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1.
ABSTRACT

The effects of the spread of residue concentrations in the samples derived from the selected supervised trials and the number of trials were studied on the magnitude and uncertainty of the short-term dietary intakes calculated with the proposed new procedure (IESTIp) and that one used currently by the FAO (Food and Agriculture Organization) and WHO (World Health Organization) Joint meeting on Pesticide Residues (JMPR) (IESTIc). The residue data of 10 pesticides were obtained from supervised trials conducted on apples and pears. The methods described in Part I were used for the calculations of the uncertainty. The results indicate that the ratio of IESTIP to IESTIcIESTI) is directly proportional to the ratio of the estimated maximum residue level (MRL), recommended by the JMPR; to the highest residue (HR) observed in supervised trials, and it may have a wide range depending on the particular conditions. The φIESTI becomes greater with the increase of the difference between the mrl or maximum residue limit (MRL, established by the Codex Alimentarius Commission, CAC) and HR, and becomes smaller if the difference between the large portion (LP) and unit mass (U) decreases. The φIESTI ranged between 2 and 5.1 in the 16 cases examined indicating that the IESTIp calculation method leads to higher intake estimates. The ratio of CVIESTIp and CVIESTIc ranged typically between 0.62 and 1.71. It rapidly increased up to 12 trials. For a larger number of trials, the ratio remained practically constant (1.69–1.71). The processing factor (PF) equally affects the MRL and HR values, therefore, it will not practically influence the φIESTI. The uncertainty of the estimated median residues depends on the spread and number of values in the residue datasets, which affects the uncertainty of the conversion factor (CF) and subsequently the uncertainty of the estimated IESTIp. Residue values obtained from minimum nine independent trials are required for the correct calculation of the 95% confidence intervals of the calculated median residues. The uncertainty of the analytical results directly affects the median, HR values and indirectly the calculated mrl and the MRL derived from it. Therefore, it should also be considered for the calculation of the combined uncertainty of the conversion factors. For the correct interpretation of the results of dietary exposure calculations, the upper 95% confidence limit of the short-term intake should also be considered. However, it is not the current practice of regulatory agencies or JMPR.  相似文献   

2.

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

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3.
Dissipation rates of boscalid [2-chloro-N-(4′ -chlorobiphenyl-2-yl)nicotinamide], pyraclostrobin [methyl 2-[1-(4-chlorophenyl) pyrazol-3-yloxymethyl]-N-methoxycarbanilate], lufenuron [(RS)-1-[2,5-dichloro-4-(1,1,2,3,3,3-hexafluoropropoxy)phenyl]-3-(2,6-difluorobenzoyl)urea] and λ-cyhalothrin [(R)-cyano(3-phenoxyphenyl)methyl (1S,3S)-rel-3-[(1Z)-2-chloro-3,3,3-trifluoro-1-propenyl]-2,2-dimethylcyclopropanecarboxylate] in green beans and spring onions under Egyptian field conditions were studied. Field trials were carried out in 2008 in a Blue Nile farm, located at 70 kilometer (km) from Cairo (Egypt). The pesticides were sprayed at the recommended rate and samples were collected at pre-determined intervals. After treatment (T0) the pesticide residues in green beans were 7 times lower than in spring onions. This is due to a different structure of vegetable plant in the two crops. In spring onions, half-life (t1/2) of pyraclostrobin and lufenuron was 3.1 days and 9.8 days respectively. At day 14th (T14) after treatment boscalid residues were below the Maximum Residue Limit (MRL) (0.34 versus 0.5 mg/kg), pyraclostrobin and λ -cyhalothrin residues were not detectable (ND), while lufenuron residues were above the MRL (0.06 versus 0.02 mg/kg). In green beans, at T0, levels of boscalid, lufenuron and λ -cyhalothrin were below the MRL (0.28 versus 2 mg/kg; ND versus 0.02 mg/kg; 0.06 versus 0.2 mg/kg, respectively) while, after 7 days treatment (T7) pyraclostrobin residues were above the MRL (0.03 versus 0.02 mg/kg). However, after 14 days the residue level could go below the MRL (0.02 mg/kg), as observed in spring onions.  相似文献   

4.
The dissipation of the fungicides captan, cyprodinil, fludioxonil, dithianon, and tebuconazole and of the insecticides chlorpyrifos, fenitrothion, and malathion was studied, following a single treatment of different cultivars of pears, apples, and peaches. The study was conducted in northern Italy, over two successive growing seasons (2004 and 2005). The treatments were performed by the farmers involved, in line with their usual practice. At various time intervals from treatment to harvest, representative samples of fruit were collected and analyzed for pesticide residues. In some cases, concentrations lower than the maximum residue levels (MRLs) were found immediately after treatment. In all trials a rapid decline in pesticide concentrations was observed leading to residues at harvest greatly below the MRLs.  相似文献   

5.
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.  相似文献   

6.
Abstract

To stipulate the rationale of spraying doses and to determine the safe interval period of boscalid suspension concentrate (SC), the degradation dynamics and residual levels were investigated in cucumber and soil using liquid chromatography-tandem mass spectrometry (LC-MS/MS). Field trials were conducted according to Chinese Guideline on pesticide residue trials. Following application, the degradation kinetics was best ascribed to first-order kinetic models with half-life of 2.67–9.90 d in cucumber. Spraying boscalid SC at 1.5-fold the recommended dosage yield terminal residues, which are clearly lower than the maximum residue limit (MRL) established by China (MRL =5?mg.kg?1) in cucumber. At variance, the dissipation dynamics in soil did not fit to first-order kinetics and the half-life was more than 17?days, the finding which denotes that the degradation behavior of boscalid in soil proceeds slowly. It has therefore been shown that boscalid is safe for use on cucumbers under the recommended dosage.  相似文献   

7.
This study was undertaken to validate the “quick, easy, cheap, effective, rugged and safe” (QuEChERS) method using Golden Delicious and Starking Delicious apple matrices spiked at 0.1 maximum residue limit (MRL), 1.0 MRL and 10 MRL levels of the four pesticides (chlorpyrifos, dimethoate, indoxacarb and imidacloprid). For the extraction and cleanup, original QuEChERS method was followed, then the samples were subjected to liquid chromatography-triple quadrupole mass spectrometry (LC-MS/MS) for chromatographic analyses. According to t test, matrix effect was not significant for chlorpyrifos in both sample matrices, but it was significant for dimethoate, indoxacarb and imidacloprid in both sample matrices. Thus, matrix-matched calibration (MC) was used to compensate matrix effect and quantifications were carried out by using MC. The overall recovery of the method was 90.15% with a relative standard deviation of 13.27% (n = 330). Estimated method detection limit of analytes blew the MRLs. Some other parameters of the method validation, such as recovery, precision, accuracy and linearity were found to be within the required ranges.  相似文献   

8.
ABSTRACT

In 2015 a scientific workshop was held in Geneva, where updating the four equations for estimating the short-term dietary exposure (International Estimated Short Term Intake, IESTI) to pesticides was suggested. The impact of these proposed changes on the exposure was studied by using residue data and large portion consumption data from Codex and Australia. For the Codex data, the exposure increased by a median factor of 2.5 per commodity when changing to the proposed IESTI equations. The increase in exposure was highest for bulked and blended food commodities (case 3 equations), followed by medium-sized food commodities (case 2a equations) and small- and large-sized food commodities (case 1 and case 2b equations). For the Australian data, out of 184 maximum residue limit (MRL) large portion combinations showing acute exposures below the acute reference dose (ARfD) with the current IESTI equations, 23 exceeded the ARfD with the proposed IESTI equations (12%). The percentage exceeding the ARfD was higher for the Australian MRL large portion combinations (12% of 184) than for those of Codex (1.3% of 8,366). However, the percentage MRL loss in the Australian dataset may not be representative of all pesticide MRLs since it concerns six pesticides only, specifically selected to elucidate the potential effects of the use of the proposed IESTI equations. For the Codex data, the increase in exposure using the proposed equations resulted in a small increased loss of 2.6% of the 1,110 MRLs estimated by the Joint FAO/WHO Meeting on Pesticide Residues (JMPR): 1.4% of the MRLs were already not acceptable with the current equations, 4.0% of the MRLs were not acceptable with the newly proposed equations. Our study revealed that case 3 commodities may be impacted more by the proposed changes than other commodities. This substantiates one of the conclusions of the Geneva workshop to gather information on bulking and blending practices in order to refine MRL setting and dietary risk assessment for case 3 commodities where possible.  相似文献   

9.
Abstract

This study investigates the oxidation of trifluralin residues during ozonation in aqueous and food matrices (tomato). Domestic ozonation equipment with average production of 23.9?mg O3 L?1 h?1 was used in the tests. Modern chromatographic systems (SPME-GC-IT/MS/MS and QuEChERS-GC-IT/MS/MS) were applied for extraction and detection of trifluralin residue in fortified samples of ultrapure water, tap water, superficial water and tomato fruit. The samples were submitted to the ozonation process during 0, 5, 10 and 20?min. Treatment at 5?min was able to degrade 71.5% of herbicide trifluralin in surface water. The removal (%) in ultrapure water reached 83.4% after 20?min of ozonation. The degradation of trifluralin in fortified tomato samples (0.025–0.1?mg kg?1) were conducted with ozonation at 20?min, and it ranged from 84.4 to 92.7%. After treatment, levels of trifluralin in tomato remained within the established MRLs to EU, USEPA and ANVISA (Brazil). The data provided evidence that ozone is effective for removing trace trifluralin from water and foods.  相似文献   

10.
Dissipation curves of azoxystrobin and of the neonicotinoids acetamiprid and thiacloprid in peach; azinphos-methyl and carbaryl in pear and azoxystrobin, chlorfenapyr and chlorpyrifos in high-tunnel tomato crops were studied in the Southern region of Uruguay. An analytical methodology based on solid phase extraction (SPE) and detection by High Performance Liquid Chromatography with Diode Array Detector (HPLC/DAD) was used for acetamiprid and thiacloprid. Coupled SPE and detection by Gas Chromatography with Mass Selective Detector (GC/MSD) was used for the detection of azinphos-methyl, azoxystrobin, carbaryl, chlorfenapyr and chlorpyrifos residues. Curves were modeled mathematically with Solver program of Microsoft Excel®. The best fit for acetamiprid and thiacloprid in peach was achieved with the exponential model (r2=0.961 and 0.944, respectively). In the case of peach fruits there is not a Maximum Residue Limit (MRL) for acetamiprid in the Codex Alimentarius, while 0.5 mg/kg is the value rated for thiacloprid. The MRLs accepted by the European Union (EU) are 0.1 mg/kg for acetamiprid and 0.3 mg/kg for thiacloprid. According to the curves determined in these experiments, thiacloprid residues 10 to 12 days after application (daa) were below the MRLs established by both sources. In the case of acetamiprid, 25 daa would be required, according to the exponential mathematical model, to get residues levels below the MRL values established by the EU. For azinphos methyl in pear, the residues detected were mathematically fitted to an exponential model (r2=0.999). According to it, residue levels under the MRL established by the EU (0.05 mg/kg) are gotten in our conditions in 20 daa. In plastic tunnel tomato chlorfenapyr residues were not detected from 16 daa, having the dissipation curve an exponential trend. In the same condition, there was not a decay of the azoxystrobin concentration during a 24-day trial, being it around 0.40 ± 0.05 mg/kg.  相似文献   

11.
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.  相似文献   

12.
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.  相似文献   

13.
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)  相似文献   

14.
This investigation was undertaken to determine whether active ingredients (AIs) of currently recommended plant protection products (PPPs) could be transferred to beehives from apple and pear trees. A field trial was carried out with apple trees of Ligol and Idared variety, and pear trees of Conference variety. For pest and diseases control of fungal origin, recommended PPPs were applied. Samples of flowers from the above-mentioned varieties of fruit trees, of bees, brood and honey from beehives located in their direct neighborhood were collected regularly and analyzed for the presence of lambda-cyhalothrin (an insecticide) and cyprodinil, captan, fluopyram, kresoxim-methyl, penthiopyrad and trifloxystrobin (fungicides). In samples of flowers of Ligol variety, fluopyram residues (on average 0.621 µg single flower?1) were at the highest levels, whereas in samples of pear flowers of Conference variety, and in flowers of Idared variety, captan residues (on average, respectively, 0.705 and 165.7 µg single flower?1). In samples of bees and honey, residues of five AIs were detected, and in brood six AIs, whereby in each case captan residues prevailed, respectively, up to 585.2, 51.52 and 126.5 µg kg?1 bees and honey. In the honey, significantly larger residues of captan were found out than maximum residue level (MRL) for this AI – 103.04% MRL. In the case of any AI, the daily intake did not exceed 0.002% acceptable daily intake (ADI).  相似文献   

15.
ABSTRACT

The calculation of the combined uncertainty of the international estimated short-term intake (IESTI) of ethephon residues in apples is shown as an example. The ethephon residues in apples were reported by the Joint FAO (Food and Agriculture Organization of the United Nations)/WHO (World Health Organization) Meeting on Pesticide Residues (JMPR). The apple consumption data were taken from the IESTI (international short-term intake) calculation template used by the JMPR. The IESTI was calculated with the currently used method (case 2a) and a proposed one recommended by the EFSA (European Food Safety Authority)/RIVM (Dutch National Institute for Public Health) Scientific Workshop co-sponsored by FAO and WHO. In this example, the ratio of IESTIproposed/IESTIcurrent and their combined relative uncertainty are about 2.8, and 1.7, respectively. The larger IESTI and uncertainty obtained with the proposed equation are the consequence of calculation only with the large portion (LP) instead of its combination with unit mass, and the MRL instead of the highest residue (HR). The LP is the major contributor to the combined uncertainty. Both the calculated IESTI and its combined uncertainty depend on the actual food – pesticide residue combination, and should be calculated for each case.  相似文献   

16.
An assessment of the error associated with conventional pesticide residue analysis has been conducted based on computer simulations and inter-laboratory residue analysis. Computational simulations were conducted based on (i) typical performance and regulatory acceptance criteria of analytical methods, and (ii) field residue distributions. In addition, field samples with incurred residues were sent to different private laboratories and the results compared. The relative difference in pesticide residues obtained when samples from the same field or produce lot are analyzed at separate laboratories was used to quantify the uncertainty associated with residue analyses performed using common analytical technology, and methods that are in compliance with current regulatory requirements. The study showed that differences of > 100% are common and should be expected when samples from the same crop are analyzed at different laboratories. The results also suggest that the error within residue measurements can be particularly detrimental when a result is reported near the maximum residue limit (MRL).  相似文献   

17.
Dissipation curves of azoxystrobin and of the neonicotinoids acetamiprid and thiacloprid in peach; azinphos-methyl and carbaryl in pear and azoxystrobin, chlorfenapyr and chlorpyrifos in high-tunnel tomato crops were studied in the Southern region of Uruguay. An analytical methodology based on solid phase extraction (SPE) and detection by High Performance Liquid Chromatography with Diode Array Detector (HPLC/DAD) was used for acetamiprid and thiacloprid. Coupled SPE and detection by Gas Chromatography with Mass Selective Detector (GC/MSD) was used for the detection of azinphos-methyl, azoxystrobin, carbaryl, chlorfenapyr and chlorpyrifos residues. Curves were modeled mathematically with Solver program of Microsoft Excel. The best fit for acetamiprid and thiacloprid in peach was achieved with the exponential model (r(2)=0.961 and 0.944, respectively). In the case of peach fruits there is not a Maximum Residue Limit (MRL) for acetamiprid in the Codex Alimentarius, while 0.5 mg/kg is the value rated for thiacloprid. The MRLs accepted by the European Union (EU) are 0.1 mg/kg for acetamiprid and 0.3 mg/kg for thiacloprid. According to the curves determined in these experiments, thiacloprid residues 10 to 12 days after application (daa) were below the MRLs established by both sources. In the case of acetamiprid, 25 daa would be required, according to the exponential mathematical model, to get residues levels below the MRL values established by the EU. For azinphos methyl in pear, the residues detected were mathematically fitted to an exponential model (r(2)=0.999). According to it, residue levels under the MRL established by the EU (0.05 mg/kg) are gotten in our conditions in 20 daa. In plastic tunnel tomato chlorfenapyr residues were not detected from 16 daa, having the dissipation curve an exponential trend. In the same condition, there was not a decay of the azoxystrobin concentration during a 24-day trial, being it around 0.40 ± 0.05 mg/kg.  相似文献   

18.
Studies were conducted to analyze the residue of commonly used pesticides viz. methyl parathion, chloropyrifos, endosulfan, cypermethrin, fenvalerate, carbendazim, imidacloprid and carbaryl in mango, Dashehari variety, integrated pest management (IPM) and non-IPM samples were collected from the IPM and non-IPM orchards, Lucknow, India. We also present a method for the simultaneous determination of these pesticides in mango samples. Residues of methyl parathion, chloropyriphos, endosulfan, cypermethrin, fenvalerate were extracted from the samples with acetone: cyclohexane: ethyl acetate in the ratio 2:1:1 followed by cleanup using neutral alumina. Analysis was performed by gas chromatography-electron capture detector (GC-ECD) with a megabore column (OV-1). Residues of carbendazim, imidacloprid and carbaryl were extracted with acetone and after cleanup, analysis was performed by high performance liquid chromatography (HPLC) using photo diode array (PDA) detector. Recoveries of all the pesticides ranged between 72.7 – 110.6%, at 0.1 and 1.0 μg g? 1 level of fortification. The residues detected in non-IPM samples of mango were found to be below the prescribed limits of maximum residue limit (MRL) while IPM samples were free from pesticide residues.  相似文献   

19.
Abstract

Paclobutrazol (PBZ) is a plant growth regulator (PGR) widely used in fruit and vegetable cultivation. However, due to the severe toxicity of PBZ, a sub-ppm level maximum residue limit (MRL) was established worldwide. Therefore, it is significant to propose a rapid, sensitive and high throughput screening method for monitoring the PBZ residues in foods. In this study, a simple and sensitive indirect competitive Enzyme-linked immunosorbent assay (icELISA) was established for PBZ detection in fruits basing polyclonal antibody. For both economy and pollution prevention, a microwave-solvent-free method was used to synthesize the PBZ hapten with high efficiency. The detection conditions, such as coating antigen concentration, antibody concentration, organic reagent concentration, ionic strength and pH, were optimized. Under the optimized conditions, this method showed high sensitivity and specificity. The detection range is 1.27-138.23?ng/mL, half-maximum inhibition concentration (IC50) is 13.26?ng/mL, and the IC20 was lower than the reported ELISAs for PBZ. Additionally, this method had high accuracy and precision. The recoveries were ranged from 88.78% to 96.80% in PBZ spiked apple samples with RSD below 4%. All the results showed that the polyclonal antibody based icELISA could be useful for PBZ screening in fruit samples.  相似文献   

20.
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 (t1/2) 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.  相似文献   

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