Factors affecting the quantitative uncertainty of the estimated short-term intake. Part I—Calculation methods

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 IESTI_proposed/IESTI_current 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.     

Distribution of pesticide residues in soil and uncertainty of sampling

Pesticide residues were determined in about 120 soil cores taken randomly from the top 15 cm layer of two sunflower fields about 30 days after preemergence herbicide treatments. Samples were extracted with acetone-ethyl acetate mixture and the residues were determined with GC-TSD. Residues of dimethenamid, pendimethalin, and prometryn ranged from 0.005 to 2.97 mg/kg. Their relative standard deviations (CV) were between 0.66 and 1.13. The relative frequency distributions of residues in soil cores were very similar to those observed in root and tuber vegetables grown in pesticide treated soils. Based on all available information, a typical CV of 1.00 was estimated for pesticide residues in primary soil samples (soil cores). The corresponding expectable relative uncertainty of sampling is 20% when composite samples of size 25 are taken. To obtain a reliable estimate of the average residues in the top 15 cm layer of soil of a field up to 8 independent replicate random samples should be taken. To obtain better estimate of the actual residue level of the sampled filed would be marginal if larger number of samples were taken.     

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).     

Estimation of measurement uncertainty associated to the determination of pesticide residues: a case study

In the analytical analysis the measurement uncertainty is a quantitative indicator of the confidence describing the range around a reported or experimental result within which the true value can be expected. Several approaches can be used to estimate the measurement uncertainty associated to the analysis of pesticide residues: a) the top-down, the estimation can be referred to default values; b) the bottom-up the estimation is related to the uncertainty sources. Concerning the bottom-up approach, the following contributions have been investigated: weight of sample, calibration solutions, final volume of sample and intermediate repeatability studies. The commodity/residue combination selected in this study was celery/tau-fluvalinate pesticide. Tau-fluvalinate is a broad-spectrum insecticide in the pyrethroid class of pesticides. The Maximum Residue Limit (MRL) of tau-fluvalinate in celery has been set at 0.01 mg/kg. The tau- Fluvalinate showed two chromatographic peaks. Since the individual standards are not available, the two peaks were integrated separately and the instrumental responses were added. The total residue was calculated on the basis of resulted peaks. The present work aims to compare the uncertainty estimated by experimental data using repeated analysis (n = 12) of a real sample and a spiked sample. The relative expanded uncertainty for two data set, incurred and spiked, was 22 % and 20 %, respectively. No differences were observed from repeated determinations of real samples and spiked samples.     

Exposure to specific polychlorinated biphenyls and some chlorinated pesticides via breast milk in Poland

The aim of our study was to obtain the data on the exposure of breast-fed infants to polychlorinated biphenyls (PCBs) and selected organochlorine pesticides (OCPs) in the Wielkopolska province (Poland). The levels of indicator PCBs, and selected OCPs, including two DDT metabolites (HCB, p,p'-DDT, p,p'-DDD, p,p'-DDE and alpha,beta,gamma-HCH) were determined in 27 human milk samples, collected in 2000-2001, according to WHO protocol. Estimated daily intakes (EDIs) of all analytes were calculated. Our results were compared with those obtained by an analysis of human milk samples from other European and non-European countries, collected in the same period time. We have stated that median exposure of Wielkopolska first breast-fed infants to OCPs is comparable (EDI(HCB) = 0.086 microg/kgbw/day; EDI(beta-HCH)=0.063 microg/kgbw/day) or higher (EDI(p,p'-DDE) = 3.495 microg/kgbw/day) than in other European countries, while exposure to PCBs (EDI(Sigma7PCB) = 0.364 microg/kgbw/day) is situated at the low end of the intake of these xenobiotics by breast-fed infants from different regions of Europe.     

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

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

Consumer health risk to pesticide residues in Salvia officinalis L. and its infusions

Salvia officinalis L. is a popular herb widely used in culinary, cosmetic, and medicinal preparations, and also as an ornamental plant. Sage crops are threatened by many diseases, such as gray mold, powdery mildew, and leaf spot, by weeds, and by pests, such as aphids. Use of crop protection products may lead to presence of pesticide residues in this herb. The aim of this work was to study presence of pesticide residues in the herb, S. officinalis L., available on the retail market in Poland, to verify their compliance with the maximum residue levels (MRLs) and to assess the chronic and acute risks associated with consumption of this herb and infusions prepared from contaminated sage plants. Ninety active substances of pesticides were analyzed, including all active substances registered in Poland for protection of the sage. Five active substances were found, one fungicide – boscalid and four insecticides: chlorpyrifos, pp′-DDT, dimethoate (residue levels above MRL) and indoxacarb. The chronic and acute exposure to pesticide residues consumed with sage did not exceed 0.02% of the acceptable daily intake (ADI) and 0.1% of the acute reference dose (ARfD), respectively.     

Factors affecting the quantitative uncertainty of the estimated short-term intake. Part II—Practical examples

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 (IESTI_p) and that one used currently by the FAO (Food and Agriculture Organization) and WHO (World Health Organization) Joint meeting on Pesticide Residues (JMPR) (IESTI_c). 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 IESTI_P to IESTI_c (φ_IESTI) 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 φ_IESTI 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 φ_IESTI ranged between 2 and 5.1 in the 16 cases examined indicating that the IESTI_p calculation method leads to higher intake estimates. The ratio of CV_IESTIp and CV_IESTIc 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 φ_IESTI. 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 IESTI_p. 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.     

Persistence and distribution of pesticide residues in fresh agricultural food consumed in the province of Bologna

The presence of pesticide residues in fresh vegetables and fruit have been qualitatively and quantitatively determined at the laboratories of the Regional Agency for Environmental Protection (ARPA), Division of the Province of Bologna. More than 1,700 samples have been tested by routine analyses. The possible risks for consumers have been evaluated by various parameters. The most important ones were: the amount of each residue; the respective ADI (Acceptable Daily Intake) limit; the contemporary presence of different residues; an estimation of the daily intake, based on the amount of fruit and vegetables consumed per person. It has been possible to evaluate that the daily intake of pesticide residues in the province of Bologna during the period 2003–06 resulted lower than the ADI limits concerning the vegetables. According to the information on fruit consumption the daily intake of omethoate (O,O-dimethyl S-methylcarbamoylmethyl phosphorothioate) resulted higher than its ADI limit, of dicofol (2,2,2-trichloro-1,1-bis(trichloromethyl)benzenemethanol) very close to the admitted limit, under the respective limits for all the other residues.     

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

ABSTRACT

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

Uncertainty estimation in the analysis of pesticide residues in olive oil using data from proficiency tests

In this work we report the results for estimating the measurement uncertainty (MU) following up the application of two different approaches, relatively the top-down procedure, by using proficiency test data. We have focused the estimation on the olive oil matrix. We used the analytical data obtained from five selected editions of the Proficiency Tests (PTs, from 2007 to 2011) on pesticide residues in olive oil to estimate the MU. These PTs have been organized by Istituto Superiore di Sanità annually in cooperation with International Olive Council (IOC) since 1997. The number of participants in each trial ranged from 10 to 43. We used a total of 34 pesticide results. The expanded uncertainty U _(c) was calculated using a covering factor k = 2 for a confidence interval of 95%. In the approach 1, the within–laboratory reproducibility standard deviation is combined with estimates of the method and laboratory bias using PTs data. In the approach 2, the way of estimating the MU is based only on the bias that the laboratory has obtained participating in a sufficient number of the IOC proficiency tests. Comparing the relative expanded uncertainty based on these different approaches we notice values quite constant and close, from 42% to 48%. Moreover, these calculated expanded uncertainties are less than the default value of 50% (corresponding to a 95% confidence level), adopted from European guidance document SANCO based on the fit-for-purpose relative standard deviation (FFP-RSD).     

Assessment of the daily intake of 62 polychlorinated biphenyls from dietary exposure in South Korea

The dietary intake of polychlorinated biphenyls (PCBs) was estimated using the sum of 62 PCB congeners (∑₆₂PCBs), including seven indicator PCBs and 12 dioxin-like PCBs, in the South Korea. In this study, 200 individual food samples belonging to 40 different foodstuffs were investigated to estimate the distribution of PCB congeners in five sampling cities. PCB exposure was estimated using Korean dietary habits as established by the National Health and Nutrition Examination Survey (NHANES). The PCB concentrations in rice, the most frequently consumed food in Korea, was relatively low in whole food samples. The mean PCB levels measured in fish were the highest in this study, but each fish is consumed in relatively small amounts by the general population. Therefore, the daily dietary intake should also be considered with regard to human exposure to PCBs, especially with the consumption of contaminated foods. Dioxin-like PCB levels were also calculated using TEF values that were established in 2005. The average levels (pg TEQ/g) were 0.0002 for rice and 0.0098 for fish. The dioxin-like PCBs accounted for a relatively small percentage of the total PCBs, compared to previous studies. According to our research, the health risks associated with exposure to PCBs could be estimated using the tolerable daily intake (TDI) of the general population.     

Nature of the field-to-field distribution of pesticide residues

The supervised trial datasets (1950), consisting of a minimum of five residue values and selected by the experts of FAO/WHO Joint Meeting on Pesticide Residues for recommending maximum residue levels between 1997 and 2011, were evaluated to obtain information on the typical spread of residue values in individual datasets. The typical relative standard deviation, CV, of field-to-field variation of pesticide residues was about 80%. The spread of residues in datasets is independent from the chemical structure of pesticides, residue level, pre-harvest interval and number of values in the datasets. The CV ranges within the Codex commodity groups and between groups overlapped and their difference were not statistically significant. The number of residues below the limit of quantification (LOQ) affects the CV at various extents depending on the ratio of LOQ/R _mean. The combined uncertainty of the highest residue in a dataset significantly affects the CV of the dataset. The lowest and intermediate ones have less influence. The residues in different fields receiving the same treatment vary within large range: 55%, 72%, 78%, 86% and 89% of the 25,766 residues values were, respectively, within 3, 4, 5, 6 and 7 times the median value of the corresponding dataset.     

Error propagation in pesticide residue measurements estimated by computational simulations and inter-laboratory sample analysis

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).     

Human exposure to 2,3,7,8-TCDD

This paper uses an environmental partitioning model to evaluate the concentration of 2,3,7,8-Tetrachlorodibenzo-p-dioxin (TCDD) in various environmental media. These concentrations are then used to estimate the amount of TCDD entering the food chain and the average daily intake of TCDD by the general population of the US. The food chain accounts for 98% of human exposure to TCDD. The model estimated the average daily intake of TCDD to be 0.05 ng/day.     

Rapid determination of residues of pesticides in honey by µGC-ECD and GC-MS/MS: Method validation and estimation of measurement uncertainty according to document No. SANCO/12571/2013

A simple and straightforward method for simultaneous determination of residues of 13 pesticides in honey samples (acrinathrin, bifenthrin, bromopropylate, cyhalothrin-lambda, cypermethrin, chlorfenvinphos, chlorpyrifos, coumaphos, deltamethrin, fluvalinate-tau, malathion, permethrin and tetradifon) from different pesticide classes has been developed and validated. The analytical method provides dissolution of honey in water and an extraction of pesticide residues by n-Hexane followed by clean-up on a Florisil SPE column. The extract was evaporated and taken up by a solution of an injection internal standard (I-IS), ethion, and finally analyzed by capillary gas chromatography with electron capture detection (GC-µECD). Identification for qualitative purpose was conducted by gas chromatography with triple quadrupole mass spectrometer (GC-MS/MS). A matrix-matched calibration curve was performed for quantitative purposes by plotting the area ratio (analyte/I-IS) against concentration using a GC-µECD instrument. According to document No. SANCO/12571/2013, the method was validated by testing the following parameters: linearity, matrix effect, specificity, precision, trueness (bias) and measurement uncertainty. The analytical process was validated analyzing blank honey samples spiked at levels equal to and greater than 0.010 mg/kg (limit of quantification). All parameters were satisfactorily compared with the values established by document No. SANCO/12571/2013. The analytical performance was verified by participating in eight multi-residue proficiency tests organized by BIPEA, obtaining satisfactory z-scores in all 70 determinations. Measurement uncertainty was estimated according to the top-down approaches described in Appendix C of the SANCO document using the within-laboratory reproducibility relative standard deviation combined with laboratory bias using the proficiency test data.     

Residues and dissipation kinetic of abamectin,chlorfenapyr and pyridaben acaricides in green beans (Phaseolus vulgaris L.) under field conditions using QuEChERS method and HPLC

Abstract

The current study estimated the dissipation rates of abamectin, chlorfenapyr and pyridaben acaricides in pods of green beans (Phaseolus vulgaris L.) under field conditions in Egypt. Pesticides were extracted and cleaned-up by QuEChERS method and were analyzed by HPLC. The dissipation of these acaricides followed the first order kinetics model with half-life (t_1/2) values 1.00, 3.50 and 1.50?days for abamectin, chlorfenapyr and pyridaben, respectively. The lowest residues, at different time intervals of field application rate of each pesticide, were observed with abamectin followed by pyridaben and then chlorfenapyr. Pre-harvest intervals (PHIs) were 10.00, 13.50 and 6.00?days for abamectin, chlorfenapyr and pyridaben, respectively and were below the established European maximum residue limits (EU MRLs) 10–14, 14–21 and 7–10?days after application, respectively. If the fresh pods will be consumed after harvest, it is expected that the presence of these pesticides in the food will have a negative impact on human health. Therefore, the elimination of the residues of these harmful pesticides must be carried out.     

Background levels and dietary intake of PCDD/Fs in domestic and imported meat in South Korea

A survey was conducted in South Korea to determine residual levels and dietary intake of polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) from meat. Altogether 119 domestic and 164 imported samples of beef, pork, and chicken were examined. The mean levels of PCDD/Fs in upper bound were 0.21, 0.22, and 0.04pg WHO-TEQ/g fat for beef, pork, and chicken, respectively. The low level of PCDD/Fs in chicken probably resulted from the low fat content in the samples used. The samples were separated into domestic and imported products in order to investigate the sources of contamination. PCDFs were the more dominant congeners in domestic beef and were similar to those found from emission of incineration. However, the congener profiles of domestic beef and incineration were difficult to compare because the environmental fate and animal metabolism were involved. The upper bound dietary intake of PCDD/Fs from beef, pork and chicken was calculated to be 0.04pg/WHO-TEQ/kgbw/day. The combined consumption of beef, pork, and chicken was found to be 84.8g per day for a person weighing 60kg and represented 5.7% of their total daily food intake.     

Estimating the contribution of precursor compounds in consumer exposure to PFOS and PFOA

The exposure of humans to perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA) was quantified with emphasis on assessing the relative importance of metabolic transformation of precursor compounds. A Scenario-Based Risk Assessment (SceBRA) approach was used to model the exposure to these compounds from a variety of different pathways, the uptake into the human body and resulting daily doses. To capture the physiological and behavioral differences of age and gender, the exposure and resulting doses for seven consumer groups were calculated. The estimated chronic doses of a general population of an industrialized country range from 3.9 to 520 ng/(kg day) and 0.3 to 140 ng/(kg day) for PFOS and PFOA, respectively. The relative importance of precursor-based doses of PFOS and PFOA was estimated to be 2-5% and 2-8% in an intermediate scenario and 60-80% and 28-55% in a high-exposure scenario. This indicates that sub groups of the population may receive a substantial part of the PFOS and PFOA doses from precursor compounds, even though they are of low importance for the general population. Similar to a preceding study, uptake of perfluorinated acids from contaminated food and drinking water was identified as the most important pathway of exposure for the general population. The biotransformation yields of telomer-based precursors and to a lesser extent perfluorooctanesulfonylfluoride-based precursors were identified as influential parameters in the uncertainty analysis. Fast food consumption and fraction of food packaging paper treated with PFCs were influential parameters for determining the doses of PFOA.     

Pesticide residues in Italian Ready-Meals and dietary intake estimation

The investigations carried out during 2005 by state-run Italian laboratories within the framework of controls seeking pesticide residues monitoring in foodstuffs involve quantifying the levels of such residues in fruit and vegetable produce and their processed products: oil, wine and fruit juices. The Italian Ready-Meal Residue Project, promoted by the pesticides working group of Italian Environmental Agencies, seeks to asses the quantity of pesticides in pre-prepared (ready-to-eat) lunches (comprising a first course, side dish, fruit, bread and wine), and to quantify the amounts consumed and compare with the acceptable daily intake ADIs.The data provided by 16 laboratories which analyzed 50 complete meals in 2005 (samples taken on 8 February, 26 May, 24 October, 21 December 2005) showed residues in 39 lunches, with an average number of 2.4 pesticides in each meal and a maximum of 10 pesticides. The most frequently found substances were: pirimiphos-methyl (20 times), procymidone (17), pyrimethanil (7), iprodione (7), cyprodinil (7), fenitrothion (6), diphenylamine (6), chlorpyrifos (6), metalaxyl (5) and chlorpyrifos-methyl (5).The distribution of residues among each dish of the meal was also examined, and the results showed that: 77.3% of the residues were present in the fruit, 14.9% in the wine, 3.0% in the main course, 2.8% in the bread and 2.1% in the side dish. Assuming that two meals are consumed per day, the daily intake of pesticide residues was calculated on a daily basis, in relation to normal body weight (60 kg for an adult, 40 kg for a teenager, 20 kg for a child) and compared with the ADI values established by the European Union. In the case of adults, the average daily intake of pesticides in relation to ADI was 2.6% with a maximum of 73.3%; for teenagers it was 4.9% with a maximum of 109% and for children it was 9.8% with a peak of 219%.