Determination of Anthelmintic and Antiprotozoal Drug Residues in Fish Using Liquid Chromatography-Tandem Mass Spectrometry.

The objective of this study is to develop a comprehensive and simple method for the simultaneous determination of anthelmintic and antiprotozoal drug residues in fish. For sample preparation, we used the "quick, easy, cheap, effective, rugged, and safe" (QuEChERS) method with a simple modification. The sample was extracted with water and 1% formic acid in acetonitrile/methanol (MeCN/MeOH) (95:5, v/v), followed by phase separation (salting out) with MgSO4 and NaCl (4:1, w/w). After centrifugation, an aliquot of the extract was purified by dispersive solid-phase extraction (d-SPE) prior to liquid chromatography-tandem mass spectrometry (LC-MS/MS) analysis. The method was validated at three concentration levels for all matrices, in accordance with the Codex guidelines (CAC/GL-71). Quantitative analysis was performed using the method of matrix-matched calibration. The recoveries were between 60.6% and 119.9%, with coefficients of variation (CV) <30% for all matrices. The limit of quantitation (LOQ) of the method ranged from 0.02 µg kg-1 to 4.8 µg kg-1 for all matrices. This comprehensive method can be used for the investigation of both anthelmintic and antiprotozoal drugs belonging to different chemical families in fishery products.

The effects of extracting procedures on occurrence of polycyclic aromatic hydrocarbons in edible oils.

Polycyclic aromatic hydrocarbons (PAHs) are one of the most hazardous naturally occurring chemical contaminants of food. Edible oils are easily contaminated by PAHs generated during high-temperature processing steps such as oil extraction and refining. In this study, the effects of different extraction methods on the levels of PAHs in sesame oils and red pepper seed oils were assessed. GC-MS was used to determine the levels of PAHs in edible oils. Sesame oils extracted from seeds by plate-pressing extraction method had lower levels of PAHs than those extracted by screw-expeller extraction method from sesame flour. Furthermore, the levels of PAHs increased by 62.2% when the extraction time was longer. Notably, the PAHs already present in oils could be effectively reduced by refining procedures such as sinking, centrifugation, filtration, and neutralization with alkali.

Determination and risk characterization of polycyclic aromatic hydrocarbons of tea by using the Margin of Exposure (MOE) approach.

Tea is one of the most frequently consumed drinks due to its favourite taste and the health benefit. Tea is produced by several processes and drying is very important step to develop the flavour and destroys the enzymes in tea. However, during drying tea, polycyclic aromatic hydrocarbons some of which are carcinogen and genotoxin are naturally produced. The risk of PAHs by drinking tea was characterized by determining contents of 4 PAHs in tea. 4 PAHs including Benz(a)anthracene (BaA), Chrysene (CHR), Benzo(b)fluoranthene (BbF) and Benzo(a)pyrene (BaP) were investigated by GC-MS in total 468 tea products, which were contaminated up to 4.63 ng g-1. Mate tea was the most highly contaminated by BaA, CHR, BbF and BaP and followed by Solomon's seal and Chrysanthemum. The Margin of Exposures calculated by the concentration of BaA, CHR, BbF and BaP and consumption amount of tea were higher than 10,000, and the risk of PAHs in tea were low concern to public health.

Determination of plutonium isotopes (238,239,240Pu) and strontium (90Sr) in seafood using alpha spectrometry and liquid scintillation spectrometry.

The present study was carried out to survey the levels of plutonium isotopes (238,239,240Pu) and strontium (90Sr) in domestic seafood in Korea. In current, regulatory authorities have analyzed radionuclides, such as 134Cs, 137Cs and 131I, in domestic and imported food. However, people are concerned about contamination of other radionuclides, such as plutonium and strontium, in food. Furthermore, people who live in Korea have much concern about safety of seafood. Accordingly, in this study, we have investigated the activity concentrations of plutonium and strontium in seafood. For the analysis of plutonium isotopes and strontium, a rapid and reliable method developed from previous study was used. Applicability of the test method was verified by examining recovery, minimum detectable activity (MDA), analytical time, etc. Total 40 seafood samples were analyzed in 2014-2015. As a result, plutonium isotopes (238,239,240Pu) and strontium (90Sr) were not detected or below detection limits in seafood. The detection limits of plutonium isotopes and strontium-90 were 0.01 and 1 Bq/kg, respectively.

Various extraction methods for detection of bistrifluron residues in Asian pear using high-performance liquid chromatography: application to dissipation patterns under open-field conditions.

The present study was carried out to develop an analytical method for the detection and quantification of bistrifluron, a benzoylphenylurea compound, in pear using high-performance liquid chromatography with UV detection. Samples were extracted using conventional, AOAC and EN quick, easy, cheap, effective, rugged and safe 'QuEChERS' methods. As expected, conventional and EN-QuEChERS methods gave higher recoveries than AOAC. In addition, interference around the analyte retention time was observed in the conventional method. Thus, the EN-QuEChERS method was selected and validated by studying various parameters, including linearity, limit of detection, limit of quantification (LOQ), recovery and precision. Linearity was excellent, with a correlation coefficient of 0.9998. Recovery rates at three spiking levels (0.05, 0.2 and 1 mg/kg) ranged from 73.76 to 98.66%. Intra- and inter-day precisions, expressed as relative standard deviations, were <6%. The LOQ of 0.05 mg/kg was considerably lower than the maximum residue limit (1 mg/kg) set by the Korean Ministry of Food and Drug Safety. The developed method was successfully applied to open-field pear samples, in which the target analyte was slowly dissipated (55% decline) over 14 days with a half-life of 10.19 days. Notably, the residue levels throughout the period of sample collection (14 days) were lower than the maximum residue limit, indicating that the residue was not hazardous for consumers. Copyright © 2016 John Wiley & Sons, Ltd.

Exposure assessment and risk characterisation of ethyl carbamate from Korean traditional fermented rice wine, Takju and Yakju.

Ethyl carbamate is one of the most hazardous chemicals naturally occurring in food, and is present in alcoholic beverages. Korean traditional rice wine, Takju and Yakju, is frequently consumed in Korea, but there have been no studies characterising the risks of ethyl carbamate in these products. In order to assess and characterise the exposure risk of ethyl carbamate in Korean traditional rice wines, ethyl carbamate was investigated by means of GC-MS. The analytical methods were optimised and validated through determining linearity, detection limit, quantification limit, recovery and precision. A total of 283 traditional Korean rice wines, including 175 Takju and 108 Yakju samples, were analysed. Exposure assessment was performed by factoring in ethyl carbamate content, daily consumption and body weight. Daily exposures of ethyl carbamate were estimated for adults in four age groups, and risks of ethyl carbamate were characterised by the margin of exposure, which is more than 10 000. Based on this study, the risks of ethyl carbamate in Korean traditional rice wine were shown to be of low concern.

Estimates of Radiation Doses and Cancer Risk from Food Intake in Korea.

The aim of this study was to estimate internal radiation doses and lifetime cancer risk from food ingestion. Radiation doses from food intake were calculated using the Korea National Health and Nutrition Examination Survey and the measured radioactivity of (134)Cs, (137)Cs, and (131)I from the Ministry of Food and Drug Safety in Korea. Total number of measured data was 8,496 (3,643 for agricultural products, 644 for livestock products, 43 for milk products, 3,193 for marine products, and 973 for processed food). Cancer risk was calculated by multiplying the estimated committed effective dose and the detriment adjusted nominal risk coefficients recommended by the International Commission on Radiation Protection. The lifetime committed effective doses from the daily diet are ranged 2.957-3.710 mSv. Excess lifetime cancer risks are 14.4-18.1, 0.4-0.5, and 1.8-2.3 per 100,000 for all solid cancers combined, thyroid cancer, and leukemia, respectively.

Effects of grilling procedures on levels of polycyclic aromatic hydrocarbons in grilled meats.

Polycyclic aromatic hydrocarbons (PAHs) are chemicals formed when muscle meat is cooked using high-temperature methods, such as grilling directly over an open flame. PAHs have been found to be mutagenic-that is, they cause changes in DNA that may increase the risk of cancer. We investigated the effects of grilling procedures on the level of 4 PAHs; benzo[a]anthracene (B[a]A), chrysene (Chr), benzo[b]fluoranthene (B[b]F), and benzo[a]pyrene (B[a]P). PAHs were extracted and determined by gas chromatography with mass detection (GC-MS). With regard to barbecuing successive meat samples with the same batch of burning charcoal, it was observed that stable combustion contribute to reduction of PAHs. Significant reductions in the sum of the four PAHs were observed through treatments which removed meat drippings and smoke with alternative grilling apparatus. The sums of 4 PAHs were reduced 48-89% with dripping removed and 41-74% with the smoke removal treatment in grilled pork and beef meats than conventional grilling. We investigated the components of meats drippings. The major constituent of meat dripping was fat. The most important factor contributing to the production of PAHs in grilling was smoke resulting from incomplete combustion of fat dripped onto the fire.

Total Diet Studies as a Tool for Ensuring Food Safety.

With the diversification and internationalization of the food industry and the increased focus on health from a majority of consumers, food safety policies are being implemented based on scientific evidence. Risk analysis represents the most useful scientific approach for making food safety decisions. Total diet study (TDS) is often used as a risk assessment tool to evaluate exposure to hazardous elements. Many countries perform TDSs to screen for chemicals in foods and analyze exposure trends to hazardous elements. TDSs differ from traditional food monitoring in two major aspects: chemicals are analyzed in food in the form in which it will be consumed and it is cost-effective in analyzing composite samples after processing multiple ingredients together. In Korea, TDSs have been conducted to estimate dietary intakes of heavy metals, pesticides, mycotoxins, persistent organic pollutants, and processing contaminants. TDSs need to be carried out periodically to ensure food safety.

Total Diet Study: For a Closer-to-real Estimate of Dietary Exposure to Chemical Substances.

Recent amendment on the Food Sanitation Act in Korea mandated the Minister of Food & Drug Safety to secure the scientific basis for management and reevaluation of standards and specifications of foods. Especially because the current food safety control is limited within the scope of 'Farm to Market' covering from production to retail in Korea, safety control at the plane of true 'Farm to Fork' scope is urgently needed and should include 'total diet' of population instead of individual food items. Therefore, 'Total Diet Study (TDS)' which provides 'closer-to-real' estimates of exposure to hazardous materials through analysis on table-ready (cooked) samples of foods would be the solution to more comprehensive food safety management, as suggested by World Health Organization and Food and Agriculture Organization of the United Nations. Although the protection of diets from hazards must be considered as one of the most essential public health functions of any country, we may need to revisit the value of foods which has been too much underrated by the meaningless amount of some hazardous materials in Korea. Considering the primary value of foods lies on sustaining life, growth, development, and health promotion of human being, food safety control should be handled not only by the presence or absence of hazardous materials but also by maximizing the value of foods via balancing with the preservation of beneficial components in foods embracing total diet. In this regard, this article aims to provide an overview on TDS by describing procedures involved except chemical analysis which is beyond our scope. Also, details on the ongoing TDS in Korea are provided as an example. Although TDS itself might not be of keen interest for most readers, it is the main user of the safety reference values resulted from toxicological research in the public health perspective.

Determination of Ethyl Carbamate in Alcoholic Beverages and Fermented Foods Sold in Korea.

Ethyl carbamate (EC) classified as a probable human carcinogen (Group 2A) is naturally formed in alcoholic beverages and fermented foods during fermentation process and/or during storage. The objective of this study was to analyze EC in 34 food items including 14 alcoholic beverages and 20 fermented foods sold in Korea. Each food was collected from 18 supermarkets in 9 metropolitan cities in Korea, and then made into composite. According to food composition and alcohol content, samples were divided into four matrices such as apple juice, milk, Soju (liquor containing about 20% alcohol), and rice porridge. The maximum EC value of 151.06 µg/kg was found in Maesilju (liquor made from Maesil and Soju). Whisky and Bokbunjaju (Korean black raspberry wine) contained 9.90 µg/kg and 6.30 µg/kg, respectively. EC was not detected in other alcoholic beverages. Of 20 fermented foods, Japanese-style soy sauce had highest level of 15.59 µg/kg and traditional one contained 4.18 µg/kg. Soybean paste had 1.18 µg/kg, however, EC was not found in other fermented foods.

Total mercury concentrations in the general Korean population, 2008-2011.

The purpose of this study was to evaluate the blood mercury levels of the general Korean population. The data from subjects of all ages were pooled from recent national surveys. In the combined surveys, the geometric means (GMs) of the blood mercury concentrations in subjects aged 0-7, 8-18, and 19years and above were 2.05 (2010-2011), 2.12 (2010-2011), and 3.74µg/L (2008-2011), respectively. There was an increasing trend in blood mercury levels with age until 59years and then a slight decline in the group above 60years. The time trend for exposure to mercury in Korea also showed a marked decline. In comparing estimated methylmercury exposure to the Korean health-based guidance value (tolerable weekly intake [TWI]: 2.0µg/kgbw/week), the GMs of methylmercury exposure for subjects aged 0-7, 8-18, and 19years and above were 0.30, 0.31, and 0.43µg/kgbw/week, respectively, while methylmercury exposure did not exceed the TWI (15.0%, 15.5%, and 21.5% compared to the TWI, respectively). The 95th percentiles of estimated methylmercury exposure ranged from 0.71 to 1.61µg/kgbw/week, which was not above the TWI (range, 35.5-80.5%).

Reference levels of blood mercury and association with metabolic syndrome in Korean adults.

PURPOSE: Mercury (Hg) is a nonessential and toxic metal that is widely distributed in the environment. This study was performed to estimate the representative blood Hg level, to determine the contributing factors to Hg exposure, and to analyze the association of blood Hg with metabolic syndrome in Korean adults. METHODS: Mercury exposure is assessed by total Hg concentration in blood. A total of 2,114 healthy adults who have not been exposed to Hg occupationally were sampled by the multistaged, sex-, and age-stratified probability method. Information was collected regarding the subjects' demographic characteristics, lifestyles, and past medical history. The participants then underwent physical examination and blood sampling. RESULTS: The geometric mean concentration of Hg in whole blood was 3.90 µg/L, which was significantly influenced by sex, age, smoking, alcoholic consumption, residence area, and seafood intake after adjustment for confounders. Significant increases in body mass index, waist circumference, diastolic blood pressure, total cholesterol, and triglyceride were observed according to the blood Hg levels after adjustment for covariates. Also, Hg exposure was significantly associated with metabolic syndrome and their components such as obesity and increased fasting glucose. CONCLUSION: The blood Hg level in Korean adults is higher than that in USA and other Western countries, while it is similar to or lower than that in other Asian countries. The blood Hg level is influenced by sociodemographic factors and individual lifestyles including dietary habits. Furthermore, blood Hg is associated with metabolic syndrome, in which Hg exposure may play a role as a possible risk factor for cardiovascular diseases.

Biomonitoring of urinary di(2-ethylhexyl) phthalate metabolites of mother and child pairs in South Korea.

Di(2-ethylhexyl) phthalate (DEHP) is one of the common phthalate plasticizers used primarily in soft polyvinyl chloride, which is a plastic polymer that makes up the total weight of goods from 1% up to 40% in many consumer products. The aims of this study were to examine the urinary DEHP metabolites in South Korean children and to investigate the correlation between mother and child DEHP urine excretion. Three kinds of urinary DEHP metabolites: mono(2-ethylhexyl) phthalate (MEHP), mono(2-ethyl-5-hydroxyhexyl) phthalate (5-OH-MEHP) and mono(2-ethyl-5-oxohexyl) phthalate (5-oxo-MEHP), were analyzed. The total of 954 samples (nChildren=392, nMothers=265, nAadults=297), including 258 mother and child pairs, were analyzed using isotope dilution gas chromatography-mass spectrometry. Many studies present higher concentration of DEHP metabolites detected from adults in reproductive age than adults in other ages. Therefore, adults who are age-matched to mothers were evaluated to serve as a standard of comparison against mothers. All statistical analysis was made by adjusting detected volume concentrations (µg/L) with respect to creatinine concentrations (mg/dL) since urinary DEHP metabolites were studied using human reference. The difference in median levels of sum of urinary DEHP metabolites was only significant when children were analyzed in relation to region (p-value≤0.005). Among the three DEHP metabolites, only MEHP of children was significantly correlated to that of paired mothers (p-value≤0.01). The present paper defines the relative metabolic rate (RMR) of DEHP metabolism for the first time in study on phthalates. Children had faster RMR than mothers and adults, specifically in the first step of DEHP metabolism (RMR1: MEHP hydroxylation to 5-OH-MEHP), and RMR1 of children between 1 and 24 months was the fastest. The above results may be used to study and assess human health risk from DEHP exposures, especially among mothers and children in Korea.

Evaluation of in vitro screening system for estrogenicity: comparison of stably transfected human estrogen receptor-α transcriptional activation (OECD TG455) assay and estrogen receptor (ER) binding assay.

The estrogenic activity of industrial chemicals, di(2-ethylhexyl) phthalate (DEHP), di(n-butyl) phthalate (DBP), benzylbutyl phthalate (BBP), diethyl phthalate (DEP), tetrabromobisphenol A (TBBPA), bisphenol A (BPA), and nonylphenol (NP), was compared using OECD test guideline 455(TG455), stably transfected transcriptional activation (STTA) and estrogen receptor (ER) binding assays. The estrogenic activity of BBP, BPA and NP were approximately 180,000-fold (PC(50), 4.32 x 10(-6 )M), 5,000-fold (PC(50), 1.26 x 10(-7) M) and 120,000-fold (PC(50), 2.92 x 10(-6 )M) less than 17ß-estradiol (PC(50), 2.43 x 10(-11)M), whereas DEHP, DBP and DEP did not show any estrogenicity activity in the STTA assay. Moreover, binding affinities to human ERα of BBP, BPA, and NP were approximately 200,000-fold (IC(50), 4.91 x 10(-4) M), 8000-fold (IC(50), 1.92 x 10(-5) M) and 1400-fold (IC(50), 3.34 x 10(-6) M) less than 17ß-estradiol (IC(50), 2.45 x 10(-9) M) in competitive human ERα binding assay. The relative potencies of STTA assay were very similar to ER binding, E-screen, and Yeast screening assays. Therefore, our results suggested that OECD test guideline TG455 may be useful as a screening test for potential endocrine disruptors.

Lead, cadmium and mercury levels in the 2010 Korean diet.

This study analysed the level of contamination of harmful heavy metals in 3820 food samples available in Korea in 2010. A total of 119 types of samples were collected, including corns, vegetables, fruits, fishes, mollusks, shellfish, crustaceans, seaweed, bean products, meats and eggs from seven major cities. These samples were analysed using ICP-MS after pre-treatment with a microwave-digestion system. Results of lead, cadmium and mercury analyses were compared with the standard specifications of Korea Food Standards Codex. As a result, high levels of Pb, Cd and Hg were detected in "cockle," "dried-squid" and "shark-meat." Acceptable intake for consumers was checked using provisional tolerable weekly intake values. Such results will be utilised as data on the exposure of human body through foods. In addition, satisfactory results were obtained through purchase and analysis of National Institute of Science and Technology-certified reference materials to obtain reliability on analysis results.

Risk assessment principle for engineered nanotechnology in food and drug.

While the ability to develop nanomaterials and incorporate them into products is advancing rapidly worldwide, understanding of the potential health safety effects of nanomaterials has proceeded at a much slower pace. Since 2008, Korea Food and Drug Administration (KFDA) started an investigation to prepare "Strategic Action Plan" to evaluate safety and nano risk management associated with foods, drugs, medical devices and cosmetics using nano-scale materials. Although there are some studies related to potential risk of nanomaterials, physical-chemical characterization of nanomaterials is not clear yet and these do not offer enough information due to their limitations. Their uncertainties make it impossible to determine whether nanomaterials are actually hazardous to human. According to the above mention, we have some problems to conduct the human exposure risk assessment currently. On the other hand, uncertainty about safety may lead to polarized public debate and to businesses unwillingness for further nanotechnology investigation. Therefore, the criteria and methods to assess possible adverse effects of nanomaterials have been vigorously taken into consideration by many international organizations: the World Health Organization, the Organization for Economic and Commercial Development and the European Commission. The object of this study was to develop risk assessment principles for safety management of future nanoproducts and also to identify areas of research to strengthen risk assessment for nanomaterials. The research roadmaps which were proposed in this study will be helpful to fill up the current gaps in knowledge relevant nano risk assessment.

Heavy metal risk management: case analysis.

To prepare measures for practical policy utilization and the control of heavy metals, hazard control related institutions by country, present states of control by country, and present states of control by heavy metals were examined. Hazard control cases by heavy metals in various countries were compared and analyzed. In certain countries (e.g., the U.S., the U.K., and Japan), hazardous substances found in foods (e.g., arsenic, lead, cadmium, and mercury) are controlled. In addition, the Joint FAO/WHO Expert Committee on Food Additives (JECFA) recommends calculating the provisional tolerable weekly intake (PTWI) of individual heavy metals instead of the acceptable daily intake (ADI) to compare their pollution levels considering their toxicity accumulated in the human body. In Korea, exposure assessments have been conducted, and in other countries, hazardous substances are controlled by various governing bodies. As such, in Korea and other countries, diverse food heavy metal monitoring and human body exposure assessments are conducted, and reducing measures are prepared accordingly. To reduce the danger of hazardous substances, many countries provide leaflets and guidelines, develop hazardous heavy metal intake recommendations, and take necessary actions. Hazard control case analyses can assist in securing consumer safety by establishing systematic and reliable hazard control methods.

An analytical method for prohexadione in Chinese cabbage and apple.

A residual determination method as a regulatory residue method was developed using HPLC-UVD for prohexadione residues in Chinese cabbage (Brassica pekinensis) and apple (Malus domestica). The developed method consisted of solid-liquid extraction with acidic acetonitrile and ion-suppression liquid-liquid partitioning, followed by anion exchange cartridge cleanup. The limits of detection and quantitation for the method were 0.005 and 0.02 mg/kg, respectively. The method gave good linearity in the range of 0.02-2.5 mg/kg. Accuracy and precision ranged from 84.1 to 94.1% and from 2.4 to 6.9%, respectively. Additionally, the confirmative conditions of LC-MS/MS for prohexadione were set in negative electrospray ionization mode with transitions of m/z 211.4 → 167.5 and m/z 211.4 → 123.5 in the selected reaction monitoring mode. The applicability of the method was demonstrated by analyzing real samples collected from local markets in Seoul, Republic of Korea. This developed method fully deserves consideration in accordance with its sensitivity, accuracy and precision required for residue analysis of prohexadione in Chinese cabbages and apples.