Development and validation of an ionic chromatography method for nitrite determination in processed foods and estimation of daily nitrite intake in Korea.

A simple ionic chromatography method for nitrite analysis in processed food products was developed and validated. Nitrite in the sample was extracted using 80 °C distilled deionized water and centrifuged. Purification of nitrite from sample solution was performed using OnGuard II Ag, OnGuard II RP and OnGuard II Na cartridge connected in order. Determination of nitrite was carried out using IonPac AG9-HC (4 × 50 mm) and IonPac AS9-HC (4 × 250 mm) columns and a 9 mM sodium carbonate mobile phase. The validated results showed good linearity (r2 > 0.999), recoveries (83.7-107.6%) and precision (1.3-5.1%). The levels of nitrite in processed food products were between n.d. to 33.5 mg/kg, and nitrite was detected in ham, sausage and bacon products. The mean nitrite intake was 2.7% of the Acceptable Daily Intake (ADI, 0.07 mg/kg bw/day) for the Korean population. The method was suitable for the analysis of nitrite in processed foods.

Improved spectrophotometric method for nitrite determination in processed foods and dietary exposure assessment for Korean children and adolescents.

A spectrophotometric method based on diazo-coupling reaction for nitrite analysis was established and validated, including inter-laboratory validation, linearity, accuracy, precision, the limit of detection (LOD) and limit of quantification (LOQ). The time-saving and high-recovery method was established by examining the filtration step, colorimetric process and concentration range of the calibration curve. This method showed good linearity (r2 > 0.999) in the range of 0.025-1.0 µg/mL. The three-level recoveries were between 86.7% and 108.6%, with the coefficient of variation (CV) below 5.8%. Mean nitrite concentration ranges in processed foods were ND-33.47 mg/kg. The mean nitrite intake was 0.8% of the Acceptable Daily Intake (ADI, 0.07 mg/kg bw/day) for all children and adolescents and 2.8% for the consumer group. The major contributors for all subjects and consumers were ham, sausage and bacon. These results indicated that the improved method was suitable for analyzing nitrite in processed foods and the nitrite exposure levels were safe.

Analysis of illegal colourants (citrus red II, diethyl yellow, dimethyl yellow, metanil yellow and rhodamine B) in foods by LC-UV and LC-MS/MS.

Synthetic colourants are highly regulated due to their correlation with a variety of health hazards. Regulatory services must be able to detect the substances in a cost-effective, efficient, and sensitive manner. LC-UV and LC-MS/MS methods have been developed to simultaneously detect five illegal colourants in foods, such as: citrus red II, diethyl yellow, dimethyl yellow, metanil yellow, and rhodamine B. This method showed good linearity (R 2 > 0.99) and low limits of detection (0.09-0.19 mg kg-1) and quantitation (0.26-0.58 mg kg-1). The recoveries at three standard concentration levels ranged between 80.9% and 120%, with relative standard deviations below 12%. The expanded uncertainties determined for the five colourants in three food matrices were 8.2-19.4%. This method was applied to monitor five illegal colourants in imported and domestic beverages, candies, and sauces. None of the five colourants were found in any of the 510 samples. The method is suitable for quantitative analysis of five illegal colourants simultaneously in various foods and can be applied to improve current surveillance and inspection services.

Dietary exposure assessment of synthetic food colours using analytical concentrations in Korea.

The safety of nine synthetic colour additives approved in Korea were assessed through hazard identification, hazard characterisation, exposure assessment, and risk characterisation. Hazard identification and characterisation were conducted using new risk information based on toxicology data. Exposure assessment calculated the estimated daily intake (EDI) of the nine colours. Finally, the risk was evaluated by comparing the EDIs of the colours with the acceptable daily intake (ADI). 1,114 samples (24 food categories) among a total of 1,454 samples contained colour additives either at a level that was not detectable or up to a quantified maximum of 288 mg kg-1. The likelihood of risk of exposure to all food colours, evaluated by comparing the EDI with the ADI, was less than 0.52% of the ADI for the general population. These results indicate that use of synthetic food colour in Korea is safe and does not result in excessive exposure to any population group.

Safety assessment of antioxidants and color fixatives for the Korean population using dietary intake monitoring.

Food additives such as antioxidants and color fixatives are substances used in food intentionally for technical effect, such as decolorizing or intensifying the color of food. Based on the necessity of re-evaluating food additives for safety and to improve consumer perception, we conducted safety assessments for food additives according to the Risk Assessment Guidelines of the Korean Ministry of Food and Drug Safety. These safety assessments evaluated new risk information based on toxicology data and estimates of dietary intake exposures to food additives in comparison with the acceptable daily intake (ADI). Estimated daily intakes (EDI) of food additives were calculated using food consumption data for the Korean population derived from the Korea National Health and Nutrition Examination Survey and monitoring data based on the analysis of food additives in food products. Unlike contaminants, antioxidants and color fixatives are purposely added as food additives, and they are largely consumed in processed foods. Therefore, EDI was compared with ADI to investigate the likelihood of potentially hazardous effects in humans. The risk likelihoods of food additives, evaluated by comparing the EDI with the ADI, were less than 2% in the total population. Thus, exposure levels to antioxidants and color fixatives do not exceed the ADI. Based on the safety assessments conducted in this study, we estimate exposure to food additives to be within safe limits for all population groups.

Naturally occurring benzoic, sorbic, and propionic acid in vegetables.

Benzoic, sorbic and propionic acid are used as preservatives in foods and can also be naturally present in processed foods. The levels of preservatives in 939 vegetables were determined. Benzoic and sorbic acid were analysed by high-performance liquid chromatography with a diode-array detector and further confirmed by liquid chromatography-tandem mass spectrometry, whereas propionic acid was analysed using a gas chromatography-flame ionization detector and further confirmed by gas chromatography-mass spectrometry. Benzoic and propionic acid were found in 10.9% and 36.2%, respectively, of the samples. In contrast, sorbic acid was not found in any of the samples. The highest amounts of benzoic and propionic acid were found in perilla leaves (0.33-298 mg kg-1) and ginseng (

Simultaneous determination of sodium iron chlorophyllin and sodium copper chlorophyllin in food using high-performance liquid chromatography and ultra-performance liquid chromatography-mass spectrometry.

A simultaneous method for analyzing sodium iron chlorophyllin (SIC) and sodium copper chlorophyllin (SCC) using high-performance liquid chromatography was developed. This method employed an Inertsil ODS-2 column and diode array detection at 395 nm, using methanol-water (97:3 and 80:20, v/v) containing 1% acetic acid as the mobile phase. Liquid chromatography-tandem mass spectrometry was used to identify the main components of SIC and SCC as Fe-isochlorine e4 and Cu-isochlorine e4, respectively. The limits of detection and quantitation of SIC were 1.2 and 4.1 mg/kg, respectively, while those of SCC were 1.4 and 4.8 mg/kg, respectively. For intraday and interday tests, the SIC recoveries from candy ranged from 81% to 101%, while SCC recoveries ranged from 100% to 109%. The developed method can be applied to the rapid determination of SIC and SCC in candy.

Improved method for the determination of 12 non-nutritive sweeteners and monitoring in various foods using liquid chromatography-tandem mass spectrometry.

An improved and highly sensitive method was developed and validated for the determination of 12 (7 permitted and 5 non-permitted in Korea) non-nutritive sweeteners in various foods using liquid chromatography-electrospray ionisation-tandem mass spectrometry. The chromatographic separation was performed on an Xbridge BEH C18 column (3 mm × 100 mm, 2.5 µm) with gradient elution using 10 mM ammonium acetate in water and 10 mM ammonium acetate in methanol. Sample preparation consisted of simple dilution, homogenisation, centrifugation and purification with a C18 cartridge prior to analysis. The relative matrix effect (%ME) was within ±20% for all sweeteners. The method also showed good linearity (R2 > 0.99). The limit of detection and limit of quantification values in sample were in the range of 0.02-2.66 and 0.06-8.05 mg kg-1, respectively. The recoveries at three concentration levels ranged between 80% and 119%, with relative standard deviation values below 10%. In addition, the expanded uncertainties determined for 12 sweeteners in 5 different food matrices were confirmed to be <14%. Finally, the method was successfully applied to the analysis of sweeteners in 681 food samples purchased in Korea, Australia and Turkey. These results demonstrate that the method is suitable for the simultaneous determination of multiple-sweeteners in a variety of foods.

Sorbic, benzoic and propionic acids in fishery products: a survey of the South Korean market.

This study was conducted to provide basic data as part of a project to distinguish naturally occurring organic acids from added preservatives. Accordingly, we investigated naturally occurring levels of sorbic, benzoic and propionic acids in fish and their processed commodities. The levels of sorbic, benzoic and propionic acids in 265 fish and their processed commodities were determined by high-performance liquid chromatography-photodiode detection array (HPLC-PDA) of sorbic and benzoic acids and gas chromatography-mass spectrometry (GC/MS) of propionic acid. For propionic acid, GC-MS was used because of its high sensitivity and selectivity in complicated matrix samples. Propionic acid was detected in 36.6% of fish samples and 50.4% of processed fish commodities. In contrast, benzoic acid was detected in 5.6% of fish samples, and sorbic acid was not detected in any sample. According to the Korean Food and Drug Administration (KFDA), fishery products and salted fish may only contain sorbic acid in amounts up to 2.0 g kg-1 and 1.0 g kg-1, respectively. The results of the monitoring in this study can be considered violations of KFDA regulations (total 124; benzoic acid 8, propionic acid 116). However, it is difficult to distinguish naturally generated organic acids and artificially added preservatives in fishery products. Therefore, further studies are needed to extend the database for distinction of naturally generated organic acids and added preservatives.

An Improved Analytical Method for the Determination of Brown FK in Food using HPLC.

In this study, an improved analytical method for the detection of the colorant Brown FK in foods using high-performance liquid chromatography was developed. The method, which employed an RC-C18 column and diode array detection at 254 nm with sodium acetate solution and methanol as mobile phases, exhibited good linearity (R2 = 1.0), and its limits of detection and quantification were determined to be 0.06 and 0.19 µg/mL, respectively. The precision was found to be 0-1.2% and the accuracy was between 86.5% and 94.8%. Liquid chromatography-tandem mass spectrometry was also performed to identify Brown FK in peaks. The pretreatment method was optimized for three different food sample groups, i.e., seafood, noodles and other, affording recoveries of 86.5-92.8%, 90.8-94.8% and 90.0-92.3%, respectively. In addition, inter-laboratory testing was also conducted to check the precision.

Identifying method validation and measurement uncertainty of brominated vegetable oil in soft drinks and carbonated waters commonly consumed in South Korea.

This study investigated a method for validating and determining the measurement uncertainty for the composition of brominated vegetable oil (BVO) in soft drinks and carbonated waters commonly consumed in South Korea. First, we studied a simple and precise qualitative colorimetric method at the maximum residues level 15 ppm. And an analytical method using ion chromatography (IC) was validated and identified with brominated fatty acids by gas chromatography electron ionization mass spectrometry (GC/EI-MS). The measurement uncertainty was evaluated based on the precisional study and confirmed by the preliminary inter-laboratory study. For IC analysis, the recovery range of BVO was from 97.8% to 107.2% with relative standard deviations between 0.18% and 0.69%. In addition, the expanded uncertainty of the BVO was 1.59. These results indicate that the validated method is appropriate for identifying of BVO and can be used to verify the safety of soft drinks or carbonated waters containing BVO residues.

Safety assessment of 16 sweeteners for the Korean population using dietary intake monitoring and poundage method.

A sweetener is a food additive that imparts a sweet taste to food products. Sweeteners have been increasingly used in Korea since the approval of sodium saccharin and d-sorbitol in 1962. Unlike food contaminants, humans are exposed to food additives only through the consumption of processed food products. For exposure assessments of sweeteners, the dietary intakes of food products containing acesulfame-K, aspartame, saccharin-Na, and sucralose were determined, and the resulting calculated estimated daily intake (EDI) values were compared directly with each additive's ADI. The poundage method was used to calculate the daily intake per capita for 12 additional sweeteners, such as lactitol, for which appropriate analytical methods for food products do not exist. The risk, as evaluated by comparing the EDI with the ADI, was determined to be 2.9% for acesulfame-K, 0.8% for aspartame, 3.6% for saccharin-Na, 4.3% for steviol glycosides, and 2.1% for sucralose. No hazardous effect was predicted for the other 11 sweeteners, including lactitol.

Perception Gaps on Food Additives among Various Groups in Korea: Food Experts, Teachers, Nutrition Teachers, Nongovernmental Organization Members, and General Consumers.

The purpose of this study was to determine the perceptions and information needs of food experts, teachers, nutrition teachers, members of nongovernmental organizations, and general consumers concerning food additives. Questions in a survey format included perceptions, information needs, and preferred communication channels. The survey was conducted both off-line and on-line via e-mail and Google Drive in March 2015. The results indicated that most Korean consumers are concerned about the safety of using food additives in processed foods and do not recognize these additives as safe and useful materials as part of a modern diet. We also identified perception gaps among different groups regarding food additives. Nutrition teachers and members of nongovernmental organizations in Korea appeared to have a biased perception of food additives, which may cause general consumers to have a negative perception of food additives. The group of food experts did not have this bias. Governmental institutions must overcome the low confidence levels of various groups as an information provider about food additives. Based on the findings in this study, it will be possible to develop a strategy for risk communication about food additives for each group.

Simultaneous determination of sodium saccharin, aspartame, acesulfame-K and sucralose in food consumed in Korea using high-performance liquid chromatography and evaporative light-scattering detection.

Four artificial sweeteners, i.e., sodium saccharin, aspartame, acesulfame-K and sucralose, are permitted for use in Korea, and recent regulatory changes have expanded the number of food categories in which they may be used. Four artificial sweeteners were determined simultaneously in more than 900 food items from 30 food categories that are commercially available in Korean markets, including both domestic and imported products, using high-performance liquid chromatography and evaporative light-scattering detection (ELSD). A new procedure using 75% acetone to remove fat was applied for sample preparation. The levels detected in all samples were below the maximum permitted use levels established in Korea. Despite the increased number of categories, the only one in which sodium saccharin was newly found was takju, an alcoholic beverage. Sodium saccharin was not found in other beverages in the food analysis or in the food label survey, even though its use was reported in a previous study, suggesting that consumer preference outweighs regulatory decisions. When the analytical results were combined with food-consumption data obtained from the Korea National Health and Nutrition Examination Survey 2010-14, the estimated daily intakes of all the sweeteners were considered safe.

An analysis method for determining residual hexane in health functional food products using static headspace gas chromatography.

A method for analyzing the contents of residual hexane in health functional food products was developed. The dissolving solvents in the health functional food products and the internal standard selected were N,N-dimethylacetamide and heptane, respectively. The analysis conditions for headspace-gas chromatography/flame ionization detection (HS-GC/FID) and headspace-gas chromatography/mass spectrometry (HS-GC/MS) were determined as 18 mL of headspace volume, 100°C of headspace oven temperature, and 30 min of equilibration time; a Durabond (DB)-624 column was selected for this analysis. To validate this method, which applies N,N-dimethylacetamide as a dissolving solvent, the limit of detection and limit of quantification (LOQ) values based on the HS-GC/FID and HS-GC/MS analyses results were found to be 0.10, 0.29 and 0.16, 0.47 mg/L, respectively. The recoveries and coefficient of variation (CV) obtained by HS-GC/MS were 96.39-119.86% and 0.04-1.25%, respectively, better than those obtained by HS-GC/FID. By applying the HS-GC/MS method, it was possible to analyze the content of the residual hexane in 60 different types of health functional food products.

Method validation and measurement uncertainty for the simultaneous determination of synthetic phenolic antioxidants in edible oils commonly consumed in Korea.

This study investigated a method for the validation and determination of measurement uncertainty for the simultaneous determination of synthetic phenolic antioxidants (SPAs) such as propyl gallate (PG), octyl gallate (OG), dodecyl gallate (DG), 2,4,5-trihydroxy butyrophenone (THBP), tert-butylhydroquinone (TBHQ), butylated hydroxyanisole (BHA), and butylated hydroxytoluene (BHT) in edible oils commonly consumed in Korea. The validated method was able to extract SPA residues under the optimized HPLC-UV and LC-MS/MS conditions. Furthermore, the measurement of uncertainty was evaluated based on the precision study. For HPLC-UV analysis, the recoveries of SPAs ranged from 91.4% to 115.9% with relative standard deviations between 0.3% and 11.4%. In addition, the expanded uncertainties of the SPAs ranged from 0.15 to 5.91. These results indicate that the validated method is appropriate for the extraction and determination of SPAs and can be used to verify the safety of edible oil products containing SPAs residues.

Assessment of the dietary intake of propylene glycol in the Korean population.

An improved method for the analysis of propylene glycol (PG) in foods using a gas chromatography-flame ionisation detector (GC-FID), with confirmation by GC-MS, was validated by measuring several analytical parameters. The PG concentrations in 1073 products available in Korean markets were determined. PG was detected in 74.1% of the samples, in a concentration range from the limit of detection (n.d., 0.39 µg ml(-1)) to 12,819.9 mg kg(-1). The Korea National Health and Nutrition Examination Survey (KNHANES) 2011-2013 reported the mean intake levels of PG from all sources by the general population and consumers were 26.3 mg day(-1) (0.52 mg kg(-1) day(-1)) and 34.3 mg day(-1) (0.67 mg kg(-1) day(-1)), respectively. The 95th percentile intake levels of the general population and consumers were 123.6 mg day(-1) (2.39 mg kg(-1) day(-1)) and 146.3 mg day(-1) (2.86 mg kg(-1) day(-1)), respectively. In all groups of the general population, breads were the main contributors to the total PG intake. These reports provide a current perspective on the daily intake of PG in the Korean population.

Validation and measurement uncertainty evaluation of the GC-MS method for the direct determination of hexamethylenetetramine from foods.

A simple GC-MS method has been developed and validated for the direct determination of hexamethylenetetramine (HMT). The separation of HMT was performed using a MXT-1 column. The calibration curve was linear over the concentration range 0.1-25 µg/mL, with a good correlation coefficient (r =0.9996). The recoveries of HMT from foods spiked at 1, 5, and 10 µg/g ranged from 91.7% to 115.2%. Intra-day (n=5) and inter-day (n=5) precision were less than 7%. The limit of detection and the limit of quantification of the method were 0.05 and 0.15 µg/mL, respectively. The uncertainties associated with food matrix and calibration contributed most to the overall expanded uncertainty. The method validation data indicated that quantitative method could be applied to the direct determination of non-hydrolyzed HMT in foods.

Development and validation of an analytical method for the determination of 4-hexylresorcinol in food.

This study presents a method validation for extraction and quantitative analysis of 4-hexylresorcinol residues in shrimp and crab meat using HPLC-FLD. We were focused on the collaboratively analysis of each shrimp and crab meat samples, and developed LC-MS/MS method for the correct confirmation of the identity of compound. Validation parameters; selectivity, linearity, LOD, LOQ, accuracy, precision, and measurement of uncertainty were attained. The measurement of uncertainty was based on the precision study, data related to the performance of the analytical process and quantification of 4-hexylresorcinol. For HPLC-FLD analysis, the recoveries of 4-hexylresorcinol from spiked samples at levels of 0.2-10.0 ppm ranged from 92.54% to 97.67% with RSDs between 0.07% and 1.88%. According to these results, the method has been proven to be appropriate for extraction and determination of 4-hexylresorcinol, and can be used to maintain the safety of shrimp and crab products containing 4-hexylresorcinol residues.

Assessment of caffeine intake in the Korean population.

An improved method for the analysis of caffeine in foods by HPLC was validated by measuring several analytical parameters. The caffeine contents of 1202 products available from Korean markets were analysed. A consumption study was conducted by using data from the Korea National Health and Nutrition Examination Survey (KNHANES), 2010-12, to estimate the caffeine intakes of the Korean population. The mean intakes of caffeine from all sources in the general population and consumers were 67.8 and 102.6 mg day(-1) for all age groups, respectively. The 95th percentile intakes of the general population and consumers were 250.7 and 313.7 mg day(-1), respectively. In those aged 30-49 years, the caffeine intakes of the general population and consumers were highest at 25.5% (101.8 mg kg(-1) day(-1)) and 36.6% (0.9 mg kg(-1) day(-1)), respectively, compared with the maximum recommended daily intake (400 mg day(-1)) for adults. In the general population, the main contributors to the total caffeine intake were carbonated beverage for the younger age groups and coffee for the adults. These data provide a current perspective on caffeine intake in the Korean population.