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.     

Pesticide residues in fruits and vegetables in Ghana: a review

Pesticides are known to improve agriculture yield considerably leading to an increase in its application over the years. The use of pesticides has shown varying detrimental effects in humans as well as the environment. Presently, enough evidence is available to suggest their misuse and overuse in the last few decades in most developing nations primarily due to lack of education, endangering the lives of farmers as well as the entire population and environment. However, there is paucity of data especially over long durations in Ghana resulting in the absence of effective monitoring programs regarding pesticide application and subsequent contamination in fruits and vegetables. Therefore, this review discusses comprehensively pesticide type and use, importation, presence in fruits and vegetables, human exposure, and poisoning in Ghana. This is to alert the scientific community in Ghana of the need to further research into the potential implications of pesticide residues in food commodities in order to generate a comprehensive and reliable database which is key in drafting policies simultaneous with food regulation, suitable monitoring initiatives, assessment, and education to minimize their effects thereon.     

LC-MS/MS determination of pesticide residues in fruits and vegetables

The aim of the research is to evaluate pesticide residue contamination of fresh and frozen fruits and vegetables, agricultural raw material, purchased from Polish farmers for production of frozen fruits and vegetables, and the estimation of the multiresidue method effectiveness expressed as the proportion of pesticides detected in food samples to the total number of pesticides analyzed by multiresidue methods. A total of 144 samples (of black currants, red currants, raspberries, cherries, strawberries, blackberries, cauliflowers and broccoli) were analyzed using LC-MS/MS method for the determination of 60 pesticides. QuEChERS extraction, matrix-matched calibration and dynamic multiple reaction monitoring method were used. Residues of 15 compounds, mainly fungicides and insecticides, were detected in 46 samples. The percentage of samples with residues above the maximum residue levels (MRL) was 15%, whereas samples with residues below MRL were 17%. A total of 13 samples contained more than one pesticide residue. Pesticide residues were detected most often in samples of black currants (50%), broccoli (36.4%), raspberries (29%) and red currants (21.8%). The most frequently detected pesticides were carbendazim and acetamiprid. The proportion of pesticides detected during our study to the total number of analyzed pesticides amounted to 25%. It was compared to literature findings. For three fourth of multiresidue methods, the proportion was below 50% for methods developed for the analysis of less than 100 pesticides, and below 30% for methods developed for the analysis of more than 100 pesticides. It appears that a lot of efforts and means is lost on pesticides never or rarely detected in examined samples. The workload and cost effectiveness of the development and application of multiresidue methods along with the range of pesticides covered by the method should be carefully and thoroughly considered anytime when a new method or workflow is developed. Including non-targeted screenings in pesticide residue control seems to be an alternative worth considering.     

Pesticide residues in fruits and vegetables from Pakistan: a review of the occurrence and associated human health risks

The main objective of the review is to document, assess and analyze the results of the previously reported data on levels of different pesticides in selected fruits and vegetables from Pakistan. The findings of the previous studies clearly indicated that more than 50 % of the samples were contaminated with organophosphate, pyrethroids and organochlorine pesticides. Many studies reported that among fresh fruits and vegetables tomato, apple, melon, mango, grapes, and plum crossed the FAO/WHO permissible limits for these contaminants residual levels. The comparison of other regions showed that observed levels were found above maximum residue limits (MRLs) in 50 % of the samples but were in agreement with the studies from neighboring countries like China and Bangladesh. Higher hazard risk index (HRI) values were calculated for dieldrin, methamidophos, o,p′-DDT, diazinon and p,p′-DDT in apple, mango, banana, melon, potato and onion. The review also highlights that data on pesticide residues in foodstuff is scarce which should be overcome by further extending studies from different areas of Pakistan. In order to ascertain the provision of food suitable for human consumption, it is imperative to monitor pesticides in food commodities by the country’s authorities and enforce guidelines based on permissible limits.     

Characterization of distribution of pesticide residues in crop units

The characteristic features of distribution of pesticide residues in crop units and single sample increments were studied based on more than 19,000 residue concentrations measured in root vegetables, leafy vegetables, small-, medium- and large-size fruits representing 20 different crops and 46 pesticides. Log-normal, gamma and Weibull distributions were found to provide the best fit for the relative frequency distributions of individual residue data sets. The overall best fit was provided by lognormal distribution. The relative standard deviation of residues (CV) in various crops ranged from 15–170%. The 100–120 residue values being in one data set was too small to identify potential effects of various factors such as the chemical and physical properties of pesticides and the nature of crops. Therefore, the average of CV values, obtained from individual data sets, were calculated and considered to be the best estimate for the likely variability of unit crop residues for treated field (CV = 0.8) and market samples (CV = 1.1), respectively. The larger variation of residues in market samples was attributed to the potential mixing of lots and varying proportion of non-detects. The expectable average variability of residues in composited samples can be calculated from the typical values taking into account the sample size.     

Simultaneous determination of acidic pesticides in vegetables and fruits by liquid chromatography—tandem mass spectrometry

A sensitive and efficient method has been developed for the simultaneous determination of 73 multi-class acidic pesticides, such as phenoxy acid and sulfonylurea herbicides, in vegetables and fruits. The sample preparation procedure was carefully optimized for the efficient removal of co-extracted matrix components. The method involves extraction of acidic pesticides with acetonitrile containing hydrochloric acid, removal of water from crude extract by salting out, and sequential cleanup by octadecylsilyl silica gel and silica gel columns. For samples containing high amounts of pigments, such as spinach, additional cleanup using a graphitized carbon column was performed prior to liquid chromatography–mass spectrometry (LC–MS/MS) analysis. Recovery tests were performed for five times for each sample of cabbage, spinach, potato, eggplant, orange, and apple fortified at 0.01 mg kg?1. Out of the 73 tested pesticides, 70 for cabbage, 67 for spinach, 69 for potato, 67 for eggplant, 64 for orange, and 70 for apple were within the range of 70–120%, with relative standard deviations below 25%. Nitenpyram and pyrasulfotole showed low recoveries for all the samples tested, probably due to low recoveries from silica gel column. The developed method effectively removed co-extracted matrix components and was highly selective, with no interfering peaks found in the chromatograms of blank samples. The overall results indicate that the developed method is suitable for the quantitative analysis of acidic pesticide residues in vegetables and fruits.     

Determination of disulfoton and permethrin residues in an organic soil and their translocation into lettuce, onion and carrot.

The residues of disulfoton and permethrin in an organic soil and in vegetables grown in soil treated with a granular formulation of the pesticides were determined by gas chromatography. The residues were removed from soil or plant samples by successive extractions with acetone and hexane. Permethrin persisted in the soil for the initial 28 days and declined slowly during the rest of the season but disulfoton after persisting for one week at the applied concentration was degraded in the next two weeks. The insecticides did not translocate into the edible parts of the vegetables but were present in the root system of onion and lettuce. Carrot and lettuce yields were not singificantly different from those of the controls but onion yields were substantially decreased by the use of permethrin.     

蔬菜中有机磷农药残留研究及对策

以西安市为例，研究了蔬菜中有机磷农药的残留问题，分析了不同农药在蔬菜中的残留特征以及不同品种蔬菜、不同类型蔬菜中农药残留的特征，讨论了蔬菜中农药残留量超标的原因及相关对策。     

Enzymatic activity and half-lives of capsaicin,dihydrocapsaicin, and pentadecanoic acid methyl ester in soil sprayed with hot pepper extract

Pest management is facing economic and ecological challenges in the United States and worldwide due to pest resistance, human and environmental hazards caused by use of synthetic pesticides. Natural product-based pesticides offer advantages that they are specific to the target species and typically have unique modes of action with little mammalian toxicity. Studies conducted at Kentucky State University revealed that the insecticidal and acaricidal performance of crude extracts from the fruits of Capsicum species justified the need for developing a natural pesticide formulation for agricultural use. Analysis of hot pepper extracts indicated the presence of three compounds having pesticidal efficacy: capsaicin, dihydrocapsaicin, and pentadecanoic acid methyl ester. The main objectives of this investigation were to: i) determine the half-live (T_1/2 value) of capsaicin, dihydrocapsaicin, and pentadecanoic acid methyl ester in soil sprayed with hot pepper formulation and ii) assess the impact of hot pepper formulation on total soil enzyme activity. Analysis of soil sprayed with pepper extracts indicated that T_1/2 values of capsaicin, dihydrocapsaicin, and pentadecanoic acid methyl ester were 7.3, 1.5, and 10.2 d, respectively. Hydrolysis of the fluorescein diacetate [3, 6-diacetylfluorescein (FDA)], used for measuring overall soil enzyme activities, indicated that total enzyme activities was slightly enhanced by 2% in soil sprayed with hot pepper extracts.     

Comparison of organochlorine pesticides and polychlorinated biphenyls residues in vegetables, grain and soil from organic and conventional farming in Poland

Organic and conventional crops were studied by identifying the relationship between persistent organic pollutants in cereals, vegetables and soil. The residues of organochlorine pesticides and polychlorinated biphenyls (PCBs) were determined in grains (rye and wheat), vegetables (carrots and beets) and soil collected from the fields. PCB residues recorded in the beets from organic farming were as high as 3.71 ppb dry weight (dry wt.), while in the soil from conventional farming of beets 0.53 ppb dry wt. Among vegetables, higher concentrations of pesticides were detected in organically grown beets (190.63 ppb dry wt.). Soil samples from the organic farming contained lower levels of organochlorine pesticide residues compared to the conventional farming. Taking into account toxicity equivalent (TEQ), the conventionally grown carrots accumulated the most toxic PCBs. Non-ortho and mono-ortho PCBs were also noted in the grain of conventionally grown rye and amounted to 3.05 pg-TEQ/g wet wt.     

The effects of particle size, organic matter content, crop residues and dissolved organic matter on the sorption kinetics of atrazine and isoproturon by clay soil

Reliable predictions of the fate and behaviour of pesticides in soils is dependent on the use of accurate ‘equilibrium’ sorption constants and/or rate coefficients. However, the sensitivity of these parameters to changes in the physicochemical characteristics of soil solids and interstitial solutions remains poorly understood. Here, we investigate the effects of soil organic matter content, particle size distribution, dissolved organic matter and the presence of crop residues (wheat straw and ash) on the sorption of the herbicides atrazine and isoproturon by a clay soil. Sorption K_d's derived from batch ‘equilibrium’ studies for both atrazine and isoproturon by <2 mm clay soil were approximately 3.5 L/kg. The similarity of K_oc's for isoproturon sorption by the <2 mm clay soil and <2 mm clay soil oxidised with hydrogen peroxide suggested that the sorption of this herbicide was strongly influenced by soil organic matter. By contrast, K_oc's for atrazine sorption by oxidised soil were three times greater than those for <2 mm soil, indicating that the soil mineral components might have affected sorption of this herbicide. No significant differences between the sorption of either herbicide by <2 mm clay soil and (i) <250 μm clay soil, (ii) clay soil mixed with wheat straw or ash at ratios similar to those observed under field conditions, (iii) <2 mm clay soil in the presence of dissolved organic matter as opposed to organic free water, were observed.     

Formation of non-extractable pesticide residues: observations on compound differences, measurement and regulatory issues

Six major use pesticides (Atrazine, Dicamba, Isoproturon, Lindane, Paraquat and Trifluralin) with differing physico-chemical properties were evaluated for the significance of 'bound' or non extractable residue formation. Investigations were carried out in purpose-built microcosms where mineralization, volatilisation, 'soil water' extractable and organic solvent extractable residues could be quantified. Extractable residues were defined as those accessible by sequential extraction where the solvent used became increasingly non-polar. Dichloromethane was the 'harshest' solvent used at the end of the sequential extraction procedure. (14)C-labelled volatilised and (14)CO(2) fractions were trapped on exit from the microcosm. The pesticides were categorised into 3 classes based on their behaviour. (i) Type A (Atrazine, Lindane and Trifluralin) in which ring degradation was limited as was the formation of non-extractable residues; the remainder of the (14)C-activity was found in the extractable fraction. (ii) Type B (Dicamba and Isoproturon) in which approximately 25% of the (14)C-activity was mineralised and a large portion was found in the non-extractable fraction after 91 days. Finally, Type C (Paraquat) in which almost all of the (14)C-activity was quickly incorporated into the non-extractable fraction. The implications of the data are discussed, with respect to the variability and significance of regulatory aspects of non-extractable residues.     

Determination of organochlorine and organophosphate pesticide residues in fruits,vegetables and sediments

Abstract

A method is described for the determination of organochlorine and organophosphate pesticide residues in fruits, vegetables and sediments. The concentrated solvent extract was sealed in a polymeric membrane tube, dialysed in cyclohexane and the solvent replaced with hexane. The organophosphates were analysed on a specific thermionic detector without further clean‐up. For the organochlorine pesticides the extract was eluted through 3 g of alumina and analysed on GC/ECD. The clean‐up for sediment extract was carried out on a10 g alumina column with 100 mL hexane containing 5% acetone and the eluate was concentrated to 5 mL.

The detection limit for organophosphates on a 40 g sample and a final volume of 10 mL was on the average 0.01 mg/kg. The detection limit for organochlorine pesticides, with the final volume of 25 mL, was 0.005 mg/kg for all pesticides except for p,p'‐DDT and endosulfan sulphate, which was 0.01 mg/kg.

The detection limit for oganochlorine pesticides in sediment, with the final volume of 2 mL, was less than 1 μg/kg and for organophosphate pesticides less than 10 μg/kg when the final volume was made to 0.5 mL. At the detection limits the method produced a very high coefficient of variation for both organochlorine and organophosphate pesticides.     

Estimation of sampling uncertainty for determination of pesticide residues in plant commodities

In order to provide residue data for refining the estimated sampling uncertainty, a coordinated research program was initiated for performing field studies on residues in individual items of leafy vegetables, small and large crops. The trials were carried out in 13 countries with 3 small fruits, 5 large crops, 2 medium/large crops and 3 leafy vegetables. The 25 pesticide active ingredients applied represented the dicarboximide (3), organophosphorus (8), synthetic pyrethroids (5), phthalimides (2), organochlorine (1) and other types of pesticides (6). In addition, 11 supervised field trials were performed in grapes and lettuce by the pesticide manufacturers, and their results were provided for evaluation. The studies represented actual agriculture practice around the world, and provide reliable data for estimation of sampling uncertainty. Based on the 12346 residue data, the best estimate for the relative sampling uncertainty for composite samples, assuming sample size of 10 for small crops and leafy vegetables and 5 for large crops, with 95% confidence limits in brackets are: small commodities: 0.25 (0.20–0.29); Brassica leafy vegetables: 0.20 (0.16–0.24); large commodities: 0.33 (0.29–0.38).     

Determination of disulfoton and permethrin residues in an organic soil and their translocation into lettuce,onion and carrot 1

Abstract

The residues of disulfoton and permethrin in an organic soil and in vegetables grown in soil treated with a granular formulation of the pesticides were determined by gas chromatography. The residues were removed from soil or plant samples by successive extractions with acetone and hexane. Permethrin persisted in the soil for the initial 28 days and declined slowly during the rest of the season but disulfoton after persisting for one week at the applied concentration was degraded in the next two weeks. The insecticides did not translocate into the edible parts of the vegetables but were present in the root system of onion and lettuce. Carrot and lettuce yields were not significantly different from those of the controls but onion yields were substantially decreased by the use of per‐methrin.     

Residue behavior of etoxazole under field conditions in Egypt and estimation of processing factors during the production of strawberry juice and purée

Abstract

The degradation under field conditions and the residue behavior of etoxazole during juicing and purée making was evaluated. Etoxazole residues were determined by HPLC-UV at six different Pre Harvest Intervals (PHIs) as to estimate the degradation of residue in fruits. Samples with significant residues were processed and residue were determined after juicing and purée making. The effect of washing was also estimated. Processing Factors (PFs) for etoxazole after each step were less than 1 and the PFs of the overall processes were lower than 0.85 for washing fruits, 0.13 for juice and 0.04 for purée. The studied processes could obviously reduce the pesticide residues that are present in the raw strawberries. Uncertainties in the use of the PFs were identified due to the potential formation of metabolites during the processes.     

Contamination of vegetables of different seasons with organophosphorous pesticides and related health risk assessment in northern India

India is an agrarian country. The use of pesticides, herbicides and fungicides were introduced in India during the mid-sixties, which are now being used on a large scale and is a common feature of Indian agriculture. The main intention of the introduction of pesticides was to prevent and control insects, pests and diseases in the field crops. Initially the use of pesticides reduced pest attack and paved way for increasing the crop yield as expected. Simultaneously, increased use of chemical pesticides has resulted in contamination of environment and also caused many long-term affect on the society. In the present study an effort has been made to evaluate the residual concentration of selected organophosphorous pesticides (methyl parathion, chlorpyriphos and malathion) in vegetables grown in different seasons (summer, rainy and winter). Data obtained was then used for estimating the potential health risk associated with the exposure to these pesticides. The pesticides residue concentrations in vegetables of different season shows that the winter vegetables are the most contaminated followed by summer and rainy vegetables. The concentration of the various pesticides were well below the established tolerances but continuous consumption of such vegetables even with moderate contamination level can accumulate in the receptor's body and may prove fatal for human population in the long term. The analysis of health risk estimates indicated that chlorpyriphos and malathion did not poses a direct hazard, however, exposure to methyl parathion has been found to pose some risk to human health.     

Determination of organochlorine and organophosphate pesticide residues in fruits, vegetables and sediments.

A method is described for the determination of organochlorine and organophosphate pesticide residues in fruits, vegetables and sediments. The concentrated solvent extract was sealed in a polymeric membrane tube, dialysed in cyclohexane and the solvent replaced with hexane. The organophosphates were analysed on a specific thermionic detector without further clean-up. For the organochlorine pesticides the extract was eluted through 3 g of alumina and analysed on GC/ECD. The clean-up for sediment extract was carried out on a 10 g alumina column with 100 mL hexane containing 5% acetone and the eluate was concentrated to 5 mL. The detection limit for organophosphates on a 40 g sample and a final volume of 10 mL was on the average 0.01 mg/kg. The detection limit for organochlorine pesticides, with the final volume of 25 mL, was 0.005 mg/kg for all pesticides except for p,p'-DDT and endosulfan sulphate, which was 0.01 mg/kg. The detection limit for organochlorine pesticides in sediment, with the final volume of 2 mL, was less than 1 microgram/kg and for organophosphate pesticides less than 10 micrograms/kg when the final volume was made to 0.5 mL. At the detection limits the method produced a very high coefficient of variation for both organochlorine and organophosphate pesticides.     

Results of the monitoring program of pesticide residues in organic food of plant origin in Lombardy (Italy)

Organic agriculture, with its restrictions on the use of synthetic chemical inputs, seems to offer a low-residue alternative to conventional methods. In Europe, the Council Regulation n. 2092/91/EEC regulates the production and trade of organic products and foodstuffs; national and regional legislation in Italy gives specific guidance on the surveillance of organic agriculture. However, monitoring of specific chemical residues in organic foodstuffs is part of the regular controls on food, aiming to safeguard consumer's health. Monitoring programs are coordinated at the national level by the Ministry of Health and at local level by Regional authorities. In Lombardy, in accordance with the provisions of the General Directorate of Health of the Region and under the supervision of the 15 Local Health Units, a monitoring program of pesticide residues in food of plant origin is undertaken every year. The International Centre for Pesticides and Health Risk Prevention (ICPS), on behalf of the General Directorate of Health of the Region of Lombardy, has been collecting and elaborating the data resulting from the analysis of food samples, carried out by the local laboratories. During the period 2002–2005, a total of 3508 samples food of plant origin were analyzed for pesticide residues, among which were 266 samples of organic farming products. Commodities were classified into groups (citrus fruits, legumes, vegetables, potatoes, processed products, cereals, and fruit other than citrus) and the outcomes of the analyses were reported by year, origin of the sample and presence/absence of pesticide residues. Results showed that the vast majority of organic farming products were in conformity with the relevant legislation and did not contain detectable pesticide residues. A limited amount of samples had residues at concentration below the Maximum Residue Limit (MRL). Only in one sample the residue level was above the MRL, however it did not pose a concern for public health, as demonstrated by the outcomes of dietary risk assessment. Organic fruits and vegetables can be expected to contain fewer agrochemical residues than conventionally grown alternatives. There is a widespread belief that organic agriculture products are safer and healthier than conventional foods. It is difficult to come to conclusions, but what should be made clear to the consumer is that “organic” does not automatically equal “safe”. In the absence of adequate comparative data, additional studies in this area of research are required.     

Organic contamination of Italian and Tunisian culinary herbs and spices

Contaminants belonging to various classes, as polychlorobiphenyls, polycyclic aromatic hydrocarbons, organochlorine pesticides, organophosphorous pesticides, pyrethroid insecticides, fungicides, herbicides, synergists, carbamates, acaricides and insect growth regulators were simultaneously analysed by GC-MS/MS in 118 Italian and Tunisian culinary herbs and spices. The results obtained in Italian samples shown that laurel samples were the most contaminated with the presence of 15 residues on 140, whereas in rosemary (max value of 35?ng/g for cis-chlorfenyvinphos) and oregano (max value of 118.16?ng/g for ethion) some occasional residues can be observed, but always lower than the maximum residue levels; all the others samples shown no contamination. Among Tunisian samples, only rosemary contains a notably high content of pollutants exceeded the EU maximum residue limits (i.e., alachlor and phosalone with level of 359.2 and 43.3?ng/g, respectively), while oregano was determined to be free of contaminant residues. Considering the comparison among the different organic pollutants in Italian and Tunisian spices and herbs evaluated and the differences observed in this study a harmonization of regulation on contaminant residues in herbs and spices for human consumption should be needed, considering their increased use in diet and cooking.