MRL Values Research Articles

English

This study was conducted to assess the presence of pesticides residues in wheat from Misha woreda, Haiya Zone, Ethiopia. Samples of wheat were collected during the period December 2015 to August 2016. Gas chromatograph (GC-MS) detection was employed after Liquid-Liquid extraction (LLE). The concentration levels of eight pesticides have been investigated in both wheat samples in farm and purchased from storage facilities. Since the method was out of scope, it was validated before application to the analysis of these pesticides. The spiked recovery results for five analytes were within the acceptable international standard. The LOD value and LOQ value are below the LCC and MRL of the analyte. Method validation for this study maintained a RSD <20% and percentage recoveries were in the range of 80-110%. The %RSD of all detected analytes was less than the acceptable international standard. Results show that out of the residues of eight analytes determined, four analytes (2,4-D; aldrin; Endosulfan; p,p-DDT) were detected in both field (pre harvest) samples and stored (post harvested) sample, whereas the remaining analytes were not detected at all. In general, the concentrations of these analytes in the wheat samples are in the order: 2, 4-D >aldrin>p,p-DDT >Endosulfan. The study observed that from the detected analytes, none of them are above the international MRL values and suggested that stringent monitoring of use of pesticides in agriculture and food storage is required. Key words: Pesticide residue, wheat, Gas chromatography–mass spectrometry (GC-MS), method validation, maximum residue limit.

Large scale studies of the influence of GMO-based corn diet after 6 months of consumption in Wistar rats

Wistar rats were fed during 6 months with 33% maize, either non genetically modified or containing MON810 or NK603 (11% and 33%). Extensive chemical analysis by MS and NMR profiling and targeted analyses were undertaken to qualify the harvests and quantify in maize and pellets macro- and micronutrients, anti-nutrients and undesirable substances and contaminants. All diets contained low levels (50 to 100 fold lower than the MRL values) of undesirable substances. Thirty rats per gender were fed with 8 different diets: MON810 (11% and 33%) plus isogenic control, NK603 (11% and 33% ± glyphosate treatment) and isogenic control. Rats were sacrificed after 3 months (sub-group A, 10 rats per diet, per gender) and 6 months (sub-group B, 12 rats and C, 8 rats per diet, per gender). Urine were collected in metabolic cages and blood at 90 (sub-group A), 90/135/180 (sub-group B) and 180 days of feeding (sub-group C). In addition to classical toxicological analysis we performed metabolomics and hormones quantification in blood and urine, transcriptomics on liver and kidney, gut barrier analysis, kidney and gonads targeted immunohistology. Statistical analyses were conducted first blindly and thereafter on the basis of relevant pair-wise comparison. We easily discriminate the rat gender or maize origin. Among the numerous statistically significant differences in pair-wise comparisons some concerned GMO and non-GMO, but no biological relevance could be established due to the lack of differences in biologically linked variables, dose-response effects or clinical disorders.

Oral fluid as material for non-invasive antibiotics detection in pigs

Intensive and massive pig production often contributes to excessive administration of antibacterials in veterinary medicine. The misuse and failures to follow the label directions of antibiotics, as well as withdrawal inadequacy, can lead to their residue occurrence in products of animal origin. The residue of drugs may result in many biological adverse effects and allergic reactions in consumers as well as the spread of drug-resistant bacteria and bacterial resistance acquisition. Consolidation of pig production requires ensuring adequate conditions of the maintenance of animals with high health conditions, consistent with the guidelines for animal welfare. At the same time, the control of antibiotics in animals is an important element providing the high quality of pigs breeding, as well as the protection of consumers. In residue monitoring programs, the primary material for the control of antibiotics presence in pigs are tissue samples, collected from animals at the slaughterhouse. However, post-mortem analysis does not give the opportunity of monitoring the usage of antibiotics on the farm during the breeding of animals. In ante mortem drug analysis blood can be used as a diagnostic biological matrix; however, blood sampling is connected with certain disadvantages for the animals and the staff responsible for material collection. The post-mortem detection and presence of antibiotic residues in pork tissues above MRL values very often lead to the recall and destruction of significant quantities of meat, which may contribute to economic losses. Therefore, a strong need to find and implement new methods for ante-mortem detection of antibiotics in animals exists, which minimize interference in animal welfare. The results of preliminary studies demonstrate that oral fluid seems to be an effective tool for monitoring the reasonable treatment and residue avoidance. It offers a cost-effective approach for the screening of large populations of animals. The method of oral fluid collection with cotton rope usage allows for the rapid sampling of material. In case of positive oral fluid ante-mortem analysis results, the slaughtering of animals can be delayed, which can bring the avoidance of costs connected with the non-compliant pig meat destruction.

MEASUREMENT OF CHEMICAL PESTICIDE RESIDUES IN CAPSICUM GROWN IN SOUTH INDIA

Capsicum (also known as peppers) is a genus of flowering plants in the nightshade family Solanaceae.Capsicum grown in five districts of Karnataka (Bangalore urban, Bangalore rural, Kolar, Chikkaballapura and Ramanagara) were analyzed for 20 pesticide residues by Gas liquid Chromatography equipped with ECD and FCD. Recovery studies performed at 0.1, 0.5 and 1.0mg kg-1 fortification levels of each compound and recoveries obtained ranged from 743%-97% with relative standard deviation lower than 7.5%. The method showed the good linearity over the range assessed 0.01-1.0mg kg-1 respectively. Capsicum was analyzed for acephate, chlorphyriphos, dichlorvos, phorate, deltamethrin, fenvalerate and cyfluthrin-ȕ residues. Except phorate none of the residues in capsicum crossed the MRL. Phorate was detected in samples from Ramanagara district while 12.5% samples from Bangalore rural, chikkaballapura and Kolar district showed phorate residues exceeding the MRL value of 0.05mg kg-1. Cyfluthrin-ȕ residue is in higher proportion in capsicum samples from Bangalore rural than Bangalore urban. It is therefore required to investigate extensively the monitoring studies covering all the vegetables crops from different agro-climatic zones of Karnataka to know the exact status of pesticide contamination.

Aflatoxin M1 in raw and UHT cow milk collected in Bosnia and Herzegovina and Croatia

Aflatoxin M1 (AFM1) concentrations were determined in raw and UHT cow milk samples collected in different regions of Bosnia and Herzegovina and Croatia during the autumn months of 2014. The mean AFM1 levels in the raw milk samples were (ng/kg): 6.22 in Bosnia and Herzegovina, 5.65 in Croatia. In all except one milk sample, AMF1 levels were below the LOQ value of 34.2 ng/kg (ELISA method). In four milk samples, AFM1 concentrations exceeded the EU MRL of 50 ng/kg. Samples were subjected to LC-MS/MS analysis which confirmed elevated values determined by ELISA. Elevated levels were in the range 56.6–132.6 ng/kg. Two positive milk samples from Bosnia and Herzegovina originated from Una Sana Canton, two from Croatia from eastern Croatia. The highest AFM1 levels of 132.6 ng/kg was measured in milk from eastern Croatia. In 214 samples of processed UHT milk from Bosnia and Herzegovina and Croatia, AFM1 ranged from 2.29 ng/kg to 21.4 ng/kg, all below the LOQ value. AFM1 exceeded the EU MRL value in only 0.62% of milk samples, indicating the sporadic use of contaminated feedstuff at farms in both countries.

Modification of the existing maximum residue levels for metconazole in various crops

In accordance with Article 6 of Regulation (EC) No 396/2005, the evaluating Member State (EMS) Belgium received an application from BASF SE Crop Protection to set import tolerances for the active substance metconazole in blueberries, potatoes, tropical root and tuber vegetables, pulses and sunflower seeds imported from the United States of America and/or Canada. Belgium drafted an evaluation report in accordance with Article 8 of Regulation (EC) No 396/2005 which was submitted to the European Commission and forwarded to EFSA. The submitted trials are sufficient to derive MRL values of 0.5 mg/kg for blueberries, the limit of quantification of 0.04 mg/kg for potatoes and tropical root and tuber vegetables, 0.15 mg/kg for pulses and 1 mg/kg for sunflower seeds. However, since the MRL values on blueberries and sunflower seeds are currently set at a level of 0.4 mg/kg and 0.7 mg/kg, respectively, in North America, EFSA proposes to set the import tolerances at these levels for these two plant commodities. Adequate analytical enforcement methods are available to control the residues of metconazole on the commodities under consideration. Based on the risk assessment results, EFSA concludes that the reported uses of metconazole on the crops under consideration will not result in a consumer exposure exceeding the toxicological reference values for the active substance, therefore are unlikely to pose a consumer health risk.

Scenario of organophosphate pollution and toxicity in India: A review.

The present study on organophosphate deals with the reports on pollution and toxicity cases throughout India. The use of pesticides was introduced in India during the 1960s which are now being used on a large scale and represents the common feature of Indian agriculture. Use of organophosphates as a pesticide came as an alternative to chlorinated hydrocarbons due to their easy degradability. Although these xenobiotics degrade under natural condition, their residues have been detected in soil, sediments, and water due to their non-regulated usage practice. The over-reliance on pesticides has not only threatened our environment but contaminations of organophosphate residues have been also detected in certain agricultural products like tea, sugars, vegetables, and fruits throughout India. This paper highlights many of the cases where different organophosphates have been detected exceeding their respective MRL values. Some organophosphates detected are so hazardous that even WHO has listed them in class 1a and class 1b hazardous group. Presence of their residues in blood, milk, honey, and tissues of human and animals revealed their excessive use and bioaccumulating capabilities. Their intentional or unintentional uptake is causing thousands of deaths and severity each year. Most of the toxicity cases presented here are due to their uptake during a suicidal attempt. This shows how easily these harmful substances are available in the market.

Dissipation kinetics and risk assessment of thiamethoxam and dimethoate in mango.

Thiamethoxam and dimethoate are two insecticides used to control hoppers and inflorescence midges in mango. Thiamethoxam (0.008 and 0.016%) and dimethoate (0.06 and 0.12%) were sprayed on Dashehari mango trees during the pre-mature stage of fruit (first week of May) to study their dissipation kinetics and risk assessment in mango fruit. Thiamethoxam dissipated in fruit from 1.93 and 3.71 mg kg(-1) after 2 h of spraying to 0.08 and 0.13 mg kg(-1) after 20 days of spraying at single and double doses, respectively. Its residue did not persist beyond 20 days in fruit. Dimethoate dissipated in fruit from 2.81 and 5.34 mg kg(-1) after 2 h of application to 0.12 and 0.19 mg kg(-1) after 10 days of application at single and double doses, respectively. No residue was detected in fruit beyond 10 days after its application. Both ready-to-harvest mature mango fruit and pulp (after 40 days of spraying) were free from any residues of these insecticides at both the concentration levels. The rate of dissipation of these insecticides followed first-order kinetics in fruit with residual half-lives of 4.0 to 4.5 days for thiamethoxam and 2 days for dimethoate. Based on their MRL values of 0.5 and 2.0 mg kg(-1) in mango, pre-harvest intervals of 7 and 11 days, and 6 and 7 days were suggested for thiamethoxam and dimethoate, respectively, after spraying at single and double doses. The theoretical maximum residue contribution (TMRC) values for both the insecticides, calculated for residues corresponding to each sampling date, were found to be below the maximum permissible intake (MPI) values on mango fruit (except for dimethoate double dose up to 3 days); hence, both thiamethoxam and dimethoate could be considered non-hazardous to consumers at the above doses and time intervals.

Occurrence and spatial distribution of pesticide residues in butter and ghee (clarified butter fat) in Punjab (India).

The present study was undertaken to monitor organochlorine, organophosphate, and synthetic pyrethroid pesticide residues in butter (n = 55) and ghee (n = 56) samples collected from three different regions of Punjab. The estimation of pesticide residues was done by multiple residue analytical technique using gas chromatography equipped with GC-ECD and GC-FTD. The confirmation of residues was done on gas chromatography mass spectrometry in both selective ion monitoring (SIM) and scan mode. Results indicated the presence of hexacholorocyclohexane (HCH) and p,p' DDE as predominant contaminant in both butter and ghee. Residues of HCH were detected in 25 and 23% samples of butter and ghee, respectively, while residues of p,p' DDE were recorded in 29 and 25% of butter and ghee samples, respectively. None of the butter and ghee sample violated the MRL values of 200 ng g(-1) for HCH and 1250 ng g(-1) for dichorodiphenyl tricholorethane (DDT). The presence of endosulfan, cypermethrin, fenvalerate, deltamethrin, and chlorpyrifos were observed in a few butter and ghee samples at traces. The spatial variation for comparative occurrence of pesticide residues indicated higher levels in the south-western region of Punjab. Additionally, the temporal variation indicated the significant reduction of HCH and DDT levels in butter and ghee in Punjab.

Ivermectin Pharmacokinetics, Metabolism, and Tissue/Egg Residue Profiles in Laying Hens.

The goals were to determine the ivermectin (IVM) plasma pharmacokinetics, tissue and egg residue profiles, and in vitro metabolism in laying hens. Experiments conducted were (1) 8 hens were intravenously treated with IVM and blood samples taken; (2) 88 hens were treated with IVM administered daily in water (5 days) (40 were kept and their daily eggs collected; 48 were sacrificed in groups (n = 8) at different times and tissue samples taken and analyzed); (3) IVM biotransformation was studied in liver microsomes. Pharmacokinetic parameters were AUC = 85.1 ng·day/mL, Vdss = 4.43 L/kg, and T1/2el = 1.73 days. Low IVM tissue residues were quantified with the highest measured in liver and skin+fat. IVM residues were not found in egg white, but significant amounts were quantified in yolk. Residues measured in eggs were greater than some MRL values, suggesting that a withdrawal period would be necessary for eggs after IVM use in laying hens.

Dissipation kinetics and residue of LH-2010A in cucumber and soil under greenhouse condition

LH-2010A is a newly developed fungicide with novel mode of action in the treatment of cucurbit downy mildew. Dissipation kinetics and residue levels of LH-2010A in cucumber were investigated using a QuEChERS method with GC-ECD. Field trials were constructed at three different sites in China in 2013 and 2014. The average recoveries of LH-2010A in fortified samples were between 94.0 and 106.2% for cucumber and between 84.4% and 98.7% for soil, with relative standard deviations within 3%. The dissipation rate of LH-2010A residue was evaluated assuming a pseudo first-order kinetics. The half-lives of LH-2010A were 2.8–4.2 days and 6.3–9.4 days in cucumber and soil samples, respectively. The terminal residues in cucumber were 0.077–0.207 mg/kg and 0.109–0.307 mg/kg on the first day after spray at the recommended dosage and 1.5 times of the recommended dosage, respectively. Using this rapid and sensitive method, we determined the dissipation kinetics and residue level of HL-2010A in cucumber. The suggested MRL value of HL-2010A in cucumber is 0.5 mg/kg. The research would provide guidance for proper and safe use of this newly developed fungicide in cucumber in greenhouse ecosystems.

Conclusion on the peer review of the pesticide risk assessment of the active substance flupyradifurone

Conclusion on the peer review of the pesticide risk assessment of the active substance flupyradifurone

Occurrence of Pesticide Residues in market and Farmgate samples of Okra crop,Abelmoschus esculentus(L.) in Meerut region

A multi pesticide residues analysis was carried out for farmgate samples (20) of okra fruits from four market places of Meerut region namely Daurala, Lawer, Kesarganj and Partapur markets. 40, 45, 30, 35, 50 and 25% samples were > MRL and 30, 40, 35, 45, 35 and 45% sam-ples were recorded MRL and 25, 30, 40, 45, 20 and 25% samples had residues MRL and 50, 45, 45, 45, 40 and 30% and 40, 40, 45, 45, 35 and 40% samples, respectively contained residues < MRL values of monocrotophos (0.20), chlorpyriphos (0.20), di-methoate (2.00), cypermethrin (0.20), endosulfan (2.00) and imidacloprid (0.05ppm), respectively. So the okra fruits samples with residues above MRL are not safe for human consumption.

Seasonal effect on aflatoxin M1 contamination in raw and UHT milk from Croatia

Aflatoxin M1 contamination was examined in raw milk (3716) and UHT milk (706) samples collected from farms of eastern Croatia and markets of central Croatia from February to July 2013. A maximal mean AFM1 of 1135.0 ng/L was measured in raw milk in March. The AFM1 levels exceeded the European Union maximum residue permitted amount (EU MRL) in 45.9% raw and 36.2% UHT milk samples in February. In total, AFM1 levels exceeded the EU MRL values in 27.8% of raw and 9.64% of UHT milk samples. A slight decrease in the number of samples exceeding the EU MRLs was recorded in the period March to June. The results showed significant statistical differences between the mean AFM1 concentrations of raw and UHT milk samples collected during February, March, May and June (P < 0.05, all). Also, statistical differences in AFM1 concentrations were found between months for raw and UHT milk (P < 0.001, both). In conclusion, the frequency of control of feed and milk samples should increase and should strive to educate breeders and those involved in milk production about the harmful effect of aflatoxins to animal feed.

Reasoned opinion on the setting of a new MRL for imazapic in genetically modified soya bean

In accordance with Article 6 of Regulation (EC) No 396/2005, the United Kingdom, hereafter referred to as the evaluating Member State (EMS), received an application from Exponent International Ltd. on behalf of BASF Corporation to set an import tolerance for the active substance imazapic in genetically modified (GM) soya bean BPS-CV127-9 grown in Brazil at the level of 0.4 mg/kg. The United Kingdom drafted an evaluation report in accordance with Article 8 of Regulation (EC) No 396/2005, which was submitted to the European Commission and forwarded to EFSA. According to EFSA the data are sufficient to derive a MRL proposal of 0.5 mg/kg for the use of imazapic on imidazolinone-tolerant soya bean imported from Brazil. As alternative option, risk manager may consider the MRL of 0.3 mg/kg, which is derived based on a previous calculation methodology and corresponds to the MRL value established in Brazil. An adequate analytical enforcement method is available to control the residues of imazapic in the crop under consideration. Based on the risk assessment results, EFSA concludes that the reported use of imazapic on soya bean BPS-CV127-9 will not result in a consumer exposure exceeding the toxicological reference value for imazapic and therefore is unlikely to pose a consumer health risk.

Immunochemical detection of apramycin as a contaminant in tissues of edible animals

Veterinary aminoglycoside antibiotic apramycin (AP) was used as hapten in different conjugation procedures for preparation of immunogen and coating antigens. Among the coating antigens one was chosen to ensure strictly selective determination of AP with no cross-reactivity of related analogs. The limit of competitive ELISA detection was 0.015 ng/ml for swine kidney and bovine muscle extracts. The dynamic range IC20–IC80 was calculated as 0.03–1.8 ng/ml (0.15–9 μg/kg). High sensitivity of assay allowed eliminating matrix effect of samples by simple dilution of tissue extracts. The experiments with tissue samples fortified with AP at half, single and double MRL values showed the recovery rate of 85–105%. Along with the other immunotests and kits for determination of aminoglycosides this for the first time developed assay of apramycin is suitable for screening of antibiotic residues in foodstuff.

Assessment of Pesticide Residues in Some Vegetables Grown in Kavrepalanchok and Bhaktapur Districts

Pesticides have wide spread use and their toxic residues have been reported in various environmental matrices. Thus, the determination of pesticide residues in food commodities such as vegetables, cereals, fruits, and other environmental components like soil, water has become increasingly essential requirement for consumers, producers and authorities for food quality control. Therefore, monitoring of residue level and exposure assessment of organophosphate group of pesticides namely dichlorovos and methyl parathion was carried out in 30 winter and summer vegetables supplied in Kathmandu valley. It was found that the MRL value of dichlorovos exceeded in three types of vegetables whereas in case of methyl parathion the MRL value exceeded in two types of vegetables only. The estimated average daily intake (EADI) of dichlorovos exceeded the acceptable daily intake (ADI) in 18 vegetables, whereas, regarding methyl parathion the EADI exceeded the ADI in 10 types of vegetables. Nepal Journal of Science and Technology Vol. 13, No. 2 (2012) 45-50 DOI: http://dx.doi.org/10.3126/njst.v13i2.7713

A Reversed-Phase High-Performance Liquid Chromatography (RP-HPLC) Determination of Pesticide Residues in Tender Coconut Water (elaneer/nariyal pani)

The occurrence of Monochrotophos, Copperoxychloride and Galaxy pesticides in 10 tender coconut water samples (Arasampattai, Sowcot pachai, kuttyaiadi (Kerala),Malayan orange, Malayan yellow, Alphanam, sowchot orange, Nettai, Kuttai and 1000 kaychi) in southern area of Tamilnadu, India was investigated. The HPLC results shows that the monochrotophos was found Malayan orange (5.847 mg kg-1) and it was above the Maximum Residual Limit (MRL (0.5-1.0 mg kg-1) and Malayan yellow (0.003 mg kg-1) and Nettai (0.323 mg kg-1) were below the Maximum Residual Limit. In Malayan yellow tender coconut samples copper oxychloride was found (0.003 mg kg-1) below the MRL value (20.0 mg kg-1). Analysis was carried out using HPLC-UV.

Feed additives diclazuril and nicarbazin in egg and liver samples from Croatian farms

In total 307 egg and 275 liver samples were examined for nicarbazin and 365 eggs for diclazuril over a 30-month period. Enzyme-linked immunosorbent assay methods used for quantification were validated according to European Commission Decision 2002/657/EC. Non-compliant samples were confirmed by LC-MS/MS. Mean diclazuril concentrations in egg samples were 0.31 µg kg−1, which is below the MRL. In only one egg sample, 2.26 µg kg−1 was determined by enzyme-linked immunosorbent assay, although confirmation by LC-MS/MS gave a value of 1.6 µg kg−1. Mean nicarbazin levels determined were 1.85 µg kg−1 in egg and 21.1 µg kg−1 in liver samples. Four samples, one egg and three livers, yielded elevated concentrations of nicarbazin, but only in the egg sample the LC-MS/MS method confirmed nicarbazin (106 µg kg−1) above the MRL value.

Thiacloprid Residues and Its Safety Evaluation in Darjeeling Tea

In order to examine the persistence behavior, safety evaluation and utilization of residue data for fixation of thiacloprid MRL, a supervised field trial in tea was conducted at Darjeeling. The HPLC analysis of thiacloprid in green tea leaves indicates that the initial deposits of 2.14 and 3.95mgkg(-1), which declined gradually and persisted until day 14 to the tune of 0.23 and 0.45mgkg(-1) respectively. The residues in processed tea samples prepared from green tea leaves of 7 and 14th day were 3.0-3.8times less. Thiacloprid did not infuse to tea liquor from processed tea. The half-life value in green tea leaves ranged from 4.29 to 4.31days. Considering the EU MRL value of 10mgkg(-1) and risk assessment calculation, thiacloprid at 30ga.i.ha(-1) appears to be safe in plant protection schedules and first round of plucking of green tea leaves on day 7 is recommended.