Method development and survey of Sudan I–IV in palm oil and chilli spices in the Washington,DC, area

Sudan I, II, III and IV dyes are banned for use as food colorants in the United States and European Union because they are toxic and carcinogenic. These dyes have been illegally used as food additives in products such as chilli spices and palm oil to enhance their red colour. From 2003 to 2005, the European Union made a series of decisions requiring chilli spices and palm oil imported to the European Union to contain analytical reports declaring them free of Sudan I–IV. In order for the USFDA to investigate the adulteration of palm oil and chilli spices with unapproved colour additives in the United States, a method was developed for the extraction and analysis of Sudan dyes in palm oil, and previous methods were validated for Sudan dyes in chilli spices. Both LC-DAD and LC-MS/MS methods were examined for their limitations and effectiveness in identifying adulterated samples. Method validation was performed for both chilli spices and palm oil by spiking samples known to be free of Sudan dyes at concentrations close to the limit of detection. Reproducibility, matrix effects, and selectivity of the method were also investigated. Additionally, for the first time a survey of palm oil and chilli spices was performed in the United States, specifically in the Washington, DC, area. Illegal dyes, primarily Sudan IV, were detected in palm oil at concentrations from 150 to 24 000 ng ml^–1. Low concentrations (< 21 µg kg^–1) of Sudan dyes were found in 11 out of 57 spices and are most likely a result of cross-contamination during preparation and storage and not intentional adulteration.     

Consideration of fluorescence properties for the direct determination of erythrosine in saffron in the presence of other synthetic dyes

Direct selective detection of erythrosine in saffron in the presence of other synthetic dyes considers its fluorescence at 532 nm excitation/548 nm emission. Saffron pre-treatment was according to the ISO 3632-2 trade standard test methods. On account of calculated quantum yield values, none of the yellow dyes is expected to interfere. Among red ones, reservations about allura red AC, azorubine and red 2G were not verified by experimentation, signifying excellent method specificity. Detection and quantification limits (0.56 and 1.70 nM) were of the same magnitude as those reported in the literature after chromatographic separation of erythrosine. The percentage recovery from spiked saffron samples ranging from 63 to 141 was acceptable for residue levels in foods. The matrix effect from crocins (saffron pigments) was evidenced only at a lower spiking level (0.02 mg kg(-1)). The minimum required performance limit (MRPL) was 0.04 mg kg(-1), indicating that the method is appropriate for determining traces of erythrosine in saffron. The approach offers improved sensitivity (by three orders of magnitude) and specificity than the direct spectrophotometric detection of certain synthetic dyes in saffron and deserves attention by the ISO Technical Committee for 'Herbs, culinary spices and condiments'.     

Assessment of the microbiological safety of dried spices and herbs from production and retail premises in the United Kingdom

A study of dried spices and herbs from retail and production premises to determine the microbiological status of such products was undertaken in the UK during 2004. According to EC Recommendation 2004/24/EC and European Spice Association specifications, 96% of 2833 retail samples and 92% of 132 production batches were of satisfactory/acceptable quality. Salmonella spp. were detected in 1.5% and 1.1% of dried spices and herbs sampled at production and retail, respectively. Overall, 3.0% of herbs and spices contained high counts of Bacillus cereus (1%, ≥10⁵ cfu g⁻¹), Clostridium perfringens (0.4%, ≥10³ cfu g⁻¹) and/or Escherichia coli (2.1%, ≥10² cfu g⁻¹). Ninety percent of samples examined were recorded as being ‘ready-to-use’, 96% of which were of satisfactory/acceptable quality. The potential public health risk of using spices and herbs as an addition to ready-to-eat foods that potentially undergo no further processing is therefore highlighted in this study. Prevention of microbial contamination in dried herbs and spices lies in the application of good hygiene practices during growing, harvesting and processing from farm to fork, and effective decontamination. In addition, the importance of correct food handling practices and usage of herbs and spices by end users cannot be overemphasised.     

Inhibitory effect of mixture herbs/spices on formation of heterocyclic amines and mutagenic activity of grilled beef

ABSTRACT

Natural antioxidants in spices and herbs have attracted considerable attention as potential inhibitors against the formation of mutagenic heterocyclic amines (HCAs) in heat-processed meat. In this study, the inhibitory activity of four spices/herbs and their mixtures on HCAs formation in grilled beef were examined. A simplex centroid mixture design with four components comprising turmeric, curry leaf, torch ginger and lemon grass in 19 different proportions were applied on beef samples before grilling at 240 ºC for 10 min. The HCAs were extracted from the samples using solid phase extraction (SPE) method and analysed using Liquid chromatography mass spectrometry LC-MS/MS. All spices/herbs in single or mixture forms were found to reduce total HCA concentrations in marinated grilled beef ranging from 21.2% for beef marinated with curry leaf to 94.7% for the combination of turmeric and lemon grass (50:50 w/w). At the optimum marinade formula (turmeric: lemon grass 52.4%: 47.6%), concentration of 2-amino-3-methylimidazo[4,5-f]quinolone (IQ), 2-amino-1-methyl-6-phenylimidazo[4,5-b]pyridine (PhIP), Harman, Norharman and AαC were 2.2, 1.4, 0.5, 2.8 and 1.2 ng/g, respectively. The results of the mutagenic activity demonstrated that this optimised marinade formula significantly (p < 0.05) diminished mutagenicity of marinated grilled beef in bacterial Ames test.     

Determination of dyes sudans in of raw foods

The number of cases using of forbidden dyes (such as Sudan-I and Para Red) in European foodstuff (including foodstuff from Russia) were increased last time. In this case it was required to adapt existing analytical methods for the control of dyes Sudan I-IV and Para Red. It was used for this purpose high performance liquid chromatography with detectings on diode-array and MS detector. Sudan I and Para Red were detected in 3 foodstuffs from examined 49 products. Concentration levels of these dyes were varied from 3 up to 500 mg/kg. Limits of determination of the methods is: HPLC-diode-array--0.1 mg/kg and HPLC-MS--0.5 mg/kg.     

Nontargeted Analytical Methods as a Powerful Tool for the Authentication of Spices and Herbs: A Review

Food fraud in herbs and spices is an important topic, which has led to new technologies being studied as potential tools for fraud identification. Nontargeted technologies have proven to be a useful tool for the authentication of herbs and spices. The present review focuses on the use of near‐infrared, hyperspectral imaging, Fourier‐transform infrared, Raman, nuclear magnetic resonance, and electron spin resonance spectroscopy for the authentication of spices, which includes the determination of origin and irradiated spices and the identification of adulterants. The methods developed based on vibrational spectroscopy combined with chemometric techniques seem to be promising tools for determining the presence of adulterants and contaminants in herbs and spices. On the other hand, nuclear magnetic resonance seems to be the most efficient technology to determine the origin of herbs and spices although, for some cases, studies with near‐infrared spectroscopy can be a viable substitute. Electron spin resonance spectroscopy is the technique par excellence used for the authentication of irradiated herbs and spices, so its use should be expanded to many more spices’ varieties. Portable devices are preferred by those involved in the food industry, due to its manageability and low cost. Data fusion and big data are shown as promising tools for spice fraud control. In conclusion, spectroscopic techniques show a great efficiency to authenticate spices, although their evaluation must be expanded to other spice varieties, to new strategies of data analysis (as data fusion and big data), and to the use of portable devices.     

A Preliminary Investigation of Naturally Occurring Aluminum in Grains,Vegetables, and Fruits from Some Areas of China and Dietary Intake Assessment

An investigation of the naturally occurring aluminum contents in grains, fruits and vegetables locally planted in some areas of China was conducted, and the aluminum dietary intake from the investigated food was estimated. A total of 2,469 samples were collected during 2013 to 2014 and tested for aluminum content using ICP‐MS method. The results showed that although 77.6% of the samples contained aluminum less than 5 mg/kg, significant variations of aluminum contents were observed in different food groups. Generally, the aluminum contents were found to be relatively high in dried grains and fresh vegetables, and low in fresh fruits. The mean value of aluminum contents in grains was 6.3 mg/kg, with wheat being the highest, followed by soybean and corn. The fresh vegetables had an average aluminum content of 4.7 mg/kg, with leafy vegetables being the highest, followed by bulb and stem vegetables. Most varieties of fresh fruits were low in aluminum, with the mean of 1.3 mg/kg. Based on the food consumption data from the China National Nutrient and Health Survey, the average weekly dietary intake of naturally occurring aluminum from the investigated foods was estimated to be 0.62 mg/kg bw for the general population and 0.55 to 1.00 mg/kg bw for different age groups. Grains and vegetables were the main contributors to the overall intake. Evaluated against the provisional tolerable weekly intake (PTWI) of 2 mg/kg bw, the dietary naturally occurring aluminum intake from the investigated foods was considered to be no safety concern.     

Citrinin Determination in Red Fermented Rice Products by Optimized Extraction Method Coupled to Liquid Chromatography Tandem Mass Spectrometry (LC‐MS/MS)

A rapid and sensitive method was developed and validated for citrinin determination in red fermented rice products by liquid chromatography tandem mass spectrometry (LC‐MS/MS) under the selected reaction monitoring mode. Sample preparation was especially focused, and the quantitative methods of LC‐MS/MS and high‐performance liquid chromatography with fluorescence detection (HPLC‐FLD) were compared. In red fermented rice samples, the limit of detection was 1.0 μg/kg for LC‐MS/MS compared to 250 μg/kg for HPLC‐FLD, the limit of quantification was 3.0 μg/kg for LC‐MS/MS compared to 825 μg/kg for HPLC‐FLD. High correlation coefficient was obtained (R² = 0.999) within the linear range (0.1 to 100 μg/L) in the MS method. The recoveries ranging from 80.9% to 106.5% were obtained in different spiking concentrations. The average intra‐ and inter‐day accuracy ranged from 75.4% to 103.1%, and the intra‐ and inter‐day precisions were from 3.3% to 7.9%. The developed method was applied to 12 commercial red fermented rice products, and citrinin was found in 10 samples ranging from 0.14 to 44.24 mg/kg. Compared to traditional qualitative and quantitative methods, the newly developed LC‐MS/MS method for citrinin determination includes the merits of using a small amount of extraction solvent, simple preparation steps, and high sensitivity.     

Determination of fungicide residues in baby food by liquid chromatography-ion trap tandem mass spectrometry

Current European Commission Directives on foods for infants and young children places emphasis on the control of pesticide residues at levels below 10 μg kg(-1). In the present work, a liquid chromatography electrospray ionisation ion trap tandem mass spectrometry (LC-Ion Trap-MS/MS) has been developed for the multiresidue of 10 multiclass fungicides (carbendazim, thiabendazole, imazalil, tridemorph, triadimefon, bitertanol, prochloraz, flutriafol, myclobutanil and diphenylamine) in fruit-based baby food. The developed method is based on a simple sample treatment (QuEChERS), which consists of a liquid-liquid extraction using acetonitrile, followed by a clean-up step based on dispersive solid-phase extraction with primary secondary amine (PSA). Subsequent identification and quantitation was accomplished by liquid chromatography/electrospray tandem mass spectrometry using an ion-trap mass spectrometer in the product ion scan MS/MS mode. Matrix effects were evaluated in LC-MS and LC-MS/MS mode experiments, obtaining a reduction of these effects when working in MS/MS mode for most of the analytes. Limits of detection (LOD) were between 0.5 and 3.0 μg kg(-1) depending on the pesticide studied, all being within European Union regulations for baby food. Finally, the proposed method was applied to 25 baby food samples obtained from local supermarkets. Imazalil, thiabendazole and carbendazim were detected in the studied samples. However, none of the samples tested were found to be upper the EU standard.     

Characterisation of a lard cured with spices and aromatic herbs

The study considered the proximate composition, pH, free acidity, MDA and peroxide values of a cured and ripened lard covered with spices and aromatic herbs, these latter parameters, due to lipolytic endoenzymatic phenomena, tended to increase until the end of the salting period. Throughout the production phases the bacterial load was very low. The final vacuum-packed product had a shelf-life of about 90 days and its fatty acid and cholesterol composition was typical of lard. A GC/MS study of the spices/herbs in the lard highlighted which components came from the spices/aromatic herbs and which came from phenomena due to lipolytic endoenzymatic processes.     

Analysis of coumarin in various foods using liquid chromatography with tandem mass spectrometric detection

Recently authorities and the media have published reports of increased coumarin levels in Christmas biscuits, gingerbread, cinnamon cookies and other foods. The maximum tolerance limits for coumarin in food are set out in EC Directive 88/388/ECC. Since the standard use of analytical techniques, such as HPLC–UV, are only limitedly suitable for verifying compliance with the regulatory limit of 2 mg/kg for coumarin in food, a selective, sensitive isotope dilution LC–MS/MS method for determining coumarin content in foods was developed, tested and validated, and the results then compared to the HPLC–UV method. This LC–MS/MS method increased selectivity and raised sensitivity by a factor of 100 compared to the HPLC–UV technique. The respective limits of determination and quantification for the method were 0.03 and 0.05 mg/kg, respectively, with an RSD of 1–8% and a linearity range of 0.1–500 ng/mL (corresponding to 0.05–250 mg/kg in food). In addition, a selection of around 500 food samples was also tested for coumarin content using the LC−MS/MS technique.     

Styrene in foods and dietary exposure estimates

ABSTRACT

Low levels of styrene may be found in foods as a result of possible migration from polystyrene-based food packaging and as a result of its formation during the biodegradation of a wide variety of naturally occurring compounds with structures similar to styrene. In this study, composite food samples from a recent (2014) Canadian Total Diet Study were analysed for styrene, and levels of styrene in samples of most food types were low in general with a few exceptions (e.g. 4934 ng/g in herbs and spices). Dietary exposures to styrene were estimated for different age-groups based on the occurrence data and the food consumption data for all persons, and they are 0.17–0.38 µg/kg body weight/day for children and 0.12–0.16 µg/kg body weight/day for adults, similar to air intakes (0.085–0.27 µg/kg body weight/day). Thus, for the general population, both food and air contribute similar portions of the total daily intake of styrene for all age groups. However, for the smoking population, intakes from cigarettes are still the major route of exposure to styrene.     

Emerging Trends in Microwave Processing of Spices and Herbs

Today, spices are integral part of our food as they provide sensory attributes such as aroma, color, flavour and taste to food. Further their antimicrobial, antioxidant, pharmaceutical and nutritional properties are also well known. Since spices are seasonal so their availability can be extended year round by adopting different preservation techniques. Drying and extraction are most important methods for preservation and value addition to spices. There are different techniques for drying of spices with their own advantages and limitations. A novel, non-conventional technique for drying of spices is use of microwave radiation. This technique proved to be very rapid, and also provide a good quality product. Similarly, there are a number of non-conventional extraction methods in use that are all, in principle, solid–liquid extractions but which introduce some form of additional energy to the process in order to facilitate the transfer of analytes from sample to solvent. This paper reviews latest advances in the use of microwave energy for drying of spices and herbs. Also, the review describes the potential application of microwave energy for extraction of essential oil/bioactive components from spices and herbs and the advantages of microwave-assisted process over the other extraction processes generally employed for extraction. It also showcases some recent research results on microwave drying/extraction from spices and herbs.     

2019年欧盟食品饲料快速预警系统通报中国输欧食品情况与风险分析

欧盟食品和饲料快速预警系统(Rapid Alert System for Food and Feed, RASFF),作为欧盟食品安全管理体系最重要的部分,为欧盟委员会以及各成员国能够及时排查出食品安全风险并及时应对提供了强有力的支撑,有效保证了欧盟各成员国食品安全。本文对2019年欧盟RASFF通报我输欧食品情况进行收集、梳理和分析,以期减少或避免类似情况发生,以期为我国出口食品企业和监管部门提供参考。     

凝胶渗透色谱净化系统与气相色谱-串联质谱法检测5种食品中14种有机磷和7种拟除虫菊酯类农药残留

建立GPC与GC-MS/MS测定5种食品中14种有机磷和7种拟除虫菊酯类农药残留的方法,初步分析GPC净化技术及MS/MS分析技术在食品农药多残留分析的优势。方法 用GPC作为样品前处理方法,处理韭菜、大白菜、辣椒、猪肉、鱼肉五种食品,用 GC-MS/MS检测并进行定性、定量分析。结果 GPC与GC-MS-MS检测食品中14种有机磷和7种拟除虫菊酯类农药方法的线性相关系数r＞0.995,定量限为0.002～0.034 mg/kg,对韭菜、猪肉样品按0.05、0.10、0.20 mg/kg三组水平加标测试,方法精密度RSD%为2.9～10.2%,回收率为78.6～108.3%。结论 本方法检测样品范围广、灵敏度高、定性可靠、定量准确,适合多种类食品中农药多残留分析。     

Free salicylic acid and acetyl salicylic acid content of foods using gas chromatography–mass spectrometry

Dietary salicylates inhibit cycloxygenase-2 and may therefore have anti-inflammatory properties similar to those of aspirin. Individuals that are sensitive to aspirin may also be intolerant to non-acetylated salicylates and could benefit from a low salicylate diet. A total of 76 foodstuffs comprising fruit (16), fresh and prepared vegetables (13), herbs and spices (12), flavourings and sauces (9), beverages (20) and miscellaneous foods (6) were analysed using gas chromatography with mass spectrometric detection and ¹³C carboxyl SA as internal standard. Thirty-seven of the samples contained detectable SA, the highest levels being found in dried herbs (up to 28.6 mg/kg), whereas only one sample (curry sauce) contained detectable ASA at 0.34 mg/kg. Limits of detection for both SA and ASA were matrix-dependent and ranged from 0.008 to 0.23 mg/kg. The results show many inconsistencies with previous data and highlight the need for analysis of a wider range of foods and drinks that are currently available.     

Comparison of GC/MS and NMR for quantification of methyleugenol in food

Methyleugenol is a substance that is possibly carcinogenic to humans, which may occur in foods containing certain herbs and spices. The European Union has set maximum levels for some product groups, but there is a lack of comprehensive market surveys for this compound. In this study, we compare two procedures for methyleugenol determination in foods, namely GC/MS, which is currently seen as gold standard for such an analytical problem, and NMR, which is hypothesized to be suitable as a faster screening. The sample preparation for GC/MS consists of homogenization in ethanol followed by liquid–liquid extraction for fat-free foods or automatic steam distillation for fat-containing foods. The extract or distillate is then measured using GC/MS either in SCAN or SIM mode (dependent on concentration) with cyclodecanone as internal standard. For ¹H NMR, the ethanolic solution can be directly measured without further extraction or distillation. Quantification using external standardization is conducted for NMR. Both procedures were validated and fulfilled the requirements for quantitative food analysis. The applicability was demonstrated by analyzing 120 samples including basil, estragon, pimento, nutmeg, several teas, alcoholic beverages, and pesto. GC/MS is more sensitive, precise, and suitable for regulatory purposes but time-consuming and expensive. NMR can be used for a faster screening analysis and appears to be ideal for conducting larger surveys to estimate human exposure.     

中药渣袋栽平菇中微量元素的分析

对中药渣袋栽平菇中微量元素进行研究,用湿法消解样品,原子吸收分光光度法进行微量元素的测定.结果表明:该方法灵敏度高,检出限低,精密度、准确度好;药渣袋栽平菇中微量元素Cu、Zn、Fe、Mn平均含量分别为:9.199mg/kg、113.9mg/kg、102.9mg/kg、8.095mg/kg,与对照组比较无明显差别.     

Estimation of intake of bisphenol-A-diglycidyl-ether (BADGE) from canned fish consumption in Europe and migration survey

The exposure to bisphenol-A-diglycidyl-ether (BADGE) from canned fish in oil was assessed from consumption data collected for each Member State of the European Union and Switzerland, and migration data from a European survey on 382 samples. Trade figures were used when no consumption data were available. The average consumption of canned fish in Europe was 2.3kg per person per year, with values ranging from 0.2kg per person per year in the United Kingdom to 5.1kg per person per year in Denmark. The exposure to BADGE was calculated as μg per person per day. The data indicated that exposure to BADGE was in the range below 4mg per person per year, i.e. 9 μg per person per day, hence a fairly low exposure in part due to the fact that canned fish is a relatively minor dietary item. An approximation assuming the general figure of a 60kg adult, would thus be 0.15 μg/kg body weight per day. This is a fairly limited exposure considering the provisional limit in food had been set a 1mg/kg and assumed 1kg of food ingested. In countries for which increased exposure was found, the reason was mainly caused by one individual sample exhibiting a high concentration rather than a larger number of samples with mildly elevated concentrations.     

2009年欧盟食品及饲料类快速预警系统对华通报及近年变化情况分析

食品及饲料类快速预警系统(RASFF)是欧盟监管当局为确保食品安全而采用的实时、快速而又有效的信息交流平台,已成为保护欧洲消费者不可或缺的工具。本文对2009年中国(大陆地区)产品RASFF通报情况及近年来通报内容的一些重要变化情况进行了统计和分析,包括通报数量、通报产品和通报原因等方面的变化,并对RASFF运行趋势与经验借鉴进行了探讨。