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Mineral oil aromatic hydrocarbons (MOAHs) include mutagenic and carcinogenic substances and are considered a potential health risk. Current methods address the total MOAH content but cannot address the actual toxicological hazard of individual components. This work presents a combined methodology closing those gaps: high-performance liquid chromatography (HPLC) coupled to gas chromatography with flame ionization detection was used to determine the MOAH content. To characterize present substance classes, comprehensive two-dimensional gas chromatography with time-of-flight mass spectrometry was applied. Preparative HPLC separated MOAHs into subgroups, which were tested with a miniaturized Ames test evaluating DNA reactivity of isolated fractions. Combining these methods allowed a correlation between present subgroups and DNA reactivity. The developed approach was applied to a mineral oil and distinguished between not DNA-reactive mono- and diaromatics and DNA-reactive tri- and polyaromatics, providing a proof of concept. Hereinafter, it will be applied to diverse sample matrices including mineral oils, food, and food contact materials.

Understanding the transfer of non-dioxin-like polychlorinated biphenyls (ndl-PCBs) into foods of animal origin is crucial for human health risk assessment. In two experiments, we investigated the transfer of ndl-PCBs from contaminated feed and soil into eggs and meat of laying hens. The transfer from the feed was investigated with 30 laying hens. The treated hens were divided into two groups fed a contaminated diet (12.8 μg/kg sum of indicator ndl-PCBs; 88% dry matter (DM)) for 28 and 63 days, respectively, and then experienced a depuration period of 100 days with control feed. The transfer from soil was investigated with 72 laying hens kept in three separate outdoor pens (with three levels of ndl-PCB soil contamination) for 168 days. In both experiments, eggs were collected and analyzed for ndl-PCBs. In the second experiment, animals (

Acrylamide is toxic aliphatic amide formed via the Maillard reaction between asparagine and reducing sugars during thermal processing of food. Herein, a specific nanobody termed Nb-7E against the acrylamide derivative xanthyl acrylamide (XAA) was isolated from an immunized phage display library and confirmed to be able to detect acrylamide. First, an indirect competitive enzyme-linked immunosorbent assay (ic-ELISA) was established for acrylamide with a limit of detection (LOD) of 0.089 μg/mL and working range from 0.23 to 5.6 μg/mL. Furthermore, an enhanced electrochemical immunoassay (ECIA) was developed based on the optimized reaction conditions. The LOD was as low as 0.033 μg/mL, threefold improved compared to that of ic-ELISA, and a wider linear detection range from 0.39 to 50.0 μg/mL was achieved. The average recoveries ranged from 88.29 to 111.76% in spiked baked biscuits and potato crisps. Finally, the analytical performance of the ECIA was validated by standard ultraperformance liquid chromatography tandem mass spectrometry (UPLC-MS/MS).

Cork stoppers are the preferred choice for sealing bottled wines around the world. However, the quality of cork stoppers is also defined by the presence of 2,4,6-trichloroanisole (TCA), which gives the wine an unpleasant moldy/musty taste. It is a matter of concern for both cork stopper manufacturers and wine producers whether TCA can be transported between stoppers. As little is known about cross contamination between stoppers, this work provides enough experimental data to discuss the extent of TCA transfer in naturally contaminated stoppers in the liquid and gas phase that can be useful to the cork industry and the wine industry. We found that when a clean stopper is soaked together with a contaminated one in hydro-alcoholic solution, 12% of the TCA can be transferred. In gas-phase contamination, only stoppers with 12 ng/L, or more, contaminate clean stoppers when enclosed together for several days. In a second experiment, where clean corks were exposed to a controlled contaminated environment, it was found that TCA contamination was not confined to the outermost layer of the stoppers. Based on these findings, some recommendations are given to prevent TCA cross contamination between stoppers during the cork stopper manufacturing, storage, wine making, and bottling.

Some components of plastic food packaging can migrate into food, and whereas migration studies of known components are required and relatively straightforward, identification of nonintentionally added substances (NIAS; unknowns) is challenging yet imperative to better characterizing food safety. To this aim, migration was investigated across 24 unique plastic food packaging products including plastic wrap, storage bags, vacuum bags, and meat trays. Gas and liquid chromatography separation systems coupled with Orbitrap mass analyzers were used for comprehensive nontargeted screening of migrants. Tentative identifications of features were assigned by searching commercial databases (e.g., NIST, MZCloud, ChemSpider, Extractables and Leachables) and filtering results based on mass accuracy, retention time indices, and mass spectral patterns. Several migrants showed elevated levels in specific food packaging types, particularly meat trays and plastic wrap, and varying degrees of migration over the 10 days. Eleven putative migrants are listed as substances of potential concern or priority hazardous substances. Additionally, migration amounts of an Irgafos 168 degradation product determined by semiquantitation exceeded proposed theoretical maximum migration values.

Widely consumed thermally processed corn-based foods can have a great contribution to acrylamide dietary intake, thus bearing a high public health risk and requiring attention and application of strategies for its reduction. This paper reviews the literature on the acrylamide content of corn-based food products present in the market around the world. The potential of corn for acrylamide formation due to its content of free asparagine and reducing sugars is described. Human exposure to acrylamide from corn-based foods is also discussed. The content of acrylamide in corn/tortilla chips, popcorn, and corn flakes, as widely consumed products all over the world, is reported in the literature to be between 5 and 6360 μg/kg, between

Non-dioxin-like polychlorinated biphenyls (ndl-PCBs) are a subclass of persistent bioaccumulative pollutants able to enter the food chain. Toxicokinetic models for the transfer of the six ndl-PCB congeners (PCBs 28, 52, 101, 138, 153, and 180) from contaminated feed and soil into chicken eggs and meat are presented. Three independent controlled feeding study datasets were used to estimate the model parameters and four studies for evaluating the model performance. The yolk deposition of ndl-PCBs is modeled in a novel way that mimics the physiology of yolk growth and development, resulting in improved prediction of the experimental data without introducing an ad hoc time delay between ovulation and oviposition. Using the models, the highest level of 2.4 μg/kg dry matter (DM) was calculated for the sum of ndl-PCBs in laying hen feed to ensure that the current maximum levels in meat and eggs (40 ng/g fat) will not be exceeded. It is also shown how this highest level in feed should be adapted in case soil, in addition to feed, is also a source of ndl-PCBs for free-range chickens.

Ochratoxins (OTs) with nephrotoxic, immunosuppressive, teratogenic, and carcinogenic properties are thermostable fungal subordinate metabolites. OTs contamination can occur before or after harvesting, during the processing, packing, distribution, and storage of food. Mold development and mycotoxin contamination can occur in any crop or cereal that has not been stored properly for long periods of time and is subjected to high levels of humidity and temperature. Ochratoxin A (OTA) presents a significant health threat to creatures and individuals. There is also a concern of how human interaction with OTA will also express the remains of OTA from feedstuffs into animal-derived items. Numerous approaches have been studied for the reduction of the OTA content in agronomic products. These methods can be classified into two major classes: inhibition of OTA adulteration and decontamination or detoxification of food. A description of the various mycotoxins, the organism responsible for the development of mycotoxins, and their adverse effects are given. In the current paper, the incidence of OTA in various fodder and food materials is discussed, which is accompanied by a brief overview of the OTA mode of synthesis, physicochemical properties, toxic effects of various types of ochratoxins, and OTA decontamination adaptation methods. To our knowledge, we are the first to report on the structure of many naturally accessible OTAs and OTA metabolism. Finally, this paper seeks to be insightful and draw attention to dangerous OTA, which is too frequently neglected and overlooked in farm duplication from the list of discrepancy studies.

In this study, the residue data for conazole fungicides were collated and analyzed in all crop samples reported by the United States Department of Agriculture Pesticide Data Program over the period of 2009-2019. Considering all individual samples, the overall detection frequencies (DFs) of conazoles are less than 13%. Among the 18 conazoles, imazalil had the highest overall DF of 6%, followed by tebuconazole and myclobutanil, with 4% each. Conazoles were detected most frequently in raisins with 28% DF, followed by cherries (frozen and fresh) and grapes, with 12, 10, and 10%, respectively. The presence of multiple conazoles in single commodity samples is very low, below 2%. The analyses found no more than four conazoles present in any given sample. Out of the 18 conazoles, 8 of them were not detected in more than 99.9% of the commodity samples from 2009 to 2019 and, therefore, can be eliminated from screening-level cumulative risk assessment for dietary contributions from food items. While conazoles are widely used on food commodities, co-occurrence of conazole residues was observed only in a very limited number of food commodities, including raisins, grapes, cherries (frozen), nectarines, and peaches. Considering the remaining individual food commodities, the co-occurrence of conazole residues in single commodity samples is very low or not even present.

Two simple and low-cost QuEChERS approaches were optimized and validated for multimycotoxin determination in grains by UPLC-MS/MS and applied to assess effectiveness of controlled atmosphere (CA) storage in preventing mycotoxin contamination. Common bean, soybean, and maize samples were stored for 6 months. CA treatments were conducted varying O2 and CO2 partial pressures, temperatures, and moisture contents of the chambers. In the validation study for common bean and maize, 8 out of 11 mycotoxins were successfully validated. For soybean, 10 out of 11 mycotoxins were validated. Aflatoxin B1 was detected in all commodities. Statistical tests suggest that storage temperature played a key role in aflatoxin B1 concentrations in common bean and soybean, but had no influence on maize. Maize was also positive for fumonisins B1 and B2. Differences in fumonisin concentrations were not significant among different treatments. Concentrations of aflatoxin B1 in some samples exceeded legislation's maximum levels. Thus, some of the CA treatments applied were effective in preventing mycotoxin contamination in common bean and soybean but were not effective for maize.

The halal food market is globally growing along with the increased risk of adulteration. We proposed an amplification-free and mix-to-read CRISPR-Cas12-based nucleic acid analytical strategy allowing rapid identification and analysis of pork components, thus enriching the toolbox for ensuring halal food authenticity. We designed and optimized guide RNA (gRNA) targeting the pork cytochrome b (Cyt b) gene. gRNA allowed specific identification of the target Cyt b gene from pork components followed by activation of Cas12 protein to abundantly cleave single-stranded DNA probes with terminally labeled fluorophore and quencher groups, thus turning on fluorescence. The presence of the pork Cyt b gene thus can be mix-and-read- and only-one-step-detected, which may indicate the risk of halal food adulteration. The method allowed specific discrimination of pork meat from beef, mutton, and chicken and yielded a detection limit of 2.7 ng/μL of total DNA from pork meat. The reliability of the method was tested using the following processed meat products: halal foods beef luncheon meat and spiced beef and non-halal foods sausage and dried pork slices. The CRISPR-Cas12-based nucleic acid test strategy is promising for rapid food authentication.

A method for the analysis of saturated mineral oil hydrocarbons (MOSH) and aromatic mineral oil hydrocarbons (MOAH) has been developed to improve interlaboratory precisions especially for amounts below 10 mg/kg. This approach was adopted as the standard method DGF C-VI 22 (20) of the German Society of Fat Sciences. Therefore, this method was evaluated on different edible oils containing a variety of interfering biogenic substances. The precision data were determined in an interlaboratory trial with an international group of 14 laboratories from Germany, Austria, and Italy. Good reproducible relative standard deviations for total MOSH (12.5-20.7%) and total MOAH (12.4-39.5%) as well as HorRat values ranging between 1.1 and 2.3 for total MOSH and between 0.9 and 2.6 for total MOAH have been achieved. As some matrices showed residual interferences in the MOAH fraction, these substances were further analyzed by online high-performance liquid chromatography-comprehensive two dimensional gas chromatography with time of flight mass detection.

Detoxification of ergot-contaminated feed by ammonia would be a practical application, given that ammonia is routinely used in the agriculture industry. To assess the effects of ammonia on ergot alkaloids, natural ergot-contaminated wheat was ammoniated. The total concentration of ergot alkaloids (

Acrylamide, a food processing contaminant with demonstrated genotoxicity, carcinogenicity, and reproductive toxicity, is largely present in numerous prominent and commonly consumed food products that are produced by thermal processing methods. Food regulatory bodies such as the U.S. Food and Drug Administration (U.S. FDA) and European Union Commission regulations have disseminated various acrylamide mitigation strategies in food processing practices. Hence, in the wake of such food and public health safety efforts, there is a rising demand for economic, rapid, and portable detection and quantification methods for these contaminants. Since conventional quantification techniques like liquid chromatography-mass spectrometry (LC-MS) and gas chromatography-mass spectrometry (GC-MS) methods are expensive and have many drawbacks, sensing platforms with various transduction systems have become an efficient alternative tool for quantifying various target molecules in a wide variety of food samples. Therefore, this present review discusses in detail the state of robust, nanomaterials-based and other bio/chemical sensor fabrication techniques, the sensing mechanism, and the selective qualitative and quantitative measurement of acrylamide in various food materials. The discussed sensors use analytical measurements ranging from diverse and disparate optical, electrochemical, as well as piezoelectric methods. Further, discussions about challenges and also the potential development of the lab-on-chip applications for acrylamide detection and quantification are entailed at the end of this review.

An increasing number of studies have suggested that PAH contamination in dairy products demands high concern. This study established an efficient determination method for the European Union 15 + 1 PAHs and four PAH derivatives in dairy samples using a QuEChERS method coupled with GC-QqQ-MS. The optimized method obtained a recovery of 63.38-109.17% with a precision of 3.82-15.62%, and the limit of detection and limit of quantification were 0.08-0.78 and 0.27-2.59 μg/kg, respectively. The validated method was then successfully applied to identify the 20 PAHs in 82 dairy samples, including 43 commercial milk samples and 39 milk powders. The total PAH concentrations ranged from 2.37 to 11.83 μg/kg, and benzo[a]pyrene was only quantified in one milk and one milk powder sample at 0.35 and 0.42 μg/kg, respectively. The concentrations of PAH4 in milk samples and milk powders were not quantified (nq)-3.99 and nq-4.51 μg/kg, respectively. The results confirmed the appreciable occurrence of PAHs in dairy products, especially in infant formula. The data in this study provide a scientific basis for assessment on origin tracing, dietary exposure, and health risk of PAHs and their derivatives.

Pesticide residues in food have been a grave concern to consumers. Herein, we have developed a dual-mode SERS chip using Cu2O mesoporous spheres decorated with Ag nanoparticles (MCu2O@Ag NPs) as both sensing and degradation/clearing unit for rapid detection of pymetrozine and thiram pesticides in tea samples. Three kinds of chemometric algorithms were comparatively applied to analyze the collected SERS spectra of pesticides. In comparison, random frog-partial least squares achieved the best performance with root mean square error of prediction and residual predictive deviation values of 0.9871, 6.17, and 0.9873, 6.64 for pymetrozine and thiram, respectively. Additionally, the prepared SERS chip showed great photocatalytic activity to degrade pesticides under visible light irradiation. Through a facile method, this work presented a novel dual-functional SERS chip for the rapid detection and degradation of low-concentration pesticides in both environmental and food samples.

It is commonly known that the widespread use of antibiotics has led to their existence in food products as residues and ingestion of these food products may create a selection pressure on bacteria inhabiting the human body. In this study, an optimized method for the analysis of antibiotic residues in different food groups, including cereals, meat, eggs, milk, vegetables, and fruits, was developed using solvent extraction, solid-phase extraction cleanup, and liquid chromatography-mass spectrometry (LC-MS/MS). The limits of detection (LODs) were achieved as 0.007-1.1, 0.008-0.46, 0.002-0.67, 0.007-0.63, 0.001-0.098, and 0.005-0.26 ng/g in ng/g in cereals, meat, eggs, milk, vegetables, and fruits, respectively. The overall average recoveries at three spiking levels of the 81 antibiotics (5, 25, and 50 ng/g dry weight) were 82 ± 26, 77 ± 26, 70 ± 34, 69 ± 31, 73 ± 29, and 62 ± 37% in cereals, meat, eggs, milk, vegetables, and fruits, respectively. The method was then applied to the analysis of the targets in the collected wheat flour, mutton, chicken egg, boxed milk, cabbage, and banana samples, with the total concentration of the antibiotics detected being 4.4, 2.3, 36, 5.5, 2.7, and 14 ng/g, respectively. This work suggests that the developed method provides a time- and cost-effective method to identify and quantify antibiotic residues in common food products.

Honeydew honey, due to its higher antibacterial and antioxidant activity in comparison to blossom honeys, is in high demand and of interest to consumers. Although a differentiation of blossom honeys from honeydew honeys by way of electrical conductivity is given in many cases, criteria for a differentiation of individual honeydew honeys, such as spruce, fir, and pine, however did not exist. For this reason, 93 authentic honeydew honeys and 63 non-honeydew honeys [35 blossom and 28 nectar-honeydew (mixed)] from 13 different botanical origins were collected within the framework of the current study, and their electrical conductivity and phenolic and sugar profiles were investigated. Results showed that the higher electrical conductivity (≥0.80 mS/cm), the higher protocatechuic acid content (≥3.5 mg/kg), and the higher percentage of the oligosaccharide content (≥120 mg/g) were suitable parameters for the differentiation of authentic coniferous honeydew honeys from non-honeydew honeys; a differentiation. A differentiation of the spruce, fir, and pine honeydew honeys however could not be reached. Through the analysis of 32 carbohydrates (2 mono-, 7 di-, 10 tri-, and 13 higher oligosaccharides) in only one run by high-performance liquid chromatography equipped with an evaporative light scattering detector, marker substances can now be utilized for the classification of individual honeydew honeys. Sugar marker compounds such as α,α-trehalose, melezitose, theanderose, nystose, or maltotetraose in honeydew honeys in combination with chemometrics highlighted the good capability of sugar profiles to discriminate the honeydew honeys both from the non-honeydew honeys and from each other. All in all, a 96.75% correct classification of all studied 156 honey samples was achieved by sugar marker compounds.

An effective and sensitive method for the determination of isopyrazam (IZM) isomers (syn-IZM and anti-IZM) and their metabolites (syn545364 and syn545449) in tomato and soil by ultraperformance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) was developed in the present study. The method showed excellent linearities (R2 = 0.999) at 0.005-5 mg/L. The recoveries were 92.0-107%, and the relative standard deviation (RSD) values were lower than 9.40% in tomato and soil matrices at 0.01, 0.1, and 10 mg/kg. The limits of detection (LODs) of the four compounds ranged from 6.88 × 10-5 to 2.70 × 10-4 mg/kg, while the limits of quantification (LOQs) ranged from 2.20 × 10-4 to 9.20 × 10-4 mg/kg. The storage stability test results showed that syn-IZM, anti-IZM, syn545449, and syn545364 were stable in tomato at -20 °C within 36 weeks, and the maximum degradation rates were 16.0, 12.0, 7.10, and 12.0%, respectively. The field dissipation test results showed that the half-lives of syn-IZM in tomato and soil were 2.60-10.2 and 13.6-33.0 days, respectively, while the half-lives of anti-IZM in soil were 21.7-46.2 days, and no residues of anti-IZM were detected in tomato. The terminal residue test results showed that the residue of syn-IZM and anti-IZM in tomato ranged from

Four difenoconazole stereoisomers were well separated on a Superchiral S-OX column. The absolute configurations of the four stereoisomers of difenoconazole eluted in an orderly fashion with the chiral column were confirmed as (2S,4S), (2S,4R), (2R,4R), and (2R,4S)-difenoconazole, respectively, by single-crystal X-ray diffraction. For the first time, a simple and efficient trace detection method for the determination of residues of the four stereoisomers of difenoconazole in a plant sample by HPLC-MS/MS was developed. The mean recoveries were 78.23-104.38% with RSDs of 0.33-9.95%. The limits of detection for the four difenoconazole enantiomers were 0.0002-0.0004 mg/kg, and the limits of quantitation were 0.0044-0.011 mg/kg in citrus leaves and whole fruits. There was no obvious enantioselectivity upon degradation of the four stereoisomers in citrus leaves and whole fruits in Hunan and Guizhou. In Guangzhou, the rate of degradation of (2R,4R)-difenoconazole was the slowest among the four stereoisomers of difenoconazole.

A zero-background method based on surface-enhanced Raman scattering (SERS) was developed for the rapid determination of cymoxanil residue in food. Because of the influence of complex matrices, conventional Raman spectroscopy has multiple peaks that overlap with those of target molecules, which makes qualitative and quantitative detection difficult. However, the cyano group (C≡N) of cymoxanil after ultraviolet irradiation has a special characteristic peak in the Raman-silent region (1800-2800 cm-1), which eliminates the possible background interference. The intensity of the characteristic peak at 2130 cm-1 exhibited a good linear relationship (R2 = 0.9907) with the concentration of cymoxanil in the range of 1.0-50.0 mg/L, whose limit of detection was 0.5 mg/L. The novel method was also applied to the detection of cymoxanil residue in real samples such as cucumber and grape, and the results were in good agreement with those from high-performance liquid chromatography analysis. This revealed that the SERS method has great potential in the detection of cymoxanil in fruits and vegetables. Moreover, ultraperformance liquid chromatography-quadrupole-time-of-flight-mass spectrometry (UPLC-QTOF/MS) was adopted to identify the photoproducts of cymoxanil. The photolysis mechanism was explored by SERS and the UPLC-QTOF/MS technique, which provided basic information on photodegradation of cymoxanil.

Heterocyclic aromatic amines (HAAs) are potential human mutagens and carcinogens mainly generated in heat-treated meat. In this work, a broad-spectrum HAAs antibody was prepared and used to develop an indirect competitive ELISA (ic-ELISA) for simultaneous determination of eight HAAs, including 2-amino-3-methylimidazo[4,5-f]quinoline (IQ), 2-amino-3,4-dimethylimidazo[4,5-f] quinoline (MeIQ), 2-amino-3-methylimidazo[4,5-f]quinoxaline (IQx), 2-amino-3,8-dimethylimidazo[4,5-f]quinoxaline (MeIQx), 2-amino-3,4,8-trimethylimidazo[4,5-f]quinoxaline (4,8-DiMeIQx), 2-amino-3,7,8-trimethylimidazo[4,5-f]quinoxaline (7,8-DiMeIQx), 2-amino-3,4,7,8-tetramethylimidazo[4,5-f]quinoxaline (4,7,8-TriMeIQx), and 2-amino-1-methyl-6-phenylimidazo[4,5-b]pyridine (PhIP) in grilled and fried meat samples. The limit of detection (LOD, calculated as IC10) and 50% inhibition concentration (IC50) of ic-ELISA were 5.29 μg/L and 99.08 μg/L, respectively. The detection results of this ic-ELISA were in good agreement with the detection results of UPLC-MS/MS in real samples, which indicated that this ic-ELISA can be applied to detect the total content of eight HAAs in heat processed meat. Use of a broad-spectrum antibody is an efficient strategy in developing immunoassay for simultaneous measuring food risk factors with similar structure.

The aim of this study was to monitor the degradation of three insecticides licensed for the control of cabbage moths during the 14-day fermentation period of sauerkraut samples. The hypothesis of this study is that the different sauerkraut fermentation processes could affect the degradation of applied insecticides. For this purpose, the fresh cabbage leaves contaminated with (λ-cyhalothrin, malathion, and chlorpyrifos-methyl) were left for fermentation with and without (natural) starter addition (Lactobacillus plantarum 112), and vacuum-packed as a control under laboratory conditions. The pH values and microbial growth were periodically monitored in sauerkraut samples during the fermentation period. During this time, the insecticide residues were determined in control and treatment samples using LC-MS-MS. In control samples, the degradation of chlorpyrifos-methyl and malathion was higher with rates of 69 and 98%, respectively, compared with the sauerkraut samples (12 and 59%; 31 and 34%, respectively) 14 days after the insecticide application. At the end of fermentation (14 d), no significant reduction in λ-cyhalothrin was detected in both treatments and control (13-19% reduction). The current study demonstrated that the presence of the lactic acid bacteria in the sauerkraut fermentation accelerated pH decline (below 4.0), and these fermentation conditions probably decelerated the degradation of malathion and chlorpyrifos-methyl. The results showed that the stability of different insecticides varied during the same fermentation process.

Conventional methods for detecting fungal contamination are generally time-consuming and sample-destructive, making them impossible for large-scale nondestructive detection and real-time analysis. Therefore, the potential of headspace-gas chromatography-ion mobility spectrometry (HS-GC-IMS) was examined for the rapid determination of fungal infection on wheat samples in a rapid and nondestructive manner. In addition, the validation experiment of detecting the percent A. flavus infection presented in simulated field samples was carried out. Because the dual separation of HS-GC-IMS could generate massive amounts of three-dimensional data, proper chemometric processing was required. In this study, two chemometric strategies including: (i) nontargeted spectral fingerprinting and (ii) targeted specific markers were introduced to evaluate the performances of classification and prediction models. Results showed that satisfying results for the differentiation of fungal species were obtained based on both strategies (>80%) by the genetic algorithm optimized support vector machine (GA-SVM), and better values were obtained based on the first strategy (100%). Likewise, the GA-SVM model based on the first strategy achieved the best prediction performances (R2 = 0.979-0.998) of colony counts in fungal infected samples. The results of validation experiment showed that GA-SVM models based on the first strategy could still provide satisfactory classification (86.67%) and prediction (R2 = 0.889) performances for percent A. flavus infection presented in simulated field samples at day 4. This study indicated the feasibility of HS-GC-IMS-based approaches for the early detection of fungal contamination in wheat kernels.

A feeding study was performed to examine the bioaccumulation of per- and polyfluoroalkyl substances (PFAS) in laying hens' tissues and plasma and feed-to-egg transfer rates and half-lives. A 25 day exposure was followed by a 42 day depuration period. A target analysis revealed substantial amounts of the precursors N-methyl and N-ethyl perfluorooctane sulfonamidoacetic acid (Me- and EtFOSAA), perfluorooctane sulfonamidoacetic acid (FOSAA), and perfluorooctane sulfonamide (FOSA). In tissues and eggs, the highest bioaccumulation was found for PFHxS, PFHpS, PFOS, and PFOA. Low levels of PFHxS (all samples), PFOS, and FOSAA (in yolk) were measurable even after the depuration period. The egg elimination half-lives of PFOS and aforementioned precursors were estimated to be 4.3 days, while the transfer rates of PFOS and all precursors taken together were 0.99. The transfer rate of PFOA was around 0.49. PFHxS and PFHpS showed apparent transfer rates of >100%, which is hypothesized to indicate the presence of precursors.

Mercury, as a global toxic pollutant, is easy to be accumulated in aquatic products and poses a great threat to human health. In this work, we proposed a mix-to-read, label-free, and robust assay for detecting mercury pollution in aquatic products by engineering a ratiometric-enhanced G-quadruplex probe. The transformation from the G-quadruplex to a hairpin-like structure allows us to confer a ratiometric and leveraged response to Hg2+, amplifying the signal-to-background ratio for Hg2+ detection. Hg2+ response was further improved by screening parallel- and antiparallel-, single-, and multiple-stranded G-quadruplex structures. Compared to the common aptamer probes, the ratiometric-enhanced G-quadruplex probe increased the sensitivity for Hg2+ detection by 4.7 times. This proposed sensing system allowed a simple and one-tube homogenous detection of Hg2+ at room temperature using a single unlabeled DNA sequence. Its application for Hg2+ detection in fish and shrimp conferred satisfactory recovery rates ranging from 98.5 to 105.9%. The label-free and mix-to-read assay is promising for the onsite detection of mercury pollution and facilitating food safety of aquatic products.

Citrinin (CIT), a known nephrotoxic mycotoxin, is mainly produced by Penicillium, Aspergillus, and Monascus species. It is a natural contaminant in cereal grains, foods, and feedstuff. Liupao tea (or Liubao tea) is a typical Chinese dark tea obtained via indigenous tea fermentation facilitated by microorganisms. Certain fungi present in Liupao tea that may produce CIT are a potential threat to consumer health. In the present study, various potential toxigenic mycoflora and the natural occurrence of CIT in Liupao tea were surveyed via the culture-dependent method, high performance liquid chromatography-fluorescence detection (HPLC-FLD), and ultrahigh performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS). Total mold counts ranged from 3.5 × 102 CFU/g to 2.1 × 106 CFU/g tea in 28 tea samples. A total of 218 fungal isolates belonging to five genera and 23 species were identified. Some of these strains, such as Aspergillus ochraceus, Aspergillus oryzae, Penicillium citrinum, and Penicillium chrysogenum, may potentially be a CIT-producing species. In addition, 32.7% of 113 Liupao tea samples were contaminated with CIT at concentrations ranging from 7.8 to 206.1 μg/kg. These CIT concentrations in Liupao tea are chiefly attributed to climatic conditions and water activity during storage that favor fungal proliferation and mycotoxin production. However, CIT could not be detected in Liupao tea stored for over 10 years. These results provide the first information about the potential toxigenic mycoflora and natural occurrence of CIT in Liupao tea. Therefore, storage conditions and fungal community must be monitored to ensure the quality of Liupao tea.

3-Chloro-1,2-propandiol (3-MCPD) dipalmitate is one of the major 3-MCPD esters formed during food processing. In this single-dose study, the metabonomic profile changes in the 48 h after orally administrated 3-MCPD dipalmitate at 1600 mg/kg BW to Sprague-Dawley (SD) rats were determined with liquid chromatography (LC) coupled with mass spectrometry (MS) system. The chemical structures of 12 potential biomarkers for 3-MCPD dipalmitate exposures early detection were detected and tentatively identified from the plasma of SD rats, including indoxyl sulfate, phenol sulfate, p-cresol sulfate, 2-phenylethanol glucuronide, p-cresol glucuronide, p-cresol, allantoin, phenylacetylglycine, pyrocatechol sulfate, phenyllactic acid, 5-hydroxyindoleacetic acid, and creatinine. Taking into account the metabolites identified from SD rats' kidney, liver, testes, and spleen samples, 3-MCPD dipalmitate might potentially disturb the phenylalanine, tryptophan, tyrosine, glycine, fatty acid, and purine metabolisms. The results suggested that the 12 plasma metabolites could be potentially applied in detecting the early exposures of 3-MCPD esters.

Food consumption has been identified as a major pathway for human exposure to short-chain chlorinated paraffins (SCCPs) and medium-chain chlorinated paraffins (MCCPs), but evaluations of SCCP and MCCP intake from major dietary sources are limited. We used the sixth Chinese Total Diet Study to perform a comprehensive investigation of SCCPs and MCCPs in cereals, vegetables, potatoes, legumes, eggs, milk, meats, and aquatic foods from nine southern provinces. The geographical distribution of CP concentrations showed higher levels in Jiangsu, Hubei, and Zhejiang provinces. The CP concentrations in most animal-origin foods were higher than those in foods of plant origin. The total estimated daily intakes (EDIs) of SCCPs and MCCPs, with average values of 7.0 × 102 and 4.7 × 102 ng kg-1 day-1, respectively, were mostly contributed by cereals, vegetables, and meats. Risk assessment indicated the EDIs of CPs posed no significant risk to residents in South China.

Antibiotic abuse in agricultural products leads to serious food safety issues. To this end, we proposed a mix-and-read and enzyme-free amplified assay for antibiotics based on a dual triple helix-aptamer probe, potentially applicable for on-site monitoring of antibiotic residues. A dual triple helix-aptamer probe can leverage the response toward target molecules without enzyme-based amplification, rendering it sensitive and robust for profiling target molecules. The proposed assay allowed mix-and-read detection of chloramphenicol with a detection limit of 0.18 nM. Besides, it accommodated for specifically resolving chloramphenicol among other antibiotics. Chloramphenicol residual in aquatic products in fish and milk can be precisely determined. Thus, the aptamer probe deems to enrich the toolbox for managing antibiotic use.

An untargeted foodomics strategy based on ultra-high-performance liquid chromatography coupled with quadrupole orbitrap and chemometrics was used to observe subtle differences in the molecule profiles of raw milk from different animal species (cow milk, goat milk, and water buffalo milk), which could prevent the fraud activities in the dairy industry. In data-dependent acquisition (DIA), spectra for all precursor ions facilitated the comprehensive identification of unknown compounds in untargeted foodomics. Chemometrics techniques were used to analyze large amounts of complex data to observe the separation of different sample groups and find the potential markers of sample groups. Finally, five markers were putatively identified by the potential marker identification workflow. The quantification results showed that β-carotene was found only in cow milk; ergocalciferol was found only in water buffalo milk; and the contents of nonanoic acid, decanoic acid, and octanoic acid were higher in goat milk than those in cow milk and water buffalo milk. The quantification of β-carotene enabled the detection of cow milk with a sensitivity threshold of 5% (w/w). This work provided an efficient approach for the discrimination of cow milk, goat milk, and water buffalo milk. Compared with proteomics and genomics, the simpler analytical procedures, lower costs, and higher speed of this work make it of great benefit for routine operations.

The addition of cheap and also readily available raw materials, such as peanut powder, to visually and chemically similar matrices is a common problem in the food industry. When peanuts are used as an adulterant, there is an additional risk of potential health hazard to consumers as a result of allergy-induced anaphylaxis. In this study, different series of peanut admixtures to visually similar food products, such as powdered hazelnuts, almonds, and walnuts, were prepared and analyzed by 1H nuclear magnetic resonance (NMR) spectroscopy. For identification, an isolated signal at 3.05 ppm in the 1H NMR spectrum of polar peanut extract was used as an indicator of peanut adulteration. The chemical marker was identified as (2S,4R)-N-methyl-4-hydroxy-l-proline by resynthesis of the compound and used as an internal standard. The signal-to-noise ratio and the integral of the signal of the marker can both be used to detect peanut impurities. Overall, an approximate limit of detection of 4% admixtures of peanut in various food products was determined using a 400 MHz spectrometer. With regard to food fraud, we present a viable screening method for detection of economic-relevant peanut adulteration.

Ochratoxin A (OTA), a common mycotoxin, has attracted great concern as many foodstuffs can suffer from OTA contamination; OTA causes harmful effects on human and animals. Rapid and sensitive detection of OTA is demanded in many fields for agricultural product quality, food safety, and health. Aptamer fluorescence polarization/anisotropy (FP/FA) assays integrate advantages of nucleic acid aptamers (e.g., easy preparation, high stability, and low cost) and FP/FA analysis (e.g., high sensitivity, rapidity, simplicity, and robustness). Here, we report the preparation of lissamine rhodamine B labeled OTA and developed competitive aptamer fluorescence anisotropy (FA) assays for OTA with signal-off or signal-on responses by using this fluorescently labeled probe. In the signal-off FA assay, the binding between the fluorescent probe and aptamer gave a large FA signal due to molecular volume increase, and the fluorescent probe was displaced from the aptamer in the presence of OTA target, causing FA to decrease. To further enhance the FA change in the signal-off assay, large-sized streptavidin was conjugated on the aptamer, and this assay allowed for a detection limit of 2.5 nM and a more remarkable FA decrease. Furthermore, we found that the fluorescent probe could interact with Tween 20, which caused the fluorescent probe to show a higher FA value than that of the aptamer-fluorescent probe complex. A signal-on FA assay was achieved in the binding buffer containing 0.1% Tween 20, with a detection limit of 10 nM. Signal-off and signal-on FA methods both were selective and enabled detection of OTA spiked in red wine samples, showing capability for target analysis in complex sample matrix.

Algae products are attracting growing interest due to their pleasant taste and their high contents in protein, essential amino acids, vitamins, and minerals. Specifically, spirulina products are widely promoted for their high vitamin B12 content. So far, knowledge regarding the contamination with cyanotoxins, heavy metals, pesticides, or polycyclic aromatic hydrocarbons (PAHs) is scarce, although some studies reported high contaminant levels in spirulina products. The regular intake of spirulina, and very likely other algae products as well, as a dietary supplement in the gram range demands a closer monitoring of potentially harmful constituents.

Since coffee is a significant contributor to the consumption of acrylamide, its reduction is required. Acrylamide is produced during the roasting of coffee beans, but the roasting process is an essential step in determining the taste of coffee. Acrylamide content in coffee has been suggested to decrease by reacting with proteins and/or other substances during storage, but details are unknown. Investigation of acrylamide adducts may contribute to a strategy for acrylamide reduction in coffee. In this study, a stable isotope labeling technique, combined with high-resolution mass spectrometry, allows the identification of acrylamide adducts (3-hydroxypyridine-acrylamide and pyridine-acrylamide) in canned milk coffee. Other acrylamide adducts derived from milk coffee proteins, Lys-acrylic acid and CysSO2-acrylic acid, were identified. During a 4-month storage period, the formation of these four adducts was found to reduce the total content of acrylamide by 75.3% in canned milk coffee. Therefore, endogenous proteins can be used in acrylamide reduction.

Excessive use of antibiotics in aquatic products is a serious problem for food safety and human health, and on-site detection of antibiotics is highly demanded. Herein, we proposed multivalence aptamer probes, allowing sensitive, label-free, and homogeneous detection of antibiotics in different aquatic products. Compared to commonly used aptamers, multivalence aptamer probes can provide multiple binding sites and a higher affinity for target molecules, and the iterative binding on different binding sites contributes to an amplified recognition effect, sharply increasing the response and sensitivity of aptamer probes. The 2-valence aptamer probes conferred a limit of detection of 0.097 nM for kanamycin detection, where it is estimated that their sensitivity is enhanced 12 times compared to 1-valence aptamer probes. Meanwhile, multivalence aptamer probes allowed us to specifically identify kanamycin among other antibiotics. It could detect kanamycin residual in aquatic products including river eel and puffer fish, as well as tap water with high precision. A multivalence design strategy of aptamer probes would significantly improve the detection performance of aptamers, facilitating the translation of aptamer for food safety control.

A feeding study was carried out to investigate the kinetics in cow milk of the 17 polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), the 12 dioxin-like polychlorinated biphenyls (DL-PCBs), and the 6 non-dioxin-like PCBs (NDL-PCBs) regulated by the European (EU) legislation. A fortified ration (ΣPCDD/Fs and DL-PCBs: 24.68 ng TEQ/day/cow; ΣNDL-PCBs: 163.99 μg/day/cow) was given to the animals for 49 days, followed by 42 days on clean feed. EU maximum limit for TEQPCDD/F+DL-PCB was exceeded in milk after 1 week of exposure, while for ΣNDL-PCBs, after 5 weeks. Milk compliance was restored after 1 week on clean feed, but to return to the basal TEQPCDD/F+DL-PCB it took 42 days. At the end of the study, ΣNDL-PCBs had not yet reached the basal level. The carryover rate of ΣNDL-PCBs was 25.4%, while the carryover rate of TEQPCDD/F+DL-PCB was 36.9%. The latter was mainly affected by the 12 congeners contributing most to the toxic equivalent (TEQ) level, explaining the fast overcome of the maximum limit in milk.

The growth conditions and age of Panax ginseng are vital for determining the quality of the ginseng plant. However, the considerable difference in price according to the cultivation method and period of P. ginseng leads to its adulteration in the trade market. We herein focused on ginseng peptides and the possibility of these peptides to be used as biomarker(s) for discrimination of P. ginseng. We applied an ultraperformance liquid chromatography-high resolution mass spectrometry-based peptidomics approach to characterize ginseng peptides and discover novel peptide biomarkers for authentication of mountain-cultivated ginseng (MCG). We identified 52 high-confidence peptides and screened 20 characteristic peptides differentially expressed between MCG and cultivated ginseng (CG). Intriguingly, 6 differential peptides were expressed significantly in MCG and originated from dehydrins that accumulated during cold or drought conditions. In addition, 14 other differential peptides that were significantly expressed in CG derived from ginseng major protein, an essential protein for nitrogen storage. These biological associations confirmed the reliability and credibility of the differential peptides. Additionally, we determined several robust peptide biomarkers for discrimination of MCG through a precise selection process. These findings demonstrate the potential of peptide biomarkers for identification and quality control of P. ginseng in addition to ginsenoside analysis.

A novel microbial consortium (NZDC-6) was screened and characterized to detoxify the estrogenic mycotoxin zearalenone (ZEA), which commonly contaminates maize and is a major threat to food and health security. We found NZDC-6 to be thermophilic and highly effective, with a 90.3% ZEA degradation ratio at an optimum temperature of 60 °C. NZDC-6 was also effective at degrading the more estrogenic ZEA cognates, α-zearalenol (α-ZAL) and β-zearalenol (β-ZAL), with >90% degradation ratios. To evaluate a practical application, ZEA-contaminated corncobs were treated with NZDC-6 via semisolid fermentation. Measurements of physicochemical parameters and 16S microbial diversity and redundancy analysis (RDA) indicated that ZEA removal was most efficient at a low corncob solid content (< 5%), as a high solid content overwhelmed the microbial metabolic load, leading to increased dissolved oxygen and lowered pH. Our results demonstrate that the control of environmental variables is crucial for effective ZEA microbial removal in practical applications.

Organically farmed rice is believed to be healthier, safer, and eco-friendlier than its conventionally farmed counterparts and sells for a premium price in global markets. Deliberate mislabeling of organic rice has become a critical consumer concern in China and elsewhere, and there is an increased risk of buying fraudulent organic rice in the market place. In this study, stable isotopic and multielemental analysis combined with chemometrics was used to differentiate organically farmed rice from green and conventional rice in a 4-year experimental field trial from 2014 to 2017. A total of 108 rice samples and their associated soils were collected during the study from three farming (fertilization) systems to investigate whether there are long-term changes in the rice farming classification accuracy from climate effects. Stable carbon and nitrogen isotopic ratios (i.e., δ13C and δ15N) and 27 elemental contents (e.g., Na, K, Ca, Fe, and Zn) of rice and soil samples were determined and then evaluated using statistical analysis [i.e., one-way analysis of variance, multivariable correlation analysis, and modeling of partial least-squares discriminant analysis]. Although δ15N values can be an effective indicator for organic rice authentication during one crop rotation, both δ13C and δ15N values of rice were easily affected by rice cultivar and interannual soil fertilization and localized agroclimatic variations. These two isotopes were not able to separate organic rice from green and conventional rice accurately. Elemental contents of green and conventional rice (especially K and Ca) were found at higher levels due to the abundant application of synthetic fertilizers (e.g., KNO3, KH2PO4, and CaHPO4), unlike organically farmed rice, which primarily used animal manure and composts. Partial least-squares discriminant analysis modeling combined isotopic and elemental signatures to correctly differentiate organic rice from green and conventional counterparts, with an accuracy up to 100% over the 4-year study. Therefore, this multi-isotope and -element strategy proposes a more rigorous, alternative tool to combat fraudulent mislabeling of organic rice, increasing the trust of organically labeled rice products and supporting the integrity of the organic sector worldwide.

Biogenic amines (BAs) are low molecular weight organic bases. BAs occurring naturally in living organisms are responsible for a number of vital functions, including (in humans) secretion of gastric acids, controlling body temperature, differentiation and growth of cells, immune reactions, and brain activity. However, if oversupplied with food, BAs may cause food poisoning and produce undesirable effects. Nine BAs and eight free amino acids (FAAs) were determined in 85 samples of 19 different varieties of fermented vegetables available on the Polish retail market. Both BA and FAA levels differed significantly among various varieties of the studied fermented vegetables. Averages for the sum of all tested BAs ranged from 30.29 ± 16.43 mg·kg-1 in fermented olives to 612.1 ± 359.33 mg·kg-1 in fermented Brussels sprout. BA profiles were dominated by putrescine (42%), tyramine (20%), cadaverine (18%), and histamine (8%); jointly, the four amines amounted to 88% of all nine studied BAs. The combined level of the latter four BAs was calculated for each vegetable variety as the so-called BA index (BAI). On that basis, the risk of BA-related adverse health effects has been assessed as high/medium/low in 6/3/10 of all 19 studied varieties of fermented vegetables. Brussels sprout and broccoli turned out to be the most risky vegetables from that point of view (BAI above 400 mg·kg-1). FAA levels ranged from 54.8 ± 12.76 (fermented olives) to 3917.42 ± 1528.73 mg·kg-1 (fermented garlic). The high content of FAAs may increase the risk of forming toxic amounts of BAs, depending on characteristics of the current and added microflora as well as on environmental and technological conditions the product is subjected to.

A UHPLC-ESI-MS/MS method was developed for the determination of 36 phenolic compounds in paprika. The proposed method showed good method performance with limits of quantitation between 0.03 - 50 µg/L for 16 compounds, and between 50 µg/L and 1 mg/L for 12 compounds. Good linearity (r2 > 0.995), run-to-run and day-to-day precisions (%RSD values