Monitoring, exposure and risk assessment of formaldehyde in alcoholic beverages in Korea.

Formaldehyde occurs naturally in food and alcoholic beverages. Formaldehyde and alcoholic beverages can cause various health problems, including irritation of the eyes, nose, and throat, respiratory problems, and skin rashes. Alcoholic beverage samples (N = 236) were collected and analyzed for formaldehyde by liquid chromatography-tandem mass spectrometry. The highest average concentrations were detected in fruit wines (1.71 µg/g), followed by wines (1.15 µg/g), cheongju (0.95 µg/g), soju (0.85 µg/g), takju (0.64 µg/g) and beers (0.61 µg/g). We assessed the exposure and risk assessment to formaldehyde from alcoholic beverages based on the monitoring data for the general population and consumers in Korea using various schemes for point estimation. The daily intakes of formaldehyde for the general population and consumers were estimated to be 83 µg and 1202 µg, respectively. The mean hazard indexes (HI) for the general population and consumers in Korea were 0.009 and 0.132, respectively. On the other hand, the mean hazard indexes (HI) for the general population and consumers in Korea were 0.009 and 0.132, respectively. The exposure to formaldehyde in these alcoholic beverages for the Korean population was shown to be of low concern, but it is necessary to monitor the level of formaldehyde in alcoholic beverages and continuously conduct exposure assessment for consumers.

Simultaneous determination of the free and total forms of nonylphenol, nonylphenol monoethoxylate, and nonylphenol diethoxylate in human urine by gas chromatography-mass spectrometry.

Nonylphenol (NP), nonylphenol monoethoxylate (NP1EO), and nonylphenol diethoxylate (NP2EO) are widely used in various daily products and have been cataloged as endocrine-disrupting chemicals. Due to their high lipophilicity and low biodegradability, these compounds remain in the environment and enter the human body through the food chain. Growing concerns regarding the potential negative effects of NP, NP1EO, and NP2EO on human health have raised the need for biomonitoring to investigate human exposure to these compounds. In this study, a simultaneous analysis method using solid-phase extraction (SPE) combined with gas chromatography-mass spectrometry (GC-MS) was established by controlling the background contamination of NP, NP1EO, and NP2EO, which are ubiquitous in laboratory environments. The proposed method showed proper linearity of over 0.999 and a recovery greater than 85.8% for all analytes. Accuracy and precision were verified in ranges of 92.97-116.30% and 0.65-9.29%, respectively. The detection limits for NP, NP1EO, and NP2EO were 0.0363 µg L-1, 0.0401 µg L-1, and 0.0364 µg L-1, respectively, which were suitable for determining the trace analytes in human urine. Therefore, this simple and integrated analytical method was applied to measure the free and total forms of the target analytes in 25 human urine samples collected in Korea. Overall, free NP, NP1EO, and NP2EO were detected with average contents of 3.94 ± 4.14 µg L-1, 4.63 ± 2.62 µg L-1, and 0.293 ± 0.638 µg L-1, respectively, and with total NP, NP1EO, and NP2EO contents of 6.14 ± 8.24 µg L-1, 5.99 ± 2.91 µg L-1, and 0.806 ± 1.10 µg L-1, respectively. These data showed that these compounds are prevalent in human urine, and indicate the need for further studies.

Analysis of Endocrine Disrupting Nonylphenols in Foods by Gas Chromatography-Mass Spectrometry.

Nonylphenols (NPs) are classified as endocrine-disrupting chemicals (EDCs), which are known to cause disorders in the endocrine systems of organisms. Due to their high lipophilicity and low degradability, these harmful substances are known to accumulate and persist in the environment, and even enter into the food chain. Analytical methods of liquid-liquid extraction using solid-phase extraction for sample clean-up combined with gas chromatography/mass spectrometry were established to determine the presence of NPs in foods. This study aimed to develop and validate these methods using four food matrices representing high-fat and low-fat solid food, as well as high-fat and low-fat liquid food, groups. The single linear isomer 4-n-NP was used to validate the quantification of NPs, which exist in complex isomer mixtures. Our results showed good linearity, with correlation coefficients exceeding 0.998 for all four matrices. The limits of detection and quantification were 0.37-1.79 and 1.11-5.41 µg/kg, respectively. Recovery rates were 86.8-108.6% and 92.6-101.9% for intraday and interday assays, respectively, and the relative standard deviations (RSDs) were below 12% for both assays. The method was applied to analyze 1185 domestic food samples consumed by Koreans, with NPs detected at concentration ranges of 2.57-269.07 µg/kg. Results for each food type over wide concentration ranges indicated that these compounds are highly dependent on the area of cultivation, and are affected by the levels of those contaminants in different environments. The contents of NPs in foods from animal sources were generally higher than those from plant sources, in particular being higher in the intestines than in lean tissue. The present findings could form the basis for determining the level of dietary exposure to NPs and how each food source contributes to it in South Korea.

Subjective Well-Being in Older Chinese and Korean Immigrants in the United States: Effects of Self-Rated Health and Employment Status.

This study examined the effects of association between self-rated health and employment status on subjective well-being among older Chinese and Korean immigrants in the United States. Data were collected from 171 Chinese and 205 Korean older adult immigrants living in Los Angeles County. The primary variables included demographic data, subjective index of well-being, self-rated health, and employment status. Data support the association between self-rated health and subjective well-being for both groups. Employment, education, and age were associated with the level of subjective well-being only for older Korean immigrants. Similarities and differences were noted in these two Asian American subgroups. Findings suggest the need to develop health promotion services for both populations and employment opportunities targeted more so for Korean older immigrants to further support their subjective well-being. Results may have implications for other for older immigrants.

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.

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.

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.

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.

Analysis method for determination of nisin A and nisin Z in cow milk by using liquid chromatography-tandem mass spectrometry.

Nisin, a polypeptide with antimicrobial properties, is known as a natural preservative. It is used in various foods, including dairy products. This study validated a novel procedure using liquid chromatography-tandem mass spectrometry (LC-MS/MS) for the determination of nisin A and nisin Z in cow milk. An extraction solution of 0.1 M acetate buffer containing 1 M NaCl (pH 2.0) and MeOH (1:1) was used to extract nisin A and nisin Z from milk samples. After the addition of extraction buffers, the samples were homogenized and centrifuged. The supernatant was filtered and injected for LC-MS/MS analysis. The linearity of the analytical method had a high correlation coefficient (r≥0.9987). The limits of quantitation of nisin A and nisin Z were approximately 12.9 and 10.9 µg/kg, respectively. The accuracy of the analytical method in milk ranged from 90.6 to 103.4% for nisin A and from 83.8 to 104.4% for nisin Z. The coefficient of variation values of intra- and interday in milk determined to be less than 5% in both nisin A and nisin Z. Because the proposed method has comparatively high recovery and low coefficient of variation, it seems appropriate for the determination of nisin A and nisin Z in milk samples. As the quantification of nisin A and nisin Z in milk samples by using LC-MS/MS has only been rarely reported until now, this study provides a meaningful technological advance for the dairy industry.

Determination of Tinopal CBS-X in rice papers and rice noodles using HPLC with fluorescence detection and LC-MS/MS.

To date there have been no reports of methods to determine Tinopal CBS-X. We developed a rapid and simple method to determine the Tinopal CBS-X content in rice noodles and rice papers using HPLC equipped with fluorescence detection. Heating the rice noodles and rice papers to 80°C after adding 75% methanol solution induced the release of Tinopal CBS-X from processed rice products. Tinopal CBS-X was separated using an isocratic mobile phase comprising 50% acetonitrile/water containing 0.4% tetrabutyl ammonium hydrogen sulphate at pH 8.0. The samples suspected to be positive by HPLC analysis were then confirmed by LC-MS/MS analysis. This study also investigated the Tinopal CBS-X content of three rice noodle products and two rice papers. The limits of quantification for rice papers and rice noodles were 1.58 and 1.51 µg kg(-1), respectively, and their correlation curves showed good linearity with r(2) ≥ 0.9997 and ≥ 0.9998, respectively. Moreover, rice papers had recoveries of 70.3-83.3% with precision ranging from 5.0% to 7.9%, whereas rice noodles had slightly lower recoveries of 63.4-78.7% and precisions of 8.5-11.5%. Only one rice noodle product contained Tinopal CBS-X, at around 2.1 mg kg(-1), whereas it was not detected in four other samples. Consequently, Tinopal CBS-X from rice noodles and rice papers can be successfully detected using the developed pre-treatment and ion-pairing HPLC system coupled with fluorescence detection.

Determination of hexamethylenetetramine in foods by high-performance liquid chromatography (HPLC).

A simple and rapid method was developed and validated for the determination of hexamethylenetetramine (HMT) in foods. Samples were homogenised and extracted with methanol, followed by centrifugation. The resulting solution was filtered and injected into the high-performance liquid chromatograph (HPLC). HMT was separated using a Zorbax SCX-300 column coupled to a photodiode array detector. The calibration curve was linear in the range of 1.0-100 µg ml(-1), with good correlation coefficients (r(2) = 0.9992). The recoveries of HMT from foods spiked at levels of 10, 50 and 100 mg kg(-1) ranged from 91.6% to 103.8%, with relative standard deviations (RSDs) between 0.9% and 5.3%. The limit of detection and the limit of quantification of HMT were 0.3 and 1.0 mg kg(-1) based on three food matrixes (provolone cheese, glass noodle and tofu snack), respectively. Uncertainty associated with accuracy contributed mostly to the expanded uncertainty. No detectable levels of HMT were found in any of the samples retailed in Korea. The method was successful in determining HMT in foods.

HPLC and UPLC methods for the determination of zearalenone in noodles, cereal snacks and infant formula.

High-performance liquid chromatography (HPLC) and ultra-performance liquid chromatography (UPLC) were compared to validate a method for determination of zearalenone (ZON) in noodles, cereal snacks, and infant formulas. The limits of detection and quantification in HPLC and UPLC were found to be 4.0 and 13.0 µg kg(-1) and 2.5 and 8.3 µg kg(-1), respectively. The average recoveries of ZON by HPLC and UPLC ranged from 79.1% to 105.3% and from 85.1% to 114.5%, respectively. The measurement uncertainties of the two methods for ZON determination were within the maximum standard uncertainty. The two methods showed that the levels of ZON in 163 naturally contaminated samples ranged from 4.3 to 8.3 µg kg(-1) by HPLC and 3.1 to 17.6 µg kg(-1) by UPLC. These findings indicate that either method is suitable for the determination of ZON in noodles, cereal snacks, and infant formulas, but UPLC gives faster results with better sensitivity.

Quantitative determination of carmine in foods by high-performance liquid chromatography.

A simple and rapid method has been developed and validated for the determination of carmine in foods. Samples were homogenised and extracted with 0.05 M NaOH, followed by centrifugation. The resulting solution was filtered and injected to HPLC. Carmine was separated by HPLC using an NovaPak C18 column coupled to a photodiode array detector. The contents of carmine were finally quantified using corresponding calibration curves over ranges of 1.0-100 µg ml(-1), with good correlation coefficients (r(2)=0.9999). The recoveries of carmine from foods spiked at levels of 10, 50, and 100 µg g(-1) which ranged from 90.4% to 96.2% with relative standard deviations between 2.8% and 6.8%. Limit of detection and limit of quantification of carmine were 0.4 and 1.0 µg ml(-1), respectively. This method was found to be useful to distinguish carmine from carminic acid, a major component of cochineal extract. The method has been successfully applied to various foods.

Comparison of four different methods for the determination of sulfites in foods marketed in South Korea.

Sulfites in foods were analysed using four methods: optimised Monier-Williams (official method), modified Rankine, HPLC and ion-exchange chromatography (IEC). The modified Rankine and HPLC methods were performed according to the previously reported methods but with some modifications. The IEC method was carried out through a combination of a modified Rankine apparatus and an anion-exchange column for the first time. In false-positive response tests, false-positive results with acetic acid and propionic acid were not observed in the modified Rankine, HPLC or IEC methods, unlike the optimised Monier-Williams method. All methods were evaluated for accuracy, precision and simple correlations. Modified Rankine, HPLC and IEC methods were determined to be suitable for foods with less than 10 mg kg(-1) of sulfur dioxide (SO2). The modified Rankine and HPLC methods were suggested to be the most appropriate for the determination of sulfites in foods due to their high correlation coefficient with the optimised Monier-Williams method (R(2) = 0.9138 and 0.9011, respectively).

Dietary assessment of human exposure to PBDEs in South Korea.

This study was conducted to measure the concentration of PBDEs in various food stuffs from Korea and to estimate levels of PBDE intake from food for the Korean population according to geographical location and age. 20 types of food samples were collected from four heavily populated cities (Seoul, Gwangju, Daejeon, Pusan) and one rural city (Gangneung) and were analyzed for 19 polybrominated diphenyl ether congeners (BDE 15, 17, 28, 33, 47, 49, 66, 71, 85, 99, 100, 119, 126, 138, 153, 154, 183, and 209). No significant differences in total PBDE levels in foods were found among four large cities (Gwangju; 10.91 ng g(-1) wet weight (ww), Seoul; 7.66 ng g(-1)ww, Daejeon; 6.91 ng g(-1)ww, Pusan; 6.87 ng g(-1)ww) and one rural city (Gangneung; 8.72 ng g(-1)ww). Daily dietary intake of PBDEs does not appear to be related to the extent of urbanization. Total dietary intake of PBDE for the average general population was 72.30 ng d(-1) (not detected (ND)=0) which was similar to other countries. In all food groups, the largest contribution to PBDE intake was from fish and shellfish (48.96 ng d(-1)). Total PBDE consumed per kilogram of body weight was estimated to range from 2.70 ng kg(-1)d(-1) for infants 1 through 2 years of age to 0.85 ng kg(-1)d for 65 years and older and was highest in young children and decreased with increasing age.

T-2 and HT-2 toxins in cereals and cereal-based products in South Korea.

A total of 214 samples, consisting of brown rice, barley, mixed grains, corn, wheat and wheat flour were analysed for T-2 and HT-2 toxins using high-performance liquid chromatography with fluorescence detection. Recovery and repeatability were 79.9%-107.5% and 4.9%-14.5% for T-2, and 74.0%-106.1% and 5.0%-17.9% for HT-2, respectively. T-2 toxin was detected in 11 (5.1%) of all samples. The highest incidence was found in corn (21.7%) followed by mixed grains and brown rice. Mean of all samples was 1.5-4.1 µg kg⁻¹, the maximum level being 41.5 µg kg⁻¹ in corn. HT-2 toxin was detected in 126 (58.9%) of all samples, and the mean values were 26.4-59.2 µg kg⁻¹. The estimated daily intakes for the sum of T-2 and HT-2 toxins were 2.56, 3.22, 2.53, 0.03, 0.01 and 2.45 ng (kg bw)⁻¹ day⁻¹ in brown rice, barley, mixed grains, corn, wheat and wheat flour, respectively.

In-house-validated liquid chromatography-tandem mass spectrometry (LC-MS/MS) method for survey of acrylamide in various processed foods from Korean market.

Acrylamide (AA) is a chemical found in starchy foods that have been cooked at high temperatures. The objective of this study is to monitor the levels of AA in a total of 274 samples of potato chips, chips (except potato chips), biscuits, French fries, breakfast cereals, chocolate products, tea, seasoned laver, and nut products sampled in Korean market. These processed foods include (1) potato chips, (2) chips (except potato chips), (3) biscuits, (4) French fries, (5) breakfast cereals, (6) chocolate products, (7) tea, (8) seasoned laver, and (9) nut products. Samples used for this study were cleaned up using HLB Oasis polymeric and Accucat mixed-mode anion and cation exchange solid-phase extraction cartridge. Liquid chromatography-tandem mass spectroscopy (LC-MS/MS) was validated in-house as an efficient analytical method for the routine analysis of AA in various food products. AA was detected with a Fortis dC18 (1.7 µm, 100 mm × 2.1 mm) column using 0.5% methanol/0.1% acetic acid in water as the mobile phase. Good results were obtained with respect to repeatability (RSDs < 5%). The recoveries obtained for a variety of food matrices ranged between 94.5% and 107.6%. Quantification during routine monitoring was sensitive enough to detect AA at a concentration of 10 µg/kg. A total of 274 food samples were analyzed for AA. The AA levels in the food groups were in the following order: potato chips > French fries > biscuits > tea > chips (except potato chips) > seasoned laver > breakfast cereals > chocolate products > nut products. AA was detected at levels ranging from not detectable to 1435 µg/kg.

Measures for a closer-to-real estimate of dietary exposure to total mercury and lead in total diet study for Koreans.

Previous Korean total diet studies (KTDSs) have estimated dietary exposure to toxic chemicals based on 110-120 representative foods selected from over 500 foods appeared in the Korea National Health & Nutrition Examination Surveys (KNHANES), which would result in a possible underestimation. In order to find measures for a closer-to-real estimate of dietary exposure to heavy metals, this study examined the feasibility of mapping foods to the representative foods in the KTDS by comparing estimates. In mapping, those foods not analyzed in the 2009 KTDS (443 out of 559 foods appeared in the 2007 KNHANES) were mapped to the 114 representative foods used in the 2009 KTDS based on the closeness in regards to biological systematics and morphological similarity. Dietary exposures to total mercury and lead were re-estimated using the content of total mercury and lead in 114 foods analyzed in the 2009 KTDS, food intake, and individual's own body weight for respondents in the 2007 KNHANES instead of mean body weight of Koreans used in the 2009 KTDS. The re-estimates of exposure with mapping were approximately 50% higher than the original estimates reported in the 2009 KTDS. In addition, mapping enabled the comparison of percentile distribution of the exposure among populations of different age groups. In conclusion, estimates via mapping resulted in a more comprehensive estimation of dietary exposure to heavy metals present in foods that Koreans consume.

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 (∑(62)PCBs), 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.

Survey of polycyclic aromatic hydrocarbons in marine products in Korea using GC/MS.

This study investigates polycyclic aromatic hydrocarbons (PAHs) in marine products on the Korean market. A total of 280 samples of fish (n = 100), shellfish (n = 80), cephalopod (n = 60) and crustacea (n = 40) were collected for analyses of PAHs (naphthalene, acenaphthylene, acenaphthene, fluorene, phenanthrene, anthracene, fluoranthene, pyrene, benz[a]anthracene, chrysene, benzo[b]fluoranthene, benzo[k]fluoranthene, benzo[a]pyrene, indeno[1,2,3-c,d]pyrene, dibenz[a,h]anthracene and benzo[g,h,i]perylene). The analytical procedure was based on the matrix solid-phase dispersion on Florisil cartridges and extraction with hexane/dichloromethane (3:1, v/v). The PAHs were determined by gas chromatography with mass spectrometric detection using selective ion monitoring. Average recoveries for all the PAHs studied were in the range 58-79%. The sum of 16 PAHs concentrations in fish, shellfish, cephalopod/crustacea were in the range 0.2-0.5, 1.2-1.6 and 0.8-1.9 µg/kg, respectively.