Fate of pesticide residues in beer and its by-products.

Sustainable beer production requires a comprehensive assessment of potential hazards such as pesticides in both the finished product and waste streams, as these streams can be used to create high-value by-products. This study presents the tracking of 13 fungicides (azoxystrobin, boscalid, epoxiconazole, fenpropidin, fenpropimorph, fluquiconazole, flutriafol, fluxapyroxad, kresoxym-methyl, spiroxamine, propiconazole, prothioconazole-desthio, and tebuconazole), two insecticides (chlorpyrifos-methyl and deltamethrin), one herbicide (glyphosate), and one growth regulator (mepiquat) through the beer brewing process. Field-treated rye, wheat, and barley samples containing pesticide residues were used as adjunct during brewing. Samples of the beer as well as the by-products (spent grain, spent hops, trub and spent yeast) were collected and extracted with a modified QuEChERS method for pesticide residues analysis using GC-MS/MS and LC-MS/MS. Results show that an average of 58% of pesticide residues are retrieved in the by-products with the highest fraction (53%) recovered in the spent grain, 4% in trub, 1% in spent hops, no residues detected in spent yeast and 9% in the beer. This is consistent with these nonpolar pesticides tending to remain adsorbed to the spent grain during brewing. Glyphosate and mepiquat, the most polar pesticides included in this study, showed a different behavior, with the largest fraction (>80%) being retrieved in sweet wort and transferred to the beer. Processing factors were generated for each pesticide from the adjunct to the beer and to the four by-products.

Synergistic effect of the coculture of Leuconostoc pseudomesenteroides and Lactococcus lactis, isolated from honeybees, on the generation of plant-based dairy alternatives based on soy, pea, oat, and potato drinks.

The production of plant-based dairy alternatives has been majorly focused on the improvement of sensorial, technological and nutritional properties, to be able to mimic and replace milk-based fermented products. The presence of off-flavours and antinutrients, the lack of production of dairy-like flavours or the metabolic inaccessibility of plant proteins are some of the challenges to overcome to generate plant-based dairy alternatives. However, in the present study, it is demonstrated how the synergistic effect of two LAB strains, when cocultured, can simultaneously solve those challenges when fermenting in four different plant-based raw materials: soy, pea, oat, and potato drinks (SPOP). The fermentation was performed through the mono- and co-culture of the two LAB strains isolated from Apis mellifera (honeybee): Leuconostoc pseudomesenteroides NFICC 2004 and Lactococcus lactis NFICC 2005. Firstly, the coculture of both strains demonstrated to increase the acidification rate of the four plant matrices. Moreover, L. pseudomesenteroides (LP) demonstrated to in situ produce high concentrations of mannitol when fructose was present as C-source. Furthermore, L. pseudomesenteroides, which encoded for PII-proteinase, demonstrated to break down SPOP proteins, releasing free amino acids that were used by L.lactis (LL) for growth and metabolism. Lastly, the analysis of their co-metabolic volatile performance showed the principal ability of removal of the main off-flavours found in SPOP, such as hexanal, 1-octen-3-ol, 2-pentylfuran, pentanal, octanal, heptanal, and nonanal, mainly led by L. pseudomesenteroides, as well as the production of dairy-like flavours, such as diacetyl and 3-methyl-1-butanol, triggered by L. lactis metabolism. Overall, these findings endorsed the use of honeybee isolated strains as starter cultures, demonstrated the potential of coupling genotypes and phenotypes of multiple strains to improve the organoleptic properties suggesting a potential of combining plant-based matrices for the generation of future high-quality plant-based dairy alternatives.

Development of Photonic Multi-Sensing Systems Based on Molecular Gates Biorecognition and Plasmonic Sensors: The PHOTONGATE Project.

This paper presents the concept of a novel adaptable sensing solution currently being developed under the EU Commission-founded PHOTONGATE project. This concept will allow for the quantification of multiple analytes of the same or different nature (chemicals, metals, bacteria, etc.) in a single test with levels of sensitivity and selectivity at/or over those offered by current solutions. PHOTONGATE relies on two core technologies: a biochemical technology (molecular gates), which will confer the specificity and, therefore, the capability to be adaptable to the analyte of interest, and which, combined with porous substrates, will increase the sensitivity, and a photonic technology based on localized surface plasmonic resonance (LSPR) structures that serve as transducers for light interaction. Both technologies are in the micron range, facilitating the integration of multiple sensors within a small area (mm2). The concept will be developed for its application in health diagnosis and food safety sectors. It is thought of as an easy-to-use modular concept, which will consist of the sensing module, mainly of a microfluidics cartridge that will house the photonic sensor, and a platform for fluidic handling, optical interrogation, and signal processing. The platform will include a new optical concept, which is fully European Union Made, avoiding optical fibers and expensive optical components.

Simultaneous determination of heterocyclic aromatic amines and N-nitrosamines in fried bacon cubes and slices using LC-(ESI/APCI)-MS/MS.

Bacon manufacturing involves several processing steps including nitrite curing, followed by cooking processes, typically frying. During these processes, harmful processing contaminants such as N-nitrosamines (NAs) and heterocyclic aromatic amines (HAAs) can be formed. Consequently, we developed and validated a multi-class method for quantification of the most frequently reported HAAs and NAs in fried bacon. Satisfactory repeatability and reproducibility with limits of quantification between 0.1 and 0.5 ng g-1 for most of the compounds were achieved. Quantification in pan-fried bacon cubes and slices revealed generally low levels of individual HAAs (≤1.5 ng g-1), except in ready-to-eat bacon (0.9-2.9 ng g-1). Differences in amounts of individual HAAs were observed in cubes and slices, most likely due to meat thickness. Among volatile NAs (VNAs), only N-nitrosopiperidine (NPIP), N-nitrosopyrolidine (NPYR), and N-nitrosodibutylamine (NDBA) were found at generally low concentrations (≤5 ng g-1). In contrast, non-volatile NAs (NVNAs) were present in all tested samples at considerably higher amounts, for example, N-nitroso-thiazolidine-4-carboxylic acid (NTCA) at 12-77 ng g-1. N-nitrosodimethylamine (NDMA), N-nitrosodiethylamine (NDEA), N-nitrosodipropylamine (NDPA) were not detected in any samples. Statistical evaluation and principal component analysis revealed some differences among tested samples. Dietary exposure estimation of the Danish population to HAAs and NAs showed the highest exposure in the teenage group (10-17 years).

Detection of Nitrated, Oxygenated and Hydrogenated Polycyclic Aromatic Compounds in Smoked Fish and Meat Products.

Polycyclic aromatic hydrocarbons (PAHs) are present in smoked food products. More toxic nitrated (NPAH) and oxygenated (OPAH) PAHs derivatives are found concomitantly to PAHs and are therefore believed to be found in smoked food products. However, only a few PAH analyses on food include these derivatives. We adjusted and successfully validated a GC-QTOFMS method including 13 NPAHs and 2 OPAHs as well as the 4 regulated PAHs for analysis of 14 smoked (13 fish and one bacon) and one pan fried fish samples.OPAHs were detected in the highest concentrations in 13 of 15 samples. Non-target screening revealed the presence of an additional four OPAHs and two methylated PAHs. Future food analysis should, based on these results, focus on PAH and oxygenated derivatives.

Analysis of four polycyclic aromatic hydrocarbons in plant-based food supplements-results of a collaborative study.

The determination of carcinogenic polycyclic aromatic hydrocarbons (PAHs) in food supplements is challenging, especially due to the presence of other e.g. heterogeneous PAH-like compounds in the matrix. A collaborative study with 12 participants was conducted in order to assess performance characteristics of a fast method intended to analyse the four regulated PAHs (PAH 4) benzo[b]fluoranthene [BbF], benz[a]anthracene [BaA], chrysene [CHR] and benzo[a]pyrene [BaP] in five different plant-based food supplements in the form of capsules, powder, and tablets. The principle of the method includes the extraction of PAHs with ethyl acetate: cyclohexane followed by a two-step SPE cleanup and final analysis by GC-MS or LC-FLD. The regulated maximum level for BaP is 10 µg/kg and, for the PAH 4, 50 µg/kg. Accordingly, the method was validated for the regulated PAH 4 analytically challenging concentration range from 2.5 µg/kg to 6.9 µg/kg. The performance criteria for the method set in European Regulation No 333/2007 for the overall repeatability, reproducibility (HorRat values below 2), and recovery (range 50-120%) were fulfilled. Based on the statistical evaluation of the results, it was concluded that the method is a suitable alternative to existing methods and should be studied for additional matrices.

Positive Influences of Ohmicsonication on Phytochemical Profile and Storage Stability of Not-from-Concentrate Mango Juice.

Processing technique and storage conditions are the main factors that affect the phytochemical profile of Not-from-Concentrate (NFC) juice, which could decrease the nutritional and bioactive properties of the corresponding juice. The aim of this study was to evaluate the quality changes that occurred in NFC mango juice after Ohmicsonication (OS) and during storage in comparison to other processing methods such as sonication (S), thermosonication (TS), ohmic heating (OH), and conventional heating (CH). Quality attributes such as polyphenoloxidase (PPO) and pectinmethylesterase (PME) activities, ascorbic acid and hydroxymethyl furfural (HMF) contents, total phenolics, total flavonoids, total carotenoids, electric conductivity, color values and microbial load (total plate count, mold, yeast, and psychrophilic bacteria) were examined. OS and OH treatments demonstrated the highest inactivation of PPO (100%), while CH and TS displaying inhibitions 89% and 90%, respectively and only S treatment exhibited insufficient inactivation of both PPO and microbial load. However, the inhibition of PME followed the order OS (96.5%) > OH (94.9%) > TS (92.5%) > CH (88.5%). The best treatment, with the highest retention of phytochemical contents (ascorbic acid, total carotenoids, antioxidant activity, total flavonoids, and total phenolic content) for NFC mango juice and during storage was obtained with OS treated samples compared to other treatments (in the order from the lowest to highest percentage, OS < OH < TS < CH). Consequently, the results indicated that OS could be applied as a new mild thermal treatment in the production of mango juice with improved quality properties of stored NFC mango juice.

Formation and mitigation of PAHs in barbecued meat - a review.

Polycyclic Aromatic Hydrocarbons (PAHs) are chemicals, which can occur in barbecued or grilled foods, and particularly in meats. They originate from incomplete combustion of the heat source, pyrolysis of organic compounds, or fat-induced flame formation. This review therefore summarizes relevant parameters for mitigation of especially carcinogenic PAHs in barbecued meat. Consumption of PAHs increases the risk of cancer, and thus the relevance for the mitigation of PAHs formation is very high for barbecued meat products. Parameters such as heat source, barbecue geometry, and meat type as well as marinating, adding spices, and other antioxidants reduce the final benzo[a]pyrene and PAHs concentrations and minimize the exposure. Overall, mitigation of carcinogenic PAHs from barbecuing includes removal of visual charring, reducing fat pyrolysis by minimizing dripping from the meat onto the heat source, the use of acidic marinades or choosing leaner cuts of meat. Estimation of human exposure to barbecued meat, includes several challenges such as substantial differences in barbecuing frequencies and practices, heat sources and meat types used for grilling.

Targeted and non-targeted unexpected food contaminants analysis by LC/HRMS: Feasibility study on rice.

A widely applicable analytical LC/HRMS method based on ion source optimization, data treatment optimization on rice matrix was developed. The effects of key parameters of ion source, and their interactions on ESI response were studied on HPLC-QTOF. Compared with center points, 40% and 20% increase of response factors in the positive and negative mode can be achieved by ion source optimization, respectively. Data processing strategies inspired from metabolomics and multi-targeted analysis were compared and developed using case and control rice samples. Highly automated workflow using XCMS achieved highest mass accuracy, highest detection rate of 96% for 5 µg/kg in a non-targeted way. A clear distinction between the control and contaminated samples by PCA and PLS-DA was also achieved by this workflow using XCMS, even for the concentration of 5 µg/kg.

Automated micro-solid-phase extraction clean-up of polycyclic aromatic hydrocarbons in food oils for analysis by gas chromatography-orbital ion trap mass spectrometry.

Food can contain unwanted compounds and need to be analyzed for compounds like carcinogenic polycyclic aromatic hydrocarbons to ensure consumer safety. The analytes need to be extracted from the sample matrix and cleaned-up to enable detection. However, established methods for clean-up are labor intensive and have a high expenditure on organic solvents. Here, we show a newly developed micro-solid-phase extraction cartridge method to automate the clean-up for analysis of polycyclic aromatic hydrocarbons in sunflower oil using gas chromatography with quadrupole-orbitrap mass spectrometry with a TriPlus autosampler. This automated micro-solid-phase extraction cartridge method needs only 4 µL of vegetable oil sample and requires only 360 µL acetonitrile for elution, and, therefore, it needs only small amounts of organic solvent. Two different micro-solid-phase extraction cartridge methods were developed, one using two commercially available cartridges with florisil and octadecylsilane/Z-Sep/CarbonX, and the other method using one commercially available cartridge with florisil followed by one self-made cartridge with octadecylsilane/Z-Sep. The latter method showed successful lipid removal and was further validated for 22 of 24 polycyclic aromatic hydrocarbon compounds in sunflower oil at a spiked level of 1090 µg/kg with recoveries ranging from 53 to 118% and relative standard deviation below 22%. This method shows promising short-time clean-up with low expenditure of solvents.

Dietary exposure to selected chemical contaminants in fish for the Danish population.

The exposure to selected chemical contaminants from fish has been calculated for the Danish population, both for adults (15-75 years of age) and children (4-14 years of age). The Danish mean consumption of fish is 21 g person-1 day-1 for adults and 12 g person-1 day-1 for children. Fish consumption is the main food group contributor for exposure to mercury and dioxins and dioxin-like polychlorinated biphenyls (PCDD/F and DL-PCB) for the Danish population. Comparison of the mean exposure with the TDI or TWI values shows for these substances as well as for perfluorooctane sulphuric acid (PFOS) that the exposure is below the TDI/TWI values. However, even without taking other food groups into account, PCDD/Fs and DL-PCB exposure is close to the actual TWI-value. Calculation of the Margin of Exposure (MOE) for the sum of hexabromocyclododecanes (HBCDD) and polycyclic aromatic hydrocarbons (PAHs) revealed fish consumption to be of low concern for the consumer health regarding these contaminants.

Impact of ohmicsonication treatment on pectinmethylesterase in not-from-concentrate orange juice.

The present study investigates the application of ohmicsonication (OS) as a new hurdle technology for pasteurization of Not-from-concentrate orange juice (NFCOJ). OS process parameters to inactivate pectinmethylesterase (PME) activity in NFCOJ were optimized using response surface methodology. The influence of Sonication (S), Thermosonication (TS), Ohmic heating (OH) and OS on inactivation of PME were compared to conventional heat (CH) treatment. Their effects on physical, chemical and microbiological contents were included. In comparison to fresh orange juice, the inactivation of PME was 96%, 95%, 89%, 90% and 29% for OS, OH, TS, CH and S treatments, respectively. Highest cloud value was obtained for OS (1.240 A) treatment. OS treatment gave a lower vitamin C loss compared to TS, OH and CH treatments. A significant increase in the total phenolic content were obtained in the following order OS > TS > OH > CH. OS treated juice also contained the lowest value of hydroxymethyl furfural (0.90 mg/L) compared to OH (0.95 mg/L), TS (1.37 mg/L) and CH (2.72 mg/L) treated samples. Overall, the results indicated that OS can be integrated as a substitute to pasteurization of NFCOJ.

Probabilistic approach for assessing cancer risk due to benzo[a]pyrene in barbecued meat: Informing advice for population groups.

BACKGROUND: Consumption of meat prepared by barbecuing is associated with risk of cancer due to formation of carcinogenic compounds including benzo[a]pyrene (BaP). Assessment of a population's risk of disease and people's individual probability of disease given specific consumer attributes may direct food safety strategies to where impact on public health is largest. The aim of this study was to propose a model that estimates the risk of cancer caused by exposure to BaP from barbecued meat in Denmark, and to estimate the probability of developing cancer in subgroups of the population given different barbecuing frequencies. METHODS: We developed probabilistic models applying two dimensional Monte Carlo simulation to take into account the variation in exposure given age and sex and in the individuals' sensitivity to develop cancer after exposure to BaP, and the uncertainty in the dose response model. We used the Danish dietary consumption survey, monitoring data of chemical concentrations, data on consumer behavior of frequency of barbecuing, and animal dose response data. FINDINGS: We estimated an average extra lifetime risk of cancer due to BaP from barbecued meat of 6.8 × 10-5 (95% uncertainty interval 2.6 × 10-7 - 7.0 × 10-4) in the Danish population. This corresponds to approximately one to 4,074 extra cancer cases over a lifetime, reflecting wide uncertainty. The impact per barbecuing event on the risk of cancer for men and women of low body weight was higher compared to higher bodyweight. However, the difference due to sex and bodyweight between subgroups are dwarfed by the uncertainty. INTERPRETATION: This study proposes a model that can be applied to other substances and routes of exposure, and allows for deriving the change in risk following a specific change in behaviour. The presented methodology can serve as a valuable tool for risk management, allowing for the formulation of behaviour advice targeted to specific sub-groups in the population.

Optimization of ohmic heating parameters for polyphenoloxidase inactivation in not-from-concentrate elstar apple juice using RSM.

In this study, optimization of ohmic heating (OH) process parameters (temperature and voltage gradient) to inactivate polyphenoloxidase (PPO) of not-from-concentrate (NFC) apple juice was conducted. Response surface methodology was used for optimization of OH parameters, where the voltage gradient and temperature on the PPO activity in the NFC apple juice was evaluated. Then the optimized condition was used to produce the NFC apple juice and the quality parameters were evaluated and compared to NFC apple juice prepared by conventional heating (CH). The studied parameters were: PPO activity, total phenolic, total carotenoids, ascorbic acid, cloud value, color as well as physical properties (i.e., TSS, acidity, electric conductivity and viscosity). The reduction of PPO activities was 97 and 91% for OH (at 40 V/cm and 80 °C) and CH (at 90 °C and 60 s), respectively. The reduction of the ascorbic acid was 66.8% for OH significantly lower than the 80% for CH treated samples. The total extracted phenolic content was increased by 5.4 and 2.5% with OH and CH treatments, respectively. The decrease in the concentration of total carotenoids for OH (13.17%) was significantly lower than for CH (34.23%). The color values (L*, a*, b* and ΔE) were only significantly increased in the OH treatment. OH is a potential mild thermal treatment in the production of apple juice with improved functional properties instead of conventional methods.

Content of heterocyclic amines and polycyclic aromatic hydrocarbons in pork, beef and chicken barbecued at home by Danish consumers.

It is a well-known fact that, when meat is barbecued, several harmful components, including heterocyclic amines (HCA) and polycyclic aromatic hydrocarbons (PAH), may be formed. The aim of this study was to determine the HCA and PAH content in meat (pork, chicken and beef) when barbecued at home by Danish consumers according to their normal practice. With regard to HCA, beef contained the highest concentrations of 9H-pyrido[3,4-b]indole (norharman) and 2-methyl-ß-carboline (harman), while chicken contained more 2-amino-1-methyl-6-phenylimidazo[4,5-b]pyridine (PhIP) than pork and beef. The analysis of PAH showed a markedly higher concentration of PAH in beef compared with pork and chicken. In general, a correlation between the HCA content and the surface colour of the meat was found, the darker the colour the higher the HCA concentrations.

Extraction of polycyclic aromatic hydrocarbons from smoked fish using pressurized liquid extraction with integrated fat removal.

Quantification of polycyclic aromatic hydrocarbons (PAHs) in smoked fish products often requires multiple clean-up steps to remove fat and other compounds that may interfere with the chemical analysis. We present a novel pressurized liquid extraction (PLE) method that integrates exhaustive extraction with fat retention in one single analytical step. The PLE parameters: type of fat retainer, flush volume, solvent composition, fat-to-fat retainer ratio (FFR), and the dimensions of the extraction cells were the most important factors for obtaining fat-free extracts with high recoveries of PAHs. A 100mL extraction cell filled with 18 g activated silica gel, dichloromethane:hexane (15:85, v/v) as extraction solvent, FFR of 0.025 and 100% flush volume was the best analytical setup for integrated extraction and fat retention. The one-step procedure provided a more rapid and cost-efficient alternative with minimization of waste generation compared to the standard reference method that is based on a multi-step procedure. Furthermore, the analytical quality of the two methods are comparable, while the new integrated approach for extraction and cleanup is less prone to analytical errors (random and systematic) because of fewer analytical steps.

Synthetic musk fragrances in trout from Danish fish farms and human milk.

Synthetic musk compounds used in detergents and cosmetics include nitro and polycyclic musk compounds. These compounds are discharged after use via domestic wastewater and sewage treatment plants to the aquatic environment. Quantitative detection of nitro musk and polycyclic musk compounds by GC/HRMS in Danish farmed trout and human milk from primiparous mothers are reported. The polycyclic musk, HHCB, dominated the synthetic musk compounds found in trout samples from 1999 with a median concentration of 5.0microg/kg fresh weight (n.d.-52.6microg/kg fresh weight) and in trout samples collected in 2003 and 2004 with a median concentration of 1.2microg/kg fresh weight (n.d.-28.0microg/kg fresh weight). It was also found that the concentration of musk xylene in trout sampled at the same fish farms decreased considerably from a median concentration of 5.1microg/kg fresh weight in 1992 to a median of 0.5microg/kg fresh weight in 1999 and to a median less than the detection limit (0.23microg/kg fresh weight) in 2003. HHCB also dominated in Danish human milk samples collected in 1999 with a median concentration of 147microg/kg fat (38.0-422microg/kg fat). Human dietary intake assessment and body burden calculations on data from 1999 indicate that the main source of exposure to human cannot be attributed to the consumption of farmed trout.