consumption of passion fruits and subsequent human health risks by combining several methods: (i) experimental field studies including the determination of pesticide residues in/on passion fruits, (ii) dynamic plant uptake modelling, and (iii) human health risk assessment concepts. Eight commonly used pesticides were applied onto passion fruits cultivated in Colombia. Pesticide concentrations were measured periodically (between application and harvest) in whole fruits and fruit pulp. Measured concentrations were compared with predicted residues calculated with a dynamic and crop-specific pesticide uptake model, namely dynamiCROP. The model accounts for the time between pesticide application and harvest, the time between harvest and consumption, the amount of spray deposition on plant surfaces, uptake processes, dilution due to crop growth, degradation in plant components, and reduction due to food processing (peeling). Measured and modelled residues correspond well (r² = 0.88-0.99), with all predictions falling within the 90% confidence interval of the measured values. A mean error of 43% over all studied pesticides was observed between model estimates and measurements. The fraction of pesticide applied during cultivation that is eventually ingested by humans is on average 10⁻⁴-10⁻⁶, depending on the time period between application and ingestion and the processing step considered. Model calculations and intake fractions via fruit consumption based on experimental data corresponded well for all pesticides with a deviation of less than a factor of 2. Pesticide residues in fruits measured at recommended harvest dates were all below European Maximum Residue Limits (MRLs) and therefore do not indicate any violation of international regulatory thresholds.     

Plant uptake of pesticides and human health: dynamic modeling of residues in wheat and ingestion intake

Human intake of pesticide residues from consumption of processed food plays an important role for evaluating current agricultural practice. We take advantage of latest developments in crop-specific plant uptake modeling and propose an innovative dynamic model to estimate pesticide residues in the wheat-environment system, dynamiCROP. We used this model to analyze uptake and translocation of pesticides in wheat after foliar spray application and subsequent intake fractions by humans. Based on the evolution of residues in edible parts of harvested wheat we predict that between 22 mg and 2.1 g per kg applied pesticide are taken in by humans via consumption of processed wheat products. Model results were compared with experimentally derived concentrations in wheat ears and with estimated intake via inhalation and ingestion caused by indirect emissions, i.e. the amount lost to the environment during pesticide application. Modeled and measured concentrations in wheat fitted very well and deviate from less than a factor 1.5 for chlorothalonil to a maximum factor 3 for tebuconazole. Main aspects influencing pesticide fate behavior are degradation half-life in plant and time between pesticide application and crop harvest, leading to variations in harvest fraction of at least three orders of magnitude. Food processing may further reduce residues by approximately 63%. Intake fractions from residues in sprayed wheat were up to four orders of magnitude higher than intake fractions estimated from indirect emissions, thereby demonstrating the importance of exposure from consumption of food crops after direct pesticide treatment.     

Determination of 28 pesticides applied on two tomato cultivars with a different surface/weight ratio of the berries,using a multiresidue GC-MS/MS method

The behavior of 28 pesticides on two tomato cultivars with a different surface/weight (S/W) ratio of the berries (S/W, Birikino vs. Tombola) was studied, in order to provide appropriate indications about their persistence on crops reaching the pre-harvest interval (PHI). Quantitative analysis was performed using a GC MS/MS method. Birikino cv. (BIR) was a “cherry type tomato” with a double S/W ratio compared with Tombola cv. (TOM). The results showed a different pesticide behavior. Azoxystrobin, Boscalid, Bupirimate, Difenoconazole, Etofenprox, Iprodione, Mepanipyrim, Myclobutanil, Tebuconazole, Zoxamide, Metalaxyl M, Pyrimethanil, Tetraconazole, Benalaxyl, Cyprodinil, Fenamidone, Famoxadone and Fludioxonil immediately after treatments showed residues on BIR higher than TOM, and this behavior is consistent with its greater exposed surface. BIR showed higher decay rates of these pesticides during the whole trial, nevertheless residue averages remained higher than TOM reaching the time of harvest. Residues at the PHI were all below their Maximum Residue Levels (MRLs), but data indicated that they could exceed their legal limits especially if the above-mentioned active ingredients were employed more than once per crop cycle on cherry type tomatoes. As regards to Chlorpyrifos, Chlorpyrifos methyl, Triadimenol, Pyridaben and Tebufenpyrad, no different residual behavior related to S/W ratio of the cultivars was observed. Even in this case, residues at the PHI were all below MRLs. As for Cyfluthrin, Deltamethrin, Lambda cyhalothrin, Etoxazole and Cyproconazole, residues were lower than the limit of quantitation (LOQ) of the analytical method just after the treatment, according to their low doses of employment.     

Transfer of pesticides to the brew during mate drinking process and their relationship with physicochemical properties

In order to evaluate the extraction of pesticide residues that are transferred to the brew during mate drinking process of P.U.1 yerba mate leaves (Ilex paraguariensis), a special device to simulate the way in which mate is drunk in Uruguay was developed. The transfer to the brew of 12 organophosphates, 5 synthethic pyrethroids and one organochlorine pesticide from spiked samples was studied. The relationship between the transfer data thus obtained and physicochemical properties like water solubility (Ws), octanol-water coefficient (Kow) and Henry's constant (H) was evaluated. The extractability of the pesticide residues from yerba mate can be correlated with log Ws and log Kow. These transfer values allowed the calculation of ARLs (acceptable residue level) for the pesticides following Food and Agriculture Organization (FAO), World Health Organizaion (WHO) guidelines. These results can help the future establishment of maximum residue levels (MRLs).     

Transfer of pesticides to the brew during mate drinking process and their relationship with physicochemical properties

In order to evaluate the extraction of pesticide residues that are transferred to the brew during mate drinking process of P.U.1 yerba mate leaves (Ilex paraguariensis), a special device to simulate the way in which mate is drunk in Uruguay was developed. The transfer to the brew of 12 organophosphates, 5 synthethic pyrethroids and one organochlorine pesticide from spiked samples was studied. The relationship between the transfer data thus obtained and physicochemical properties like water solubility (Ws), octanol-water coefficient (Kow) and Henry's constant (H) was evaluated. The extractability of the pesticide residues from yerba mate can be correlated with log Ws and log Kow. These transfer values allowed the calculation of ARLs (acceptable residue level) for the pesticides following Food and Agriculture Organization (FAO), World Health Organizaion (WHO) guidelines. These results can help the future establishment of maximum residue levels (MRLs)     

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.     

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.     

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 EXtrelutNT 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 (r(2)≥ 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.     

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.     

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.     

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.     

Human intake fractions of pesticides via greenhouse tomato consumption: comparing model estimates with measurements for Captan

Human intake due to pesticide residues in food commodities can be much higher than those related to water consumption and air inhalation, stressing the importance to correctly estimate pesticide uptake into plants and predict subsequent intake by humans. We calculated the human intake fraction of captan via tomato consumption taking into account the time between pesticide application and harvest, the time between harvest and consumption, the absorption of spray deposit on plant surfaces, transfer properties through the cuticle, degradation inside the plant and loss due to food processing. Human population intake fractions due to ingestion were calculated for complete, washed and peeled tomatoes. The calculated intake fractions were compared with measurements derived from an experimental setup in a Mediterranean greenhouse. The fraction of captan applied in the greenhouse as plant treatment that eventually is ingested by the human population is on average 10(-2)-10(-5), depending on the time between pesticide application and ingestion of tomatoes and the processing step considered. Model and experimentally derived intake fractions deviated less than a factor of 2 for complete and washed tomatoes and a factor of 3 for peeled tomatoes. Intake fractions due to air inhalation and consumption of drinking water are expected to be significantly lower (5-9 orders of magnitude) than those induced by the intake of tomatoes in this case study.     

National short-term dietary exposure assessment of a selected group of pesticides in Argentina

ABSTRACT

An evaluation of acute dietary exposure to pesticide residues, applying deterministic and stochastic methods, was performed for a selected group of pesticides in two representative age groups from Argentina. Thus, 28 active ingredients (a.i.) and 75 food items were evaluated for the group of 2–5-year-old children, while 9 a.i. and 59 food items were considered for the 10–49-year-old women group. A deterministic assessment was conducting following the Food and Agriculture Organization (FAO) and World Health Organization (WHO) procedure but using the national maximum residue limits (MRLs) as pesticide residue concentration data, while in the stochastic approach, a theoretical distribution modeled with the available information was used. Food consumption data were obtained from the 2004–2005 comprehensive national nutrition and health survey. The risk was estimated by comparing the short-term dietary exposure with the acute reference dose (ARfD) values for each pesticide-food combination evaluated. In the deterministic assessment, 173 (39.1%) and 40 (31.3%) combinations exceeded the ARfD thresholds for the 2–5-year-old children and 10–49-year-old women groups, respectively. This conservative study generated relevant information as a first stage of acute dietary risk assessment in Argentina.     

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.     

Behaviour of forchlorfenuron residues in grape,soil and water

Persistence of forchlorfenuron residues in grape berries at harvest following its dip application as single or split doses to grape berry clusters and periodic dissipation of forchlorfenuron residues in grape berries following foliar spray application were studied. Periodic dissipation of forchlorfenuron residues following its fortification in soil and water were also studied. Splitting the dip application concentration of forchlorfenuron to grape berries reduced its residues in the berries at harvest, which persisted for more than 65 days from all treatments. In case of foliar application, however, the residues of forchlorfenuron in/on the grape berries persisted for 15-20 days only from three treatment concentrations of 2, 3 and 4 ml/l and dissipated with half-lives of 3.4-4.5 days. The residues of forchlorfenuron dissipated faster in soils maintained at field capacity moisture condition than in air dry soils. There was wide variation in its residue persistence in soil (DT50 = 15.1-121.3 days) depending on soil type and moisture condition. Forchlorfenuron residues persisted for more than 30 days in water and its dissipation was fastest at a water salinity level of 3.85 mmho/ cm although the rate of dissipation was not significantly affected by the change in salinity level from <0.04 to 5.90 mmho/cm.     

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.     

Persistence of residues in water and sediment of a fresh-water lake after surface application of technical chlordane

A fresh-water lake, free from detectable pesticide residues before this study, was treated with a commercial formulation of technical chlordane. Water and sediment samples were analysed for chlordane residues 7, 24, 52, 279. and 421 days after treatment. Residues moved rapidly from the water to the lake bottom, supporting earlier results of a laboratory study with other organochlorines. In water, alpha- and gamma-chlordane concentrations remained proportional to total chlordane concentrations, as determined by total-peak area measurements of gas-liquid chromatogrammes. But in bottom sediments, alpha- and gamma-chlordane were more persistent than other constituents of technical chlordane, supporting recent evidence that quantification of technical chlordane residues on the basis of gamma-chlordane quantification only (or that of alpha- and gamma-chlordane only), can lead to incorrect results and that this method, although simple and fast, should no longer be recommended.     

Pesticide residues in thermal mineral water in Greece

Eight different hot springs (SPA) in Greece were monitored over a one-year survey for priority pesticide residues. A specific and effective procedure including solid phase extraction in combination with HPLC and GC analytical methods were applied. Samples that were sensitive to nitrogen-phosphorus (NPD) and/or electron capture (ECD) detectors were analysed by capillary gas chromatography. From the twenty-six water samples, pesticide residues were detected in fourteen of them (54%) but no one exceeding the European Union Maximum Acceptable Concentration (MAC). Lindane (gamma-BHC) was the most frequently detected pesticide. It was found in nine samples (35%) in concentrations from < 0.005 to 0.01 microg/L. Other pesticides detected were phorate (in five samples), propachlor (in two samples) and chlorpyriphos ethyl (in three samples) but in concentrations far below the permissible levels.     

PESTICIDE RESIDUES IN THERMAL MINERAL WATER IN GREECE

Eight different hot springs (SPA) in Greece were monitored over a one-year survey for priority pesticide residues. A specific and effective procedure including solid phase extraction in combination with HPLC and GC analytical methods were applied. Samples that were sensitive to nitrogen-phosphorus (NPD) and/or electron capture (ECD) detectors were analysed by capillary gas chromatography.

From the twenty-six water samples, pesticide residues were detected in fourteen of them (54%) but no one exceeding the European Union Maximum Acceptable Concentration (MAC).

Lindane (γ-BHC) was the most frequently detected pesticide. It was found in nine samples (35%) in concentrations from <0.005 to 0.01 μg/L. Other pesticides detected were phorate (in five samples), propachlor (in two samples) and chlorpyriphos ethyl (in three samples) but in concentrations far below the permissible levels.