Identification of acid-stable carmine in imported apple syrup product

An unknown red pigment was purified from an apple syrup product imported from Canada, using a DIAION HP-20 column with methanol as the eluent. By spectroscopic means and chemical synthesis, the isolated pigment was identified as 4-aminocarminic acid, which is the major pigment of acid-stable carmine (a red colorant illegal in Japan). In addition, HPLC and TLC methods were proposed to detect this illegal colorant. While the color of carminic acid changed from yellow to red in the pH range of McIlvaine buffer (3.0-7.0), the color of 4-aminocarminic acid was always red, and also the ultraviolet/visible (UV/Vis) spectra did not change. These characteristics are useful to distinguish 4-aminocarminic acid from carminic acid.     

Structure of acid-stable carmine

Acid-stable carmine has recently been distributed in the U.S. market because of its good acid stability, but it is not permitted in Japan. We analyzed and determined the structure of the major pigment in acid-stable carmine, in order to establish an analytical method for it. Carminic acid was transformed into a different type of pigment, named acid-stable carmine, through amination when heated in ammonia solution. The features of the structure were clarified using a model compound, purpurin, in which the orientation of hydroxyl groups on the A ring of the anthraquinone skeleton is the same as that of carminic acid. By spectroscopic means and the synthesis of acid-stable carmine and purpurin derivatives, the structure of the major pigment in acid-stable carmine was established as 4-aminocarminic acid, a novel compound.     

Aminocarminic acid in E120-labelled food additives and beverages

An analytical method was developed for investigating aminocarminic acid occurrence in E120-labelled red-coloured-beverages and in E120 additives, with the aim of controlling the purity of the carmine additive in countries where the use of aminocarminic acid is forbidden. The carminic acid and the aminocarminic acid were separated by high-performance liquid chromatography–photodiode array–tandem mass spectrography (HPLC-PDA-MS/MS). The method was statistically validated. The regression lines, ranging from 10 to 100?mg/L, showed r^2?>?0.9996. Recoveries from 97% to 101% were obtained for the fortification level of 50?mg/L; the relative standard deviations did not exceed 3%. The LODs were below 2?mg/L, whereas the LOQs did not exceed 4?mg/L. The method was successfully applied to 27 samples of commercial E120-labelled red-coloured beverages and E120 additives, collected in Italy during quality control investigations conducted by the Ministry. The results demonstrated that more than 50% of the samples contained aminocarminic acid, evidencing the alarming illicit use of this semi-synthetic carmine acid derivative.     

Retrospective analysis for the identification of 4-aminocarminic acid photo-degradation products in beverages

This article deals with the identification of the photo-degradation products of 4-aminocarminic acid potentially present in commercial beverages. Sixteen beverages of different composition but all containing the E120 dye were previously analysed by ultra-high-performance liquid chromatography (UHPLC) coupled with quadrupole-time of flight mass spectrometry to identify the common degradation products of the E120 dye. Since it is plausible to find unauthorised 4-aminocarminic acid in beverages which report generic E120 dye on the label, retrospective analysis was employed here not only to search for the possible presence of 4-aminocarminic acid but also to investigate the potential formation of photo-degradation products derived from this compound. For this purpose, a statistical approach based on Student’s t-test was used to compare the degraded beverages containing 4-aminocarminic acid with all the others. Five degradation products were identified and their structures were elucidated on the basis of the high-accuracy and high-resolution of mass and mass/mass spectra. The toxicity of the degradation products was evaluated through the Ames Salmonella/microsome mutagenicity assay. No evidence of mutagenicity was obtained for the beverages subjected or not to irradiation, whereas a toxic effect of the 4-aminocarminic acid standard solution already at 100.0 µg l^?1 was found. This leads, once again, to the conclusion that the toxicity study must be carried out on the beverages in order to take into account of all the possible masking/protection interactions among the ingredients.     

Methods for the determination of European Union-permitted added natural colours in foods: a review

Coupled to increasing consumer demand, food manufacturers have moved towards increased usage of approved natural colours. There is a legal requirement for governments to monitor the consumption of all food additives in the European Union to ensure the acceptable daily intakes (ADIs) are not exceeded, especially by young children. Validated analytical methods are needed to fulfil this requirement. The aim of this paper is to review the available literature on methods of extraction for approved natural colours in food and drink. Available analytical methods for the determination of European Union-permitted natural food colour additives in foods and beverages have been assessed for their fitness for purpose in terms of their key extraction and analysis procedures, selectivity and sensitivity, especially with regard to maximum permitted levels, and their applicability for use in surveillance and in an enforcement role. The advantages and disadvantages of available analytical methods for each of nine designated chemical classes (groups) of natural colours in different food and beverage matrices are given. Other important factors such as technical requirements, cost, transferability and applicability are given due consideration. Gaps in the knowledge and levels of validation are identified and recommendations made on further research to develop suitable methods. The nine designated natural colour classes covered are: 1. Curcumin (E100), 2. Riboflavins (E101i-ii), 3. Cochineal (E120), 4. Chlorophylls--including chlorophyllins and copper analogues (E140-141), 5. Caramel Classes I-IV (E150a-d), 6. Carotenoids (E160a-f, E161b, E161g), 7. Beetroot red (E162), 8. Anthocyanins (E163), and 9. Other colours--Vegetable carbon (E153), Calcium carbonate (E170), Titanium dioxide (E171) and Iron oxides and hydroxides (E172).     

Qualitative determination of carbon black in food products

Carbon black (C.I. 77266) is an insoluble pigment produced by the partial combustion of hydrocarbons. The pigment is known by several synonyms, including vegetable carbon, lamp black and carbon ash, that correspond to the raw materials and methods used for its production. Vegetable carbon (E153) is permitted for use in colouring food in the European Union. The US Food and Drug Administration (USFDA) has not approved the use of any type of carbon black for colouring food, although the agency batch certifies the pigment as D&C Black No. 2 for use in colouring certain cosmetics. Since carbon black (as vegetable carbon) may be present in food products offered for import into the United States, the USFDA's district laboratories need a qualitative analytical method for determining its presence. We have developed an extraction method for this purpose. A sample is broken down and dissolved with nitric acid. The resulting solution is filtered and treated with hydrochloric acid to dissolve any black iron oxide also present as a colour additive. A black residue remaining on the filter paper indicates the presence of carbon black in the food. We confirmed the presence of carbon black in residues from several standards and food products using Raman spectroscopy. The limit of detection for this method is 0.0001%.     

Food and feed chemical contaminants in the European Union: Regulatory,scientific, and technical issues concerning chemical contaminants occurrence,risk assessment,and risk management in the European Union

A priority of the European Union is the control of risks possibly associated with chemical contaminants in food and undesirable substances in feed. Following an initial chapter describing the main contaminants detected in food and undesirable substances in feed in the EU, their main sources and the factors which affect their occurrence, the present review focuses on the “continous call for data” procedure that is a very effective system in place at EFSA to make possible the exposure assessment of specific contaminants and undesirable substances. Risk assessment of contaminants in food atances in feed is carried currently in the European Union by the CONTAM Panel of EFSA according to well defined methodologies and in collaboration with competent international organizations and with Member States.     

Qualitative determination of carbon black in food products

Carbon black (C.I. 77266) is an insoluble pigment produced by the partial combustion of hydrocarbons. The pigment is known by several synonyms, including vegetable carbon, lamp black and carbon ash, that correspond to the raw materials and methods used for its production. Vegetable carbon (E153) is permitted for use in colouring food in the European Union. The US Food and Drug Administration (USFDA) has not approved the use of any type of carbon black for colouring food, although the agency batch certifies the pigment as D&C Black No. 2 for use in colouring certain cosmetics. Since carbon black (as vegetable carbon) may be present in food products offered for import into the United States, the USFDA's district laboratories need a qualitative analytical method for determining its presence. We have developed an extraction method for this purpose. A sample is broken down and dissolved with nitric acid. The resulting solution is filtered and treated with hydrochloric acid to dissolve any black iron oxide also present as a colour additive. A black residue remaining on the filter paper indicates the presence of carbon black in the food. We confirmed the presence of carbon black in residues from several standards and food products using Raman spectroscopy. The limit of detection for this method is 0.0001%.     

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.     

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.     

Confirmation of non-permitted dyes detected in Akasu (red vinegar) by LC/MS

Suitable liquid chromatography/mass spetrometry (LC/MS) conditions were examined for Amaranth, Red 2G (R2G), Azo Rubine (Azo), Fast Red E (FRE) and Brilliant Blue FCF, which were detected in Akasu, a red vinegar made in Hong Kong from sake lees, on both thin layer chromatography (TLC) and photodiode array high-performance liquid chromatography (PDA-HPLC). Molecular-related ions for each dye were detected with excellent sensitivity by LC/MS using electro-spray ionization with negative ion mode, capillary voltage 3.00 kV, cone voltage 50 V and desolvation temperature 400 degrees C. LC/MS analysis of refined Akasu under these conditions enabled us to obtain clear mass spectra of R2G, Azo and FRE, which were present at trace levels in the Akasu. The results were consistent with those from TLC and PDA-HPLC. These experiments suggested that LC/MS analysis is applicable for confirmation of dyes in food.     

Tiger Nut (Cyperus esculentus) Commercialization: Health Aspects,Composition, Properties,and Food Applications

Abstract: Tiger nut (Cyperus esculentus) is a weed plant (yellow nut sedge) of tropical and Mediterranean regions. Its sweet almond‐like tubers are highly appreciated for their health benefits and nutritive value: high content of fiber, proteins, and sugars. They are rich in oleic acid and glucose, as well as in phosphorus, potassium, and vitamins C and E. In Spain, these tuberous “nuts” are mainly used to manufacture a milky beverage called “horchata de chufa.” Tiger nut has attracted very little scientific and technological interest, except for the production of “horchata de chufa” and some studies on its oil. Development of new products from the tubers could enhance more interest in this crop. In this respect, various opportunities are offered: source of dietary fiber, use of its oil in cooking or salad preparation, production of caramel to be used as a food additive. This review presents an overview of the tiger nut, its products, and the co‐products obtained during commercial processing.     

2012~2015年贵州省餐饮食品中色素检测结果分析

目的 对贵州省餐饮服务食品中柠檬黄、诱惑红、日落黄、胭脂红和苏丹红5种色素进行检测与分析, 掌握我省餐饮食品安全状况。方法 根据GB/T 5009.35-2003《食品中合成着色剂的测定》, SNT 1743-2006《食品中诱惑红、酸性红、亮蓝、日落黄的含量检测 高效液相色谱法》和GB/T 19681-2005《食品中苏丹红染料的检测方法 高效液相色谱法》, 对2012~2015年贵州省餐饮服务食品中5种色素进行检测, 按GB/2760-2011《食品添加剂使用卫生标准》和《食品中可能违法添加非食用物质名单》判断是否合格。结果 3054批食品中, 柠檬黄、诱惑红、日落黄、胭脂红和苏丹红的合格率分别为95.6%、99.1%、98.5%、99.3%和100%。结论 贵州省4年内餐饮服务食品中色素的总体安全状况较好。     

Analysis of diglycolic acid in food packaging,over the counter products,direct additive carboxymethyl cellulose,and retail foods

ABSTRACT

Carboxymethyl cellulose (i.e. CMC or cellulose gum) is used as a direct additive for foods and drugs to change texture and act as a binder. CMC can also be a fluid absorbent used in food packaging and food contact materials. CMC and other carboxymethyl starches are synthesised by condensing glycolic acid with monochloroacetic acid. Diglycolic acid (DGA) is a byproduct produced by this condensation which cannot be completely removed. Currently, there are no analytical methods to accurately detect and quantify DGA in foods and food packaging materials. A method using a methanol/water extraction coupled with weak anion exchange solid phase extraction cleanup for more complex matrices was developed. A novel LC-MS/MS method was used to determine the DGA concentration in food contact materials, food grade direct additive CMC, and foods containing CMC. This paper will discuss the development of a new method for the preparation and cleanup of various food matrices and LC-MS/MS analysis for the presence of DGA.     

超高效液相色谱-质谱法测定动物性膳食中全氟辛烷磺酸和全氟辛酸

目的 建立三类动物性膳食中典型全氟有机化合物的超高效液相色谱-串联质谱( UPLC-MS/MS)测定方法.方法 实验优化了样品提取方法和液相色谱质谱条件.样品经冷冻干燥后用甲醇提取,弱阴离子交换固相萃取柱净化;使用C18色谱柱,甲醇和2 mmol/L醋酸铵水溶液为流动相进行分离;采用ESI负离子源并在多反应监测模式(MRM)下进行测定.结果 目标化合物的回收率为82％～115％,检测限分别为76～129 pg/g干重和88～319 pg/g干重.运用该方法分析了9份膳食样品,三类样品中均检出目标化合物.结论 本方法简便快速、准确可靠,灵敏度足以满足动物性膳食样品的检测.     

Identification of the monobrominated derivative of Acid Red 52 (Food Red No. 106) in pickled vegetables

Two unknown dyes (purple and purplish-red) were detected by TLC in two pickled vegetable (sakura-zuke daikon) samples containing Acid Red 52 (AR) and New Coccine as food colorants. HPLC with diode-array detection and LC/MS analyses suggested that the purple dye is monobrominated AR and the purplish-red dye is its N-desethyl derivative, which would be generated mainly during sample preparation. For the identification of the purple dye, a reference compound was prepared by bromination of AR followed by isolation of the monobrominated AR, the structure of which was elucidated as 4′-brominated AR (4′BrAR) by LC/ToF-MS and ¹H-NMR spectroscopy. The purple dye was confirmed as 4′BrAR by comparison of its retention time, ultraviolet-visible spectrum and mass spectrum with those of the prepared reference compound. To our knowledge, this is the first report of the detection of 4′BrAR in foods.     

北京市地区小包装食用油中真菌毒素污染状况调查

在北京市地区随机抽取120份小包装食用油,采用高效液相色谱法或液相色谱-质谱联用法检测AF、AFB1、ZEN、DON、OTA和FB 6种真菌毒素的含量,并进行危害性评估。结果表明:120份样品中,黄曲霉毒素和玉米赤霉烯酮的检出率分别为6. 67%和17. 50%,且检出黄曲霉毒素的食用油都为花生油,检出玉米赤霉烯酮的食用油都为玉米油,未检出其他真菌毒素;黄曲霉毒素虽然没有超出我国食用油真菌毒素的限量标准,但超出了欧盟的真菌毒素限量标准;玉米赤霉烯酮检出率虽然很高,但没有超出人体的每日最大耐受摄入量。     

Profitability of wine grape growing in the EU member states

The aim of this work is to examine the profitability of European Union wine grape growing by comparing some economic indicators extrapolated from information in the Farm Accountancy Data Network, data banks already widely used to analyse the income of European agricultural holdings. The results show that in recent years the profitability of European wine grape growing has grown overall, but to overcome the current economic crisis and face the challenge of “New World” wine producers, it is necessary to make an effort towards public intervention to increase the profitability of wine farms. In this context, the new reform of wine Common Market Organisation (2008) and new Common Agricultural Policy (2007–2013) aimed at improving the profitability of wine grape growing by reducing production costs, increasing added value of wine, promoting the participation of farmers in food quality schemes, etc.     

The content of high-intensity sweeteners in different categories of foods available on the Polish market

The objective of this study was to measure the concentrations of nine high-intensity sweeteners (acesulfame-K, aspartame, alitame, cyclamate, dulcin, neohesperidin DC, neotame, saccharin and sucralose) in different categories of food available on the Polish market. Over 170 samples of different brands of beverages, yoghurts, fruit preparations, vegetable preserves and fish products were analysed using an analytical procedure based on SPE and LC/MS. The results indicated that foodstuffs under the study generally comply with European Union legislation in terms of sweetener content. However, a few cases of food product mislabelling were detected, i.e. the use of cyclamate for non-approved applications.     

Al3+荧光增敏快速检测酸奶和乳酸菌饮料中的胭脂虫红酸（英文）

研究溶剂、浓度、pH值以及金属离子对胭脂虫红酸荧光性能的影响,表明胭脂虫红酸在pH 4且其物质的量浓度为2.0×10^-4 mol/L的水溶液中荧光最强;而胭脂虫红酸对金属离子选择性识别的结果显示,Al^3+能使胭脂虫红酸的荧光强度显著增强从而提高检测的灵敏度。以Al^3+(2.0×10^-3 mol/L)为标准溶液检测样品中胭脂虫红酸含量时,胭脂虫红酸的物质的量浓度在1.0×10^-5~8.0×10^-5 mol/L范围内与其荧光强度呈良好的线性关系,检测限为5.0×10^-6 mol/L。实际应用结果表明,用荧光法检测不同酸奶和乳酸菌饮料中添加的胭脂虫红酸的含量,样品回收率在96.6%~110.5%之间,相对标准偏差小于5.9%。本研究为快速、有效、定量地检测食品中的胭脂虫红酸提供了一种有效的方法。