Pesticide residues intake of French adults under increased consumption of fresh fruits and vegetables – A theoretical study

The increase of fresh vegetable and fruit (FVF) intake could contribute to the prevention of obesity and several major pathologies and thus represents a major public health goal in industrial countries. Nutritional recommendations for increased consumption of FVF could lead to ingestion of unwanted amounts of pesticides. This study was undertaken to evaluate theoretical exposure of French adults to pesticide residues under increasing amounts of FVF intake. Balanced menus with 200 – 400 – 600 – 800 and 1200 g FVF/day were established. Amounts of active substances brought by every FVF vector, at the maximum residue level (MRL) were summed up to determine the intake for each active substance. Values were compared to the Acceptable Daily Intake (ADI) to point out any potential over exposure. A maximalistic approach was adopted and no reducing factor due to processing was taken into account. It was found that under minimal recommended consumption of fruit and vegetables (400 g/d), no active substance reached the ADI, but 18 vs 144 were over 10% of the ADI. Raising FVF to 600 g/d increased the number of active substances over 10 % of the ADI to 24, but again in no case was the ADI exceeded. Doubling the intake to 800 g/d gives values over the ADI for 2 active substances only (cyhexatin and thirame). It was concluded that the increase in fruit and vegetables up to 800 g per day should not expose adults over the ADIs for a majority of authorized pesticides. In this regard, residues levels of ten active substances in fruit and vegetables should deserve particular attention.     

Heavy metal content in vegetables and fruits cultivated in Baia Mare mining area (Romania) and health risk assessment

Information about heavy metal concentrations in food products and their dietary intake are essential for assessing the health risk of local inhabitants. The main purposes of the present study were (1) to investigate the concentrations of Zn, Cu, Pb, and Cd in several vegetables and fruits cultivated in Baia Mare mining area (Romania); (2) to assess the human health risk associated with the ingestion of contaminated vegetables and fruits by calculating the daily intake rate (DIR) and the target hazard quotient (THQ); and (3) to establish some recommendations on human diet in order to assure an improvement in food safety. The concentration order of heavy metals in the analyzed vegetable and fruit samples was Zn?>?Cu?>?Pb?>?Cd. The results showed the heavy metals are more likely to accumulate in vegetables (10.8–630.6 mg/kg dw for Zn, 1.4–196.6 mg/kg dw for Cu, 0.2–155.7 mg/kg dw for Pb, and 0.03–6.61 mg/kg dw for Cd) than in fruits (4.9–55.9 mg/kg dw for Zn, 1.9–24.7 mg/kg dw for Cu, 0.04–8.82 mg/kg dw for Pb, and 0.01–0.81 mg/kg dw for Cd). Parsley, kohlrabi, and lettuce proved to be high heavy metal accumulators. By calculating DIR and THQ, the data indicated that consumption of parsley, kohlrabi, and lettuce from the area on a regular basis may pose high potential health risks to local inhabitants, especially in the area located close to non-ferrous metallurgical plants (Romplumb SA and Cuprom SA) and close to T?u?ii de Sus tailings ponds. The DIR for Zn (85.3–231.6 μg/day kg body weight) and Cu (25.0–44.6 μg/day kg body weight) were higher in rural areas, while for Pb (0.6–3.1 μg/day kg body weight) and Cd (0.22–0.82 μg/day kg body weight), the DIR were higher in urban areas, close to the non-ferrous metallurgical plants SC Romplumb SA and SC Cuprom SA. The THQ for Zn, Cu, Pb, and Cd was higher than 5 for <1, <1, 12, and 6 % of samples which indicates that those consumers may experience major health risks.     

Chlorpyrifos residues levels in fruits and vegetables after field treatment

Chlorpyrifos (O,O-diethyl O-3,5,6-trichloro-2-pyridyl phosphorothioate) was applied with three different formulations on oranges, peaches, tomatoes, wine and table grapes, and its behaviour was evaluated after field treatment. The formulations applied were emulsifiable concentrates (EC), microencapsulates (ME), and wettable granules (WG). The residues were similar in all crops studied in the EC and WG experiments, except peaches with WG treatment, the residue amount was lower than EC values. Tomatoes which were grown in greenhouse showed similar residues in all treatments just after treatment. Wine and table grapes showed different decline curves in the EC experiments ascribable to the different growing technology. Instrumental limit of determination (LOD) and limit of quantification (LOQ) for all matrices were 0.01, and 0.03 mg kg?1, respectively. Repeated treatments showed that Chlorpyrifos can accumulate leading to residue levels at the preharvest interval (PHI) over the maximum residue level (MRL), especially on oranges and peaches. Among the formulates used ME showed the higher risk of residues over the MRL at harvest.     

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 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.     

Multiresidue analysis of pesticides in fruits and vegetables by gas chromatography-mass spectrometry

A multiresidue method was assessed for the determination of several pesticides (organochlorine, organophosphorus, pyrethroids, triazole, amidine) using gas chromatography/mass spectrometry. The extraction of pesticides was carried out by liquid-liquid extraction (LLE) and solid-phase extraction (SPE) using two types of columns (CN and C18). The extracts were cleaned by the addition of florisil, the pesticides were separated by capillary column gas chromatography and detected by mass spectrometry in the electron impact mode. The extraction using C18 column provided the best results for most of the analyzed pesticides. The majority of pesticides recoveries from the four fruits and vegetables (apples, pears, tomatoes and pepper) were greater than 60%. Linearity and precision were satisfactory. The estimated limits of detection and limits of quantification ranged from 0.01 to 0.1 mg/kg and from 0.02 to 0.3 mg/kg, respectively. The proposed procedure was found to be useful for the multiresidue analyses of pesticides in agricultural products for routine monitoring programs.     

Multiresidue analysis of pesticides in fruits and vegetables by gas chromatography-mass spectrometry

A multiresidue method was assessed for the determination of several pesticides (organochlorine, organophosphorus, pyrethroids, triazole, amidine) using gas chromatography/mass spectrometry. The extraction of pesticides was carried out by liquid-liquid extraction (LLE) and solid-phase extraction (SPE) using two types of columns (CN and C18). The extracts were cleaned by the addition of florisil, the pesticides were separated by capillary column gas chromatography and detected by mass spectrometry in the electron impact mode. The extraction using C18 column provided the best results for most of the analyzed pesticides. The majority of pesticides recoveries from the four fruits and vegetables (apples, pears, tomatoes and pepper) were greater than 60%. Linearity and precision were satisfactory. The estimated limits of detection and limits of quantification ranged from 0.01 to 0.1 mg/kg and from 0.02 to 0.3 mg/kg, respectively. The proposed procedure was found to be useful for the multiresidue analyses of pesticides in agricultural products for routine monitoring programs.     

Determination of etoxazole residues in fruits and vegetables by SPE clean-up and HPLC-DAD

A method for determination of etoxazole residues in apples, strawberries and green beans was developed and validated. The analyte was extracted with acetonitrile from foodstuff and a charcoal-celite cartridge was used for clean-up of raw extracts. Reversed phase high performance liquid chromatography with photodiode array detector (HPLC-DAD) was used for the determination and quantification of etoxazole residues in the studied samples. The calibration graphs of etoxazole in a solvent or three blank matrixes were linear within the tested intervals 0.01–2 mg L^?1, with correlation coefficient of determination >0.999. The combined solid phase extraction (SPE) clean-up and the chromatographic method steps were sensitive and reliable for simultaneous determination of etoxazole residues in the studied samples. The average recoveries of etoxazole in the tested foodstuffs were between 93.4 to 102% at spiking levels of 0.01, 0.10, and 0.50 mg kg^?1, with relative standard deviations ranging from 2.8 to 4.7%, in agreement with directives for method validation in residue analyses. The limit of detection (LOD) of the HPLC-DAD system was 100 pg. The limit of quantification of the entire method was 0.01 mg kg^?1.     

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.     

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.     

A cost-effective screening method for pesticide residue analysis in fruits, vegetables, and cereal grains

This paper reports the results of studies performed to investigate the potential of applying thin layer chromatography (TLC) detection in combination with selected extraction and cleanup methods, for providing an alternative cost-effective analytical procedure for screening and confirmation of pesticide residues in plant commodities. The extraction was carried out with ethyl acetate and an on-line extraction method applying an acetone-dichloromethane mixture. The extracts were cleaned up with SX-3 gel, an adsorbent mixture of active carbon, magnesia, and diatomaceous earth, and on silica micro cartridges. The Rf values of 118 pesticides were tested in eleven elution systems with UV, and eight biotest methods and chemical detection reagents. Cabbage, green peas, orange, and tomatoes were selected as representative sample matrices for fruits and vegetables, while maize, rice, and wheat represented cereal grains. As an internal quality control measure, marker compounds were applied on each plate to verify the proper elution and detection conditions. The Rf values varied in the different elution systems. The best separation (widest Rf range) was achieved with silica gel (SG)--ethyl acetate (0.05-0.7), SG--benzene, (0.02-0.7) and reverse phase RP-18 F-254S layer with acetone: methanol: water/30:30:30 (v/v) (0.1-0.8). The relative standard deviation of Rf values (CV(Rf)) within laboratory reproducibility was generally less than 20%, except below 0.2 Rf, where the CVRf rapidly increased with decreasing Rf values. The fungi spore inhibition, chloroplast inhibition, and enzyme inhibition were found most suitable for detection of pesticides primarily for confirming their identity or screening for known substances. Their use for determination of pesticide residues in samples of unknown origin is not recommended.     

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.     

Evaluation of pesticide residues in fruits and vegetables from the Aegean region of Turkey and assessment of risk to consumers

Environmental Science and Pollution Research - Pesticides may cause a potential risk to human health when applied in excess to control pests, diseases, and weeds in crop fields. In the current...     

Rapid determination of polar pesticides and plant growth regulators in fruits and vegetables by liquid chromatography/tandem mass spectrometry

ABSTRACT

A simple high-throughput liquid chromatography/tandem mass spectrometry (LC-MS/MS) multiresidue analysis method was developed for the simultaneous determination of polar pesticides, plant growth regulators and other polar compounds. These included amitrole, chlormequat, mepiquat, cyromazine, ETU, PTU, perchlorate, and daminozide using a mixed-mode column. A 10 g test portion was shaken with acidified methanol for 10 min. After centrifugation, the sample extract was injected and analyzed within 11 min by LC-MS-MS. This column eliminated the need for derivatization or the use of ion paring reagent. Two MS-MS transitions were monitored in the method for each target compound to achieve true positive identification. Eight isotopically-labeled internal standards corresponding to each analyte were used to correct for matrix suppression effect and/or instrument signal drift. The average recovery for all analytes at 20, 40, and 250 ng/g (n = 6) ranged from 73–136%, with a relative standard deviation of ≤ 20%.     

Validation of an efficient method for the determination of pesticide residues in fruits and vegetables using ethyl acetate for extraction

In this study, a version of the "quick, easy, cheap, effective, rugged, and safe" (QuEChERS) method was modified to use ethyl acetate (EtOAc) rather than acetonitrile (MeCN) for extraction in the determination of multiple pesticide residues in fruits and vegetables. EtOAc is better suited than MeCN for gas chromatographic (GC) analysis with electron capture detection (ECD) and nitrogen-phosphorus detection (NPD). The method entailed extraction of 30 g chopped sample plus 5 g NaHCO(3) and 30 g anhydrous Na(2)SO(4) with 60 mL EtOAc using a probe blender. After a centrifugation step, removal of residual water and cleanup were performed using dispersive solid-phase extraction (dispersive-SPE) with MgSO(4) and primary secondary amine (PSA) sorbent. (14)C-labeled chlorpyrifos with liquid scintillation counting was used to assist in optimizing and characterizing the method, and GC-ECD and GC-NPD were used for analysis of 24 selected pesticides. The method was validated using tomato, apple and frozen green bean matrices spiked at 0.05, 0.5, and 5 mg/kg. For 22 of the analytes, recoveries averaged 93% for all three commodities over the validation range with a relative standard deviation of 10% (n = 1182). Lower recoveries of dichlorvos were obtained with the method and iprodione determination was compromised in the green beans by an interfering peak. Typical limits of detection were 0.005-0.01 mg/kg with the method.     

Validation of a multiclass multiresidue method and monitoring results for 210 pesticides in fruits and vegetables by gas chromatography-triple quadrupole mass spectrometry

A rapid, sensitive, accurate and reliable multiresidue method for the identification and quantification of 210 relevant pesticides in four representative fruit and vegetable commodities (tomato, potato, spring onion and orange) has been developed and validated by gas chromatography in tandem with triple quadrupole mass spectrometry. The method has been fully validated and applied to 292 samples from different countries. Prior to instrumental analysis, an extraction procedure based on a sample extraction of multiclass analytes, using the ethyl acetate method was employed. Mass spectrometric conditions were individually optimized for each compound in the selected reaction monitoring (SRM) mode to achieve maximum sensitivity. The pesticides were separated in less than 25 min. This was followed by an exhaustive control of the retention times. The Retention Time Locking Method was applied, working at a constant pressure throughout the analysis. System maintenance was reduced by using a purged capillary flow device that provided backflush capabilities by reversing column flow immediately after elution of the last compound of interest. Istotopically labelled internal standards were employed to improve the quality of the analytical results.     

Phthalic acid esters in grains,vegetables, and fruits: concentration,distribution, composition,bio-accessibility,and dietary exposure

Environmental Science and Pollution Research - Grain, vegetable, and fruit samples were collected from Xi’an City in Northwest China and analyzed for the characteristics, bio-accessibility,...     

Mercury and organochlorine content of Dipper Cinclus cinclus eggs in south-west Ireland: trends during 1990-1999

A sample of 124 deserted/infertile dipper (Cinclus cinclus) eggs was collected in south-west Ireland during six seasons (1990-1994 and 1999) and analysed for mercury and organochlorines. Mercury was detected in three of the 6 years but no trend was observed. DDT occurred above the limit of detection in only two eggs, one each in 1993 and 1994. In contrast, two derivatives of DDT (DDE and TDE) were found much more commonly. DDE occurred in over 87% of eggs, while TDE contamination was less widespread and reached a maximum of 60% in 1993, with none detected in 1991 or 1999. There was no trend in occurrence of DDE or TDE across years. PCB contamination was present consistently over the 10-year period, with little change in the proportion of contaminated eggs collected over time. In all years, the lowest recorded occurrence of total PCBs was 69% expressed on a formulation basis as Arochlor 1254. PCB congeners 138, 153 and 180 dominated. The congener pattern was similar across years with the exception of 1990 when congener 118 dominated. A distinct trend of high values of contaminants was observed in 1990 and 1993. In 1990, PCB 118 was the dominant contaminant, while in 1993, HEOD, DDE, PCB 138 and PCB 153 were primary contributors to the observed result. Other contaminants (HCB, PCB 101, gamma-HCH, PCB 170 and PCB 180) showed little obvious patterns between years and occurred at relatively low levels. No pattern was observed in contaminants when eggs were grouped according to river or altitude. These data provide a baseline for organochlorine contamination levels in Irish freshwater ecosystems against which future trends can be assessed.     

Mercury content in roach (Rutilus rutilus L.) in circumneutral lakes--effects of catchment area and water chemistry

The environmental influence on the mercury content in roach (Rutilus rutilus L.) is investigated using partial least square regression on 46 environmental variables describing the land use in the catchment area, various catchment area and lake characteristics, lake water chemistry, and fish stock. The Hg content in the fish from the 78 investigated circumneutral lakes is heavily influenced by the land use in their surroundings. The boreal forest lakes possessed the highest Hg levels in roach, whereas fish from lakes surrounded by arable land had lower levels. The Hg levels also showed a negative relationship to the amount of dissolved ions and the total amount of nutrients in lake water. Lake pH did not have any significant influence on the Hg content in roach in these non-acidified lakes. The Hg levels in lakes influenced by large amounts of wetland were less well explained by the presently investigated environmental variables, which implies that the Hg burden in fish from this kind of lake is governed by other factors.