Heavy metals in spices and herbs from wholesale markets in Malaysia

As, Cd, Pb and Hg were analysed in commonly consumed spices and herbs in Malaysia. The range of As, Cd, Pb and Hg content was 0.24–2.54, 0.23–8.07, 1.54–8.94 and 0.06–0.52?µg?g^–1, respectively. The highest concentration of Cd, Pb and Hg in spices and herbs exceeded the maximum permitted proportion, which are 1, 2 and 0.05?µg?g^?1, respectively. This study suggests further monitoring of Cd, Pb and Hg on daily consumption of spices and herbs and its toxicological implication for consumers since only the amount of As was lower than the permitted concentration.     

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.     

Sensitivity of four foodborne moulds to essential oils from turkish spices,herbs and citrus peel

The antifungal effects of 22 essential oils from Turkish spices, herbs and citrus peel on four foodborne moulds were evaluated for fungistatic and fungicidal activity. The most active oils were wild thyme (Thymus rariflorus L) and thyme (Thymus serpyllum L). Parsley (Penloselinum sativum Hoffin) and savory (Satureja hortensis L) oils were found to be the least active oils. Rhizopus sp displayed the greatest tolerance, and the most sensitive mould was Penicillium chrysogenum. Prolonged incubations reduced the fungistatic and fungicidal effects of oils. It was concluded that some oils may be useful as mould inhibitors at food additive levels.     

The phenolic composition and antioxidant capacity of soluble and bound extracts in selected dietary spices and medicinal herbs

Phenolic compounds, commonly found in plant‐based foods, exist in free or bound form. Despite much research on the soluble phenolics in spices and herbs, their bound phenolics have not been intensively investigated. In this study, six common dietary spices and medicinal herbs (Padang cassia, oregano, clove, Chinese cassia, Japanese knotweed and peel of pomegranate) were selected to evaluate and compare their phenolic composition and antioxidant capacity in soluble extracts (SEs) and bound extracts (BEs). Generally, the samples had high total phenolic content and antioxidant capacity, with lower levels in the BEs. From the HPLC results, (+)‐catechin, (?)‐epicatechin, eugenol, cinnamaldehyde and carvacrol were the major phenolic compounds in the SEs, and gallic acid, p‐coumaric acid and ellagic acid in the BEs. Phenolic compounds are likely the major contributors to the antioxidant capacity of these plant samples. Overall, these dietary spices and medicinal herbs can be excellent sources of natural antioxidant phenolics.     

Bacterial spores in spices and dried herbs: The risks for processed food

Production and world consumption of spices are constantly increasing. Although the antimicrobial properties of some spices are well documented, their use in the agri-food industry is also responsible for microbial contamination and spoilage. Bacterial spores introduced by spices can withstand different preparation processes, particularly thermal treatments, leading to food alterations during storage. This review brings together data from the literature about the prevalence and concentrations of spore-forming bacteria in all commercially available spices. The sporeformers found in spices belong mainly to the genera Bacillus and Clostridium. Such contaminations are very common and sometimes reach high levels, as in pepper and turmeric. Bacillus licheniformis and Bacillus cereus are the most frequently detected species. Studying the harvesting, processing, and storage procedures for spices provides elements to explain why high prevalence and concentrations are observed. Spices are mostly produced in developing countries on small farms using traditional production methods. Spices become contaminated by bacterial spores in two main ways: by contact with soil during harvesting or drying, as for pepper, or by cross-contamination during the water-cooking step, as for turmeric. From these observations, we propose some recommendations. Different methods that can be used to eliminate bacterial spores from spices are presented indicating their efficiency and the limitations of their use.     

Mycotoxins,pesticides and toxic metals in commercial spices and herbs

ABSTRACT

A total of 300 samples representing six condiments (black pepper, basil, oregano, nutmeg, paprika, and thyme) were analysed for 11 mycotoxins, 134 pesticides and 4 heavy metals by ultra-high performance liquid chromatography–tandem quadrupole mass spectrometry and inductively coupled plasma mass spectrometry. Mycotoxins were detected in 4%, 10% and 30% of all nutmeg, basil and thyme samples, respectively. The residues of 24 pesticides were detected in 59% of the analysed condiments. The maximum residue levels of pesticides were exceeded in 10% of oregano and 46% of thyme samples. A risk assessment of heavy metals was performed, indicating daily intake levels far below the tolerable intake levels.     

美国应对经济利益驱动型掺假和食品欺诈的经验及对我国的启示

食品欺诈自古就有,但是近年来随着食品供应链全球化和复杂化,以及商业竞争日趋激烈等原因,受经济利益驱动进行的食品掺假和欺诈活动愈演愈烈。美国是最早提出经济利益驱动型掺假概念的国家,并为应对经济利益驱动型掺假提出了一系列措施。本文首先将美国关于经济利益驱动型掺假和食品欺诈的定义进行了梳理,并将这两个概念与其他食品保护概念进行对比;其次,对比美国和中国经济利益驱动型掺假和食品欺诈的应对措施;最后,对我国应对经济利益型掺假和食品欺诈提出了四点建议。     

Rhodamine B in spices determined by a sensitive UPLC-MS/MS method

Rhodamine B (RhB) is a banned food additive and has been classified as illegal colourant. Therefore, the risk of RhB contamination should be strictly monitored. In this study, a sensitive UPLC-MS/MS method was applied to monitor RhB in 292 various spices such as chilli, pepper and tomato products. The results showed 22.7% of chilli powder samples, 18.5% of pepper powder samples, 11.1% of chilli oil samples and 9.1% of pepper oil samples were contaminated with RhB. Chilli powder contained RhB up to 44,935 μg/kg with an average of 743 μg/kg, pepper powder up to 65.9 μg/kg with an average of 4.1 μg/kg, chilli oil up to 14.6 μg/kg with an average of 1.0 μg/kg and pepper oil up to 1.1 μg/kg with an average of 0.2 μg/kg, respectively. Considering the common consumption of chilli products and pepper products by so many consumers, RhB exposure is significant and should be decreased.     

Comparison of multiple methods for the determination of sulphite in Allium and Brassica vegetables

Sulphites are a family of additives regulated for use worldwide in food products. They must be declared on the label if they are present in concentrations greater than 10 mg kg^–1, determined as sulphur dioxide (SO₂). The current US regulatory method for sulphites, the optimised Monier–Williams method (OMW), produces false-positive results with vegetables from the Allium (garlic) and Brassica (cabbage) genera due to extraction conditions that are thought to cause endogenous sulphur compounds to release SO₂. Recently, modifications to the OMW method (2x MW) were published that reportedly reduced this false-positive in garlic. However, no other vegetables from these genera have been investigated. In addition, an LC-MS/MS method was developed for sulphite analysis, but it has not yet been tested with these problematic matrices. Ten vegetable species were analysed using these sulphite methods (OMW titration, OMW gravimetric, 2x MW and LC-MS/MS) to determine the false-positive rate. Sulphite concentrations > 10 mg kg^–1 SO₂ were observed with the OMW analyses. The 2x MW method reduced the measured concentration in unsulphited samples to ≤ 10 mg kg^–1 SO₂ for all matrices analysed. The LC-MS/MS method showed concentrations < 10 mg kg^–1 for the Brassica samples, but only displayed a slight reduction in the Allium matrices. Spiked recovery studies were conducted to determine if these methods can detect added sulphite. The 2x MW had recoveries of 17% and 42% for water and fresh garlic, respectively, and the LC-MS/MS had recoveries of 108%, 125%, 116% and 107% for water, fresh garlic, roasted garlic, and hummus, respectively. The low recoveries of the 2x MW may indicate that sulphur compounds cannot be properly quantified with this method. The ability to eliminate false-positives will enable accurate determination of added sulphite to ensure compliance with sulphite labelling requirements.     

Characterization and Pharmacokinetic Profile of Herbs and Spices' Phytochemicals over 24 h after Consumption in Overweight/Obese Adults

Scope

This study aims to characterize the phytochemicals in commonly consumed herbs/spices (H/S) in the United States and their pharmacokinetic profile (PK) over 24 h in humans after consumption.

Method and results

The clinical trial is a randomized, single-blinded, four-arm, 24 h, multi-sampling, single-center crossover design (Clincaltrials.gov NCT03926442) conducted in obese/overweight adults (n = 24, aged 37 ± 3 years, BMI = 28.4 ± 0.6 kg m⁻²). Study subjects consume a high-fat high-carbohydrate meal with salt and pepper (control) or the control meal with 6 g of three different H/S mixtures (Italian herb: rosemary, basil, thyme, oregano, and parsley in the same ratio; cinnamon; and pumpkin pie spice containing cinnamon, ginger, nutmeg, and allspice, the ratio is unknown). Three H/S mixtures are analyzed and 79 phytochemicals are tentatively identified and quantified. Following H/S consumption, 47 metabolites are tentatively identified and quantified in plasma samples. The PK data suggest that some metabolites appear in blood as early as 0.5 h while others can extend up to 24 h.

Conclusion

Phytochemicals from H/S include in a meal are absorbed and undergo phase I and phase II metabolism and/or catabolized to phenolic acids peaking at different times.     

UPLC-ESI-MS/MS analysis of Sudan dyes and Para Red in food

An analytical method for the simultaneous determination of Sudan dyes (Sudan Red G, Sudan I, Sudan II, Sudan III, Sudan Red 7B and Sudan IV) and Para Red in food by ultra-performance liquid chromatography-electrospray tandem mass spectrometry (UPLC-ESI-MS/MS) was developed. Samples were extracted with acetonitrile, and water added into the extract. The supernatant was analysed by UPLC-MS/MS after refrigeration and centrifugation. The sample was separated on an Acquity BEH C₁₈ column, and detected by MS/MS with the multiple reaction monitoring mode. Matrix calibration was used for quantitative testing of the method. The linear matrix calibrations of Sudan dyes and Para Red were 2–50 and 10–250 ng g^?1, respectively, and the regression coefficients were >0.9945. The recoveries were 83.4–112.3% with good coefficients of variation of 2.0–10.8%. The limits of detection were between 0.3 and 1.4 ng g^?1 for the six Sudan dyes, and between 3.7 and 6.0 ng g^?1 for Para Red. The limits of quantification were between 0.9 and 4.8 ng g^?1 for the six Sudan dyes, and between 12.2 and 19.8 ng g^?1 for Para Red.     

Validation and application of an LC-MS/MS method for the determination of cyclic oligomers originating from polyamide 6 and polyamide 66 in food simulant

Polyamides (PAs) are used in the production of various food contact materials (FCMs) and articles such as kitchen utensils and packaging material. Cyclic oligomers have been identified as potential migrants from PA. This study describes the development, validation and application of a multi-oligomer analytical method based on LC-ESI-MS/MS for the identification and quantification of eight cyclic oligomers of PA 6 and four PA 66 migrating from FCMs into food simulant B (3% acetic acid) and beverages. It was proved that doubly charged precursor ions of the cyclic PA 6 and PA 66 oligomers above a mass of 500 Da are formed during the ionisation process of the electrospray technique used. Direct injection of a diluted food simulant into the LC-ESI-MS/MS system after migration makes the validated method a valuable tool for investigating migration of cyclic PA oligomers. The validation results demonstrate that the multi-oligomer method is applicable for the analysis of cyclic PA 6 and PA 66 oligomers in food simulant B. For all investigated cyclic PA oligomers, detection limits were in the range of 0.1–1.1 µg/l. Linearity (r² ≥ 0.99), trueness values between 91% and 122%, and intra-day (RSD_r < 10%) and inter-day precision (RSD_R < 19%) were determined and satisfied validation criteria set out by the European Reference Laboratory for FCMs. The method was extended to tap water and tea. Finally, the multi-oligomer method was successfully applied to determine cyclic PA oligomers in migration solutions originating from different PA FCMs. In all migration solutions, concentrations of cyclic PA oligomers were determined above the LOQ. A preliminary risk assessment based on in silico tools was performed. The results demonstrate the urgent need for toxicological data that would facilitate the evaluation of the health risk of cyclic PA oligomers.     

液质联用快速鉴定减肥类保健食品中4种违禁添加药物

目的建立快速鉴定减肥类保健食品中咖啡因、盐酸麻黄碱、盐酸芬氟拉明和盐酸西布曲明的液质联用方法。方法使用Agilent 1100液相色谱和离子阱质谱联用,ESI源,C18柱梯度洗脱。结果使用本方法对12种市售减肥保健食品中的4种违禁添加药物进行了快速筛查鉴定,其中2种检出西布曲明。结论方法简便快速,专属性好。     

A rapid method for tetrodotoxin (TTX) determination by LC-MS/MS from small volumes of human serum,and confirmation of pufferfish poisoning by TTX monitoring

A simple and rapid detection method for tetrodotoxin (TTX), a powerful sodium channel blocker, in small volumes of the serum of patients with pufferfish poisoning, was developed using an ultrafiltration spin column. The separation and identification of TTX was performed by liquid chromatography (LC) with a multi-mode ODS column and tandem mass spectrometry. TTX and an internal standard (voglibose) were monitored and quantitated using ion transitions: the respective precursor-to-product ion combinations, m/z 320/162 for TTX and 268/92 in MRM mode. The recoveries of TTX and voglibose were 91.0–110.8% and 104.7–107.4%, respectively, and with high accuracy (intra-run, 4.35–5.29%; inter-run, 2.95–5.79%) and linearity (0.5–200 ng/ml serum: r = 0.9994). The lower limit of quantification was 0.5 ng/ml serum. In patients, maximum serum TTX concentrations were 30.2 ng/ml serum for patient 1 on day 0 and 56.1 ng/ml serum for patient 2 on day 1. These results are important for the treatment of patients and for the identification of poisoning as well as for the determination of the cause of the food poisoning.     

液相色谱-串联质谱法与离子色谱-串联质谱法测定食品中氯酸盐和高氯酸盐方法比较研究

目的 考察离子色谱-串联质谱法（ion chromatography-tandem mass spectrometry,IC-MS/MS）和液相色谱-串联质谱法（liquid chromatography-tandem mass spectrometry,LC-MS/MS）在测定不同食品中氯酸盐和高氯酸盐的一致性。方法 利用乙腈/水（3:2, V:V）提取鸡蛋、奶粉和菠菜中的目标物,经石墨化炭黑（graphitized carbon black, GCB）小柱净化,以IonPacTM AS20离子色谱柱和CSHTM Fluoro-Phenyl液相色谱柱为分析柱,三重四极杆质谱仪检测,内标法定量。对两种方法测得的数据进行正态性检验和差异性分析。比较两种方法的保留时间漂移,考察色谱稳定性。对两种方法测得的浓度进行线性回归和B-AbBland -aAltman（B-A）图可视化考察方法一致性。结果 两种方法测得氯酸盐（高氯酸盐）的浓度在1~500（0.1~50.0） ?g/L范围内线性良好（r2＞0.999）。IC-MS/MS与LC-MS/MS测定高氯酸盐的定量限均为0.5 ?g/kg,氯酸盐的定量限分别为5.7 ?g/kg和4.2 ?g/kg。回收率范围分别为82.3%~107.4%和94.8%~109.4%,相对标准偏差分别为1.5%~13.6%和1.2%~9.6%。IC-MS/MS（LC-MS/MS）测得鸡蛋、奶粉、菠菜中氯酸盐和高氯酸盐的基质效应分别为12.1%（22.1%）、9.0%（27.4%）、-11.8%（-24.0%）和-16.8%（-18.5%）、-18.6%（-28.4%）、-20.2%（-21.1%）。线性回归法显示两种方法测定氯酸盐和高氯酸盐浓度的回归曲线斜率分别为1.0144和1.0908。B-A图显示绝大多数数据点位于平均值±1.96标准偏差范围。结论 两种方法的准确度和精密度均符合化学检验方法验证通则的要求,两种方法测得的氯酸盐、高氯酸盐浓度结果基本一致,但氯酸盐在LC-MS/MS系统中的保留时间稳定性更好,IC-MS/MS在测定食品中氯酸盐、高氯酸盐时的抗基质干扰能力更强。     

Development and validation of an LC-MS/MS method for the detection of phomopsin A in lupin and lupin-containing retail food samples from the Netherlands

Phomopsins (PHO) are mycotoxins produced by the fungus Diaporthe toxica (also referred to as Phomopsis leptostromiformis). Lupin is the most important host crop for this fungus and PHO are suspected as cause of lupinosis, a deadly liver disease, in sheep. Lupin is currently in use to replace genetically modified soy in many food products available on the European market. However, a validated method for analysis of PHO is not available until now. In this work, a dilute-and-shoot LC-MS/MS-based method was developed for the quantitative determination and identification of phomopsin A (PHO-A) in lupin and lupin-containing food. The method involved extraction by a mixture of acetonitrile/water/acetic acid (80/20/1 v/v), dilution of the sample in water, and direct injection of the crude extract after centrifugation. The method was validated at 5 and 25 µg PHO-A kg^?1 product. The average recovery and RSD obtained were 79% and 9%, respectively. The LOQ (the lowest level for which adequate recovery and RSD were demonstrated) was 5 µg PHO-A kg^?1. Identification of PHO-A was based on retention time and two transitions (789 > 226 and 789 > 323). Using the average of solvent standards from the sequence as a reference, retention times were all within ± 0.03 min and ion ratios were within ± 12%, which is compliant with European Union requirements. The LOD (S/N = 3 for the least sensitive transition) was 1 µg PHO-A kg^?1 product. Forty-two samples of lupin and lupin-containing food products were collected in 2011–2012 from grocery stores and internet shops in the Netherlands and analysed. In none of the samples was PHO-A detected.     

Analytical method for fast screening and confirmation of multi-class veterinary drug residues in fish and shrimp by LC-MS/MS

A multi-class, multi-residue analytical method based on LC-MS/MS detection was developed for the screening and confirmation of 28 veterinary drug and metabolite residues in flatfish, shrimp and eel. The chosen veterinary drugs are prohibited or unauthorised compounds in Korea, which were categorised into various chemical classes including nitroimidazoles, benzimidazoles, sulfones, quinolones, macrolides, phenothiazines, pyrethroids and others. To achieve fast and simultaneous extraction of various analytes, a simple and generic liquid extraction procedure using EDTA-ammonium acetate buffer and acetonitrile, without further clean-up steps, was applied to sample preparation. The final extracts were analysed by ultra-high-performance liquid chromatography coupled with tandem mass spectrometry (UHPLC-MS/MS). The method was validated for each compound in each matrix at three different concentrations (5, 10 and 20 ng g^–1) in accordance with Codex guidelines (CAC/GL 71-2009). For most compounds, the recoveries were in the range of 60–110%, and precision, expressed as the relative standard deviation (RSD), was in the range of 5–15%. The detection capabilities (CCβs) were below or equal to 5 ng g^–1, which indicates that the developed method is sufficient to detect illegal fishery products containing the target compounds above the residue limit (10 ng g^–1) of the new regulatory system (Positive List System – PLS).