Occurrence of polycyclic aromatic hydrocarbons and their hydroxylated metabolites in infant foods

Eleven polycyclic aromatic hydrocarbons (PAHs) have been analysed in commercial milk formulae and infant cereals. Two hydroxylated PAHs metabolites (1-OH-Pyr and 3-OH-B[a]P) and their conjugates were also analysed in milk samples. To determine the selected PAH metabolites, a simple, fast quantitative and economic method was developed. This method comprising ultrasound-assisted solvent extraction, enzymatic hydrolysis, solid-phase clean-up and detection by liquid chromatography with fluorescence detection (LC–FD) and liquid chromatography tandem mass spectrometry (LC–MS/MS) as confirmatory technique. The method was evaluated by constructing calibration curves, measurement of recovery, precision and the limits of detection. The purpose of this survey was to determine the selected analytes, to assess the exposure of babies and infants and to produce data for comparison with proposed limits that were being considered at the time of the survey. The results showed that not only no samples would have exceeded the limit for benzo[a]pyrene which is used as an indicator for the presence of PAHs, but also no hydroxy PAH metabolites have been detected.     

Determination of polycyclic aromatic hydrocarbons in Italian milk by HPLC with fluorescence detection

The presence of polycyclic aromatic hydrocarbons (PAHs) in Italian commercial milk samples is reported. The study was carried out on lactating (cow and goat) and plant (rice, soya, oat) milk. The quantitative determination involved liquid–liquid extraction of PAHs, a pre-concentration and determination by HPLC using a fluorescence detector. The recovery of analytes was in the range of 70–115%. The precision of the method was found to be between 6% and 24%. The detection limit ranged from 0.66 to 33.3 µg l^–1 corresponding to 0.03–1.66 µg kg^–1 milk (wet weight), at a signal-to-noise ratio of 3, depending on the compound. By this procedure, the levels of more volatile PAHs (two to three aromatic rings) were confirmed in 34 commercial milk and three plant milk samples, whereas benzo[a]pyrene was found only in five pasteurised milk samples at a mean concentration of 0.17 µg kg^–1 milk. These results provide evidence that PAH levels are influenced by heat treatments and skimming processes of milk production.     

Concentrations and health hazards of polycyclic aromatic hydrocarbons in selected commercial brands of milk

The concentrations and profiles of polycyclic aromatic hydrocarbons (PAHs) were determined in twenty popular commercial brands of milk in the Nigerian market after saponification with ethanolic KOH and cyclohexane extraction and clean up using a gas chromatography with flame ionization detection. The concentrations of the Σ16 PAHs in these brands of milk ranged from 15.6 to 1,711.8 μg kg^?1. The dominant PAH compounds in these brands of milk were 3-and-4-rings PAHs. The dietary intake of BaP, PAH2, PAH4 and PAH8 were 0–53.9 and 0–369.6 ng kg^?1 bw day^?1 respectively. Using these indicators for occurrence and effects (BaP, PAH2, PAH4 and PAH8) PAHs in food, the margin of exposure were <10,000 in 15–30 % of the brands.     

Polycyclic aromatic hydrocarbons in milk powders marketed in Argentina and Brazil

The aim of this study was to quantify polycyclic aromatic hydrocarbon (PAH) levels in milk powder samples commercialised in Argentina and Brazil during 2012. Thirty-one samples were available from the retail market. An HPLC method for the determination of PAHs was applied involving a clean-up step with silica cartridges. Recoveries were greater than 79% for all PAHs analysed. Reproducible determination with adequate detection and quantification limits (LOD and LOQ) were attained by HPLC with fluorescence detection for 14 PAHs. Acenaphthylene was determined with a UV–VIS detector. There is no significant difference in any PAHs or in the sum of them between the Argentinean and Brazilian samples. Therefore, the samples were evaluated together. The highest concentration of benzo(a)pyrene (BaP) detected was 0.57 µg kg^?1 in milk powder. Contamination of samples expressed as the sum of 15 analysed PAHs varied between 11.8 and 78.4 µg kg^?1 and as PAH4 (BaP, chrysene, benzo(a)anthracene and benzo(b)fluoranthene) was between 0.02 and 10.16 µg kg^?1. The correlation coefficient for PAH2 (BaP and chrysene) and PAH4 groups was 0.95, for PAH2 and PAH8 it was 0.71, and for PAH4 and PAH8 it was 0.83. All the samples were below the regulatory limit for BaP, but 65% of commercial milk powders do not comply with the European Union limit for PAH4. This is the first report of PAH contamination in powder milk from Argentina and Brazil.     

Polycyclic aromatic hydrocarbons in a semiaquatic plant and semipermeable membrane devices exposed to air in Thailand

Semipermeable membrane devices (SPMDs) were deployed at six sites in the Bangkok region, Thailand, to investigate spatial variations in atmospheric concentrations of polycyclic aromatic hydrocarbons (PAHs). Sampling sites affected by various levels of traffic intensity were studied. In addition, PAH levels were determined in a common human food plant (water spinach) harvested from canals and ponds in the sampling areas. Significant differences in atmospheric PAH concentrations between sites were found, with 10 times higher PAH levels in the urban areas compared to the rural areas. Increasing concentrations of 1-methylphenanthrene relative to phenanthrene were found in the urban air close to the city center, indicating that traffic probably contributed to the higher PAH concentrations detected. Due to SPMD's passive sampling technique, their long-term operation and high ability to detect spatial differences, they proved to be suitable for semiquantitative field studies of PAHs. The PAH compounds sampled with SPMDs were mainly associated with gaseous PAHs, while both gas phase and particle-bound PAHs were detected in the plant samples. The relative abundance ratios of some PAHs in the plants were not well correlated with the ratios detected in the SPMDs, indicating that gas-phase exposure made low contribution to the PAH concentrations in the plants. However, similarities in the profiles of 3-ring PAHs between the SPMD and plant samples indicate that gas-phase exchange occurs between the atmosphere and the plants.     

Distributed sequestration and release of PAHs in weathered sediment: the role of sediment structure and organic carbon properties

Polycyclic aromatic hydrocarbon (PAH) contaminated sediments from Piles Creek (PC) and Newtown Creek (NC) in the NY/NJ Harbor estuary were separated into size fractions and further separated into low (<1.7 g cm(-3)) and high (>1.7 g cm(-3)) density fractions. The fractionated sediments were characterized for carbon content pore structure, surface area, and PAH concentration. Most PAHs (50-80%) in both sediments were associated with the low-density fraction, which represents only 3-15% of total sediment mass, at levels greater than expected based on equilibrium partitioning. PC low-density sediment had 10 times greater organic carbon-normalized equilibrium partitioning coefficients (Koc) than the other size fractions and whole sediment. Characterization of the sediment organic matter suggested that the preferential sequestration observed in PC sediment was not correlated with soot carbon but was likely due to the presence of detrital plant debris, an important food source for benthic animals. Fractional PAH desorption from whole PC sediment was significantly higher than from NC sediment after 3 months. For both sediments, a smaller percentage of the total PAHs was desorbed from the low-density fraction. However, because PAH concentrations were greatly elevated in these fractions, more PAH mass was desorbed than from the corresponding bulk and high-density fractions. These results demonstrate that PAHs are preferentially sequestered in a separable, low-density fraction at levels not predictable by equilibrium partitioning theory. Further, the low-density fraction apparently controls whole-sediment PAH release. Although plant debris appears to be an important sorbent for PAHs, this material may readily release PAHs into the aqueous phase.     

基于单链DNA模板合成铜纳米簇的四环素无标记检测

以聚T单链DNA为模板合成的铜纳米簇作为荧光探针,建立了一种快速、非标记型的荧光生物传感检测新方法,并用于实际样品中四环素的检测.结果表明,该方法用于检测四环素残留的检出限为0.01μmol/L,用于实际样品四环素残留的测定低限为48μg/kg,而且无需要任何荧光染料标记或复杂的DNA序列设计,所有过程均在室温下10 ...     

Effect-based and chemical analysis of polycyclic aromatic hydrocarbons in smoked meat: a practical food-monitoring approach

Polycyclic aromatic hydrocarbons (PAHs), which are generated by heat treatment and smoke curing of meat, pose a risk to human health. At present, the determination of these unwanted contaminants requires costly, time-consuming chemical analysis of smoked meat. An alternative is effect-directed high-throughput bioassays, which could also be used as a pre-screening method. The authors recently adapted the in vitro chemical-activated luciferase gene expression (CALUX) assay as a rapid, sensitive, and inexpensive screening technique for compounds such as dioxins, polychlorinated biphenyls, and PAHs. The aim of the present study was to apply a practical approach under realistic conditions. Custom-made meat samples produced under defined conditions with different PAH levels were analysed using this bioassay and gas chromatography-mass spectrometry (GC/MS) to determine the influence of different smoking conditions (temperature and duration) on PAH levels. It was found that cold smoking for up to 6 h did not result in strong PAH contamination, whereas hot (65°C) and longer smoking times caused a considerable increase in both the bioassay response and the levels of 31 individually determined PAHs. The response in the effect-based bioassay was in good agreement with the values of chemical analysis. The bioassay made it possible to determine accurately the degree of contamination. The results show that this assay is suitable for high-throughput screening for unknown levels of toxicologically relevant PAHs in meat samples and is sensitive enough to differentiate between different PAH levels generated under various smoking conditions. Effect-based screening techniques, therefore, provide a new instrument for official food monitoring.     

Techno-environmental and life cycle assessment of ‘oat-milk’ production in Ecuador: A cradle-to-retail life cycle assessment

There is an increase in consumer demand for plant-based alternatives to common food products. A critical segment of the food industry is the dairy market, where milk alternatives are becoming the choice of many people throughout the world. Consumers purchase milk alternatives as they provide an environmentally friendly and healthier option than cow’s milk. The beef and cattle industry's negative impact on the environment has been well reported. The cattle industry accounts for almost 3% of the overall greenhouse gases emitted each year in climate change. This study analyses the life cycle assessment for the cradle-to-retail system in the production of oat-based milk in Ecuador. Importing the oat was considered, and a techno-environmental perspective was applied to the system modelling. It introduces oat milk as a new alternative to plant-based beverages. Soy and almond milk are compared as established options in the market. Results showed better environmental performance from the oat beverage when compared to the traditional cow’s milk (+80% lower GHG emitted). Also, it can be established as a competitor for plant-based alternatives. For instance, it requires significantly less water consumption than almond milk. The oat-milk beverage has a better environmental performance than the traditional cow milk-based options.     

高效液相色谱-荧光法测定油炸型膨化食品中4种多环芳烃

建立了高效液相色谱-荧光法(HPLC-FLD)测定油炸型膨化食品中苯并[a]蒽(BaA)、(CHR)、苯并[b]荧蒽(BbF)、苯并[a]芘(BaP)4种多环芳烃(PAHs)的分析方法。样品经饱和氯化钠分散后,采用正己烷萃取,经BAP-3分子印迹柱净化,Waters PAH C₁₈色谱柱分离,荧光检测器进行测定,外标法定量。在0.5~40 μg/L浓度范围内4种PAHs均有良好的线性(r>0.999),定量限为(LOQ)0.3~0.5 μg/kg。在空白样品中进行1、5、25 μg/kg 3个水平的加标回收实验,方法的平均回收率在90.3%~107.4%之间,精密度在6.5%以下。该方法简单、快速、灵敏、重现性好,可用于油炸型膨化食品中4种PAHs的定量测定。     

Rapid point-of-need detection of bacteria and their toxins in food using gold nanoparticles

Biosensors need to meet the rising food industry demand for sensitive, selective, safe, and fast food safety quality control. Disposable colorimetric sensors based on gold nanoparticles (AuNPs) and localized surface plasmon resonance are low-cost and easy-to-perform devices intended for rapid point-of-need measurements. Recent studies demonstrate various facile and versatile AuNPs-based analytical platforms for the detection of bacteria and their toxins in milk, meat, and other foods. In this review, we introduce the general characteristics and mechanisms of AuNPs calorimetric biosensors, and highlight optimizations needed to strengthen and improve the quality of devices for their application in food matrices.     

Urinary PAH metabolites as biomarkers of exposure in aquatic environments

While immunoassays have been extensively applied to evaluate environmental contamination, to date they have rarely been used for the analysis of biological fluids outside of human medicine. These media are important because pollutants such as polycyclic aromatic hydrocarbons (PAHs) and their metabolites become concentrated in tissues, body fluids, and excreta, thereby offering a measure of exposure to biologically available contaminants. Such analyses also provide a nondestructive tool for monitoring exposure. Crabs (Carcinus maenas) were exposed to phenanthrene and pyrene (separately) at concentrations ranging from 0 to 200 microg L(-1). After 48 h, urine samples were taken and analyzed by immunoassay and UV-fluorescence spectrophotometry. Urinary levels (calibrated against hydroxylated metabolites) proved to be dose dependent for both compounds, and good agreementwas demonstrated between the immunoassay and the fluorescence techniques. The cross reactivity of the immunochemical technique (ELISA) for pyrene and hydroxy-metabolites was lower than for phenanthrene. HPLC analyses demonstrated that urine from the crabs exposed to pyrene contained mainly conjugate PAH metabolites whose concentrations (the sum of the four main pyrene metabolites/conjugates) showed very good agreement with the ELISA (r2 > 0.94) and fluorescence (r2 > 0.91) data. Environmental samples were also analyzed by ELISA and UV-fluorescence, and both techniques detected PAH (mainly petrogenic) contamination in the urine samples from a polluted harbor. These data demonstrate the potential of urine analyses by ELISA and UV-fluorescence to measure exposure of crabs to PAH.     

Comparison of donor–acceptor and alumina columns for the clean-up of polycyclic aromatic hydrocarbons from edible oils

Two methods for clean-up and sample enrichment for the analysis of polycyclic aromatic hydrocarbons (PAHs) in edible oils are compared; a clean-up based on a donor–acceptor complex chromatography (DACC) column and a standardized method widely used in the food industry consisting in a low pressure column chromatography with alumina as stationary phase. Both methods are followed by a reversed-phase high-performance liquid chromatography with fluorescence detection for the separation and quantitation of each PAH. Certified materials were used in order to validate the methods. The limits of detection were lower than 1 ng/g and good selectivity was achieved in both cases. The DACC column clean-up is faster and better accuracies were obtained. The advantages and disadvantages of both methods are discussed.     

A gas chromatography-mass spectrometry-based metabolomic approach for the characterization of goat milk compared with cow milk

In this work, the polar metabolite pool of commercial caprine milk was studied by gas chromatography-mass spectrometry and multivariate statistical data analysis. Experimental data were compared with those of cow milk and the discriminant analysis correctly classified milk. By the same means, differences due to heat treatments (UHT or pasteurization) on milk samples were also investigated. Results of the 2 discriminant analyses were combined, with the aim of finding the discriminant metabolites unique for each class and shared by 2 classes. Valine and glycine were specific to goat milk, talose and malic acid to cow milk, and hydroxyglutaric acid to pasteurized samples. Glucose and fructose were shared by cow milk and UHT-treated samples, whereas ribose was shared by pasteurized and goat milk. Other discriminant variables were not attributed to specific metabolites. Furthermore, with the aim to reduce food fraud, the issue of adulteration of caprine milk by addition of cheaper bovine milk has been also addressed. To this goal, mixtures of goat and cow milk were prepared by adding the latter in a range from 0 to 100% (vol/vol) and studied by multivariate regression analysis. The error in the level of cow milk detectable was approximately 5%. These overall results demonstrated that, through the combined approach of gas chromatography-mass spectrometry and multivariate statistical data analysis, we were able to discriminate between milk typologies on the basis of their polar metabolite profiles and to propose a new analytical method to easily discover food fraud and to protect goat milk uniqueness. The use of appropriate visualization tools improved the interpretation of multivariate model results.     

Controlled exposure chamber study of uptake and clearance of airborne polycyclic aromatic hydrocarbons by wheat grain

Polycyclic aromatic hydrocarbons (PAHs) can partition from the atmosphere into agricultural crops, contributing to exposure through the dietary pathway. In this study, controlled environmental chamber experiments were conducted to investigate the transfer of PAHs from air into wheat grain, which is a major food staple. A series of PAHs ranging in size from naphthalene to pyrene were maintained at elevated gas-phase concentrations in the chamber housing mature and dry wheat grain both on the plant and with the husk removed. The PAHs did not achieve equilibrium between the air and grain over the 6.5 month monitoring period used in this study. Therefore, PAH uptake under field conditions is expected to be kinetically limited. A clearance study conducted for the grain showed the half-life of clearance was approximately 20 days for all compounds studied. The results suggest that atmospheric contaminants that partition into grain may remain in the grain long enough to contribute to dietary exposure for humans. Mass transfer across the air/grain interface appeared to be limited by grain-side resistance. The grain may act as a multicompartment system with rapid exchange at the surface followed by slower transfer into the grain. A grain/air concentration relationship was derived for the uptake time that is relevant to field conditions.     

Recent developments and applications of surface plasmon resonance biosensors for the detection of mycotoxins in foodstuffs

Over the past 10 years, great efforts on the development of methods for rapid mycotoxin detection in foodstuffs have been made. As one of the relatively new analytical techniques, surface plasmon resonance (SPR) has been proven particularly advantageous for rapid, label-free, sensitive analyte detection. Using SPR, qualitative and quantitative analysis can be performed in real-time. Mycotoxins are a group of small, toxic products formed as secondary metabolites by a few fungal species. They can contaminate foodstuffs on a large scale and consequently threaten human health through food chain. Thus, rapid, sensitive, and selective determination of mycotoxin is of great significance for the food safety. This contribution addresses the basic principle of SPR, the existing detection methods, and the progress on mycotoxin detection using SPR biosensor.     

Application of a simplified HPLC assay for the determination of phylloquinone (vitamin K1) in animal and plant food items

The lack of precise data in food composition tables demands intensive investigation of phylloquinone content in human food, for the purpose of nutritional intake assessment and support of anticoagulant drug therapy. The determination of small phylloquinone amounts requires sensitive and selective detection methods. Based on a RP-HPLC assay using post-column derivatization and fluorescence detection, and combined with a liquid-liquid sample clean-up, a rapid and routinely usable assay is presented. The application to foods is shown in the items of milk (0.36 ± 0.07 μg/100 g), other dairy products (yoghurt, 0.34 ± 0.04 μg/100 g), eggs (1.85 ± 0.99 μg/100 g), edible oils (from 0.97 to 112 μg/100 g), oatmeal (4.07 ± 0.35 μg/100 g), broccoli (195 ± 40 μg/100 g), cauliflower (12.0 ± 6.1 μg/100 g), carrots (5.94 ± 3.39 μg/100 g) and potatoes (1.62 ± 1.21 μg/100 g). The samples cover a range of foods, from those of fairly low to those of high phylloquinone content. High precision and wide application range both offer valuable instruments for food analysis and construction of current food composition and nutrition tables in the future.     

Detection of cow milk adulteration in yak milk by ELISA

In the current study, a simple, sensitive, and specific ELISA assay using a high-affinity anti-bovine β-casein monoclonal antibody was developed for the rapid detection of cow milk in adulterated yak milk. The developed ELISA was highly specific and could be applied to detect bovine β-casein (10–8,000 μg/mL) and cow milk (1:1,300 to 1:2 dilution) in yak milk. Cross-reactivity was <1% when tested against yak milk. The linear range of adulterant concentration was 1 to 80% (vol/vol) and the minimum detection limit was 1% (vol/vol) cow milk in yak milk. Different treatments, including heating, acidification, and rennet addition, did not interfere with the assay. Moreover, the results were highly reproducible (coefficient of variation <10%) and we detected no significant differences between known and estimated values. Therefore, this assay is appropriate for the routine analysis of yak milk adulterated with cow milk.     

Determination of polycyclic aromatic hydrocarbons in smoked pork by effect-directed bioassay with confirmation by chemical analysis

Polycyclic aromatic hydrocarbons (PAHs) are generated during smoke curing and other heating treatments of food and represent a large class of chemical pollutants including a number of carcinogens. At present, PAHs are frequently detected by costly and time-consuming chemical analysis. Effect-directed in vitro cell-based bioassays of contaminants can offer a rapid, sensitive, and relatively inexpensive alternative for screening of contaminants in comparison to instrumental analysis. They enable estimation of total biological activity of all compounds acting through the same mode of binding. The aryl hydrocarbon receptor as a binding site plays an important role in PAH-induced carcinogenesis. The in vitro chemical-activated luciferase expression assay (using conditions to detect PAH) was investigated for its applicability for effect-directed analysis of PAH levels in smoked meat. There was an intra-assay variability of 0 to 15% and a mean coefficient of variation of 25% (3 to 50%) for the cleanup and bioassay analysis of the smoked pork samples. There was a correlation between the total responses of the bioassay and the individual amounts of the PAHs with a high molecular weight. The comparison of 2,3,7,8-tetrachlorodibenzo-p-dioxin and benzo[k]fluoranthene used as standard in the in vitro chemical-activated luciferase expression assay resulted in benzo[k]fluoranthene being able to be used as an alternative, nontoxic standard in the bioassay. This bioassay is an applicable effect-directed functional prescreening method for the analysis of PAHs in smoked meat and appears to have potential in being used for food control in the future.     

牛羊乳混掺检测鉴别技术研究进展

近年来,羊乳以其较好的营养特性渐成流行趋势,由于季节波动的影响,其价格远高于牛乳。在经济利益的驱动下,羊乳中掺入牛乳的现象时有发生,且呈现日趋严重的趋势,制约了羊奶产业的良性发展,迫切需要建立快速准确的牛羊乳混掺定性定量检测技术体系。本文对牛羊乳的差异及据此建立的、业已报道的相关检测技术进行了比较分析。常用检测技术主要包括色谱技术(气相色谱、气相色谱-质谱联用、高效液相色谱-质谱联用、高效液相色谱)、电泳技术(聚丙烯酰胺凝胶电泳、等电点聚焦电泳、毛细管电泳)、酶联免疫技术、聚合酶链式反应技术等,介绍了各种检测技术的原理及特点,并分析其可行性,为探索新的高效检测方法提供了思路,为牛羊乳混掺检测分析提供文献参考。