Study of pesticide transformation processes in different wheat varieties and their effects on plant metabolism.

BACKGROUND: This study aims to obtain systematic understanding of the way by which pesticides are metabolized in plants and the influence of this process on plants' metabolism as this process has a key impact on plant-based food safety and quality. The research was conducted under field conditions, which enabled to capture metabolic processes taking place in plants grown under multihectare cultivation conditions. RESULTS: Research was conducted on three wheat varieties cultivated under field conditions and treated by commercially available preparations (fungicides, herbicides, insecticides, and growth regulator). Plant tissues with distinctions in roots, green parts, and ears were collected periodically during spring-summer vegetation period, harvested grains were also investigated. Sample extracts were examined by chromatographic techniques coupled with tandem mass spectrometry for: dissipation kinetics study, identification of pesticide metabolites, and fingerprint-based assessment of metabolic changes. CONCLUSION: Tissue type and wheat varieties influenced pesticide dissipation kinetics and resulting metabolites. Metabolic changes of plants were influenced by type of applied pesticide and its concentration in plants tissues. Despite differences in plant metabolic response to pesticide stress during cultivation, grain metabolomes of all investigated wheat varieties were statistically similar. 4-[cyclopropyl(hydroxy)methylidene]-3,5-dioxocyclo-hexanecarboxylic acid and trans-chrysantemic acid - metabolites of crop-applied trinexapac-ethyl and lambda-cyhalothrin, respectively, were identified in cereal grains. These compounds were not considered to be present in cereal grains up to now. The research was conducted under field conditions, enabling the measurement of metabolic processes taking place in plants grown under large-scale management conditions. © 2024 Society of Chemical Industry.

Changes in Chemical Composition of Lentils, Including Gamma-Aminobutyric Acid and Volatile Compound Formation during Submerged and Solid-State Fermentation with Pediococcus acidilactici.

The aim of this study was to evaluate and compare the characteristics of non-treated and fermented [via submerged (SMF) and solid-state (SSF) fermentation using Pediococcus acidilactici] lentils (Lens culinaris) grown either in pure stands (L) or relay intercropped with winter rye (LR). It was observed that the lentils were suitable substrate for lacto-fermentation. Most of the free amino acid concentrations increased in lentils after both fermentations. The highest concentration of γ-aminobutyric acid was found in SSF LR samples. However, fermentation led to higher biogenic amines (BA) content in lentils. The most abundant fatty acid in lentils was C18:2. SSF lentils showed more complex volatile compound (VC) profiles (with between nine and seventeen new VCs formed), whereas, in SMF samples, between two and five newly VCs were formed. When comparing lentil grown types, L contained significantly higher concentrations of Na, K, Ca, P, Mn, and Se, while LR contained significantly higher concentrations of Fe and Ni. To sum up, fermentation with lactic acid bacteria (LAB) contributed to the improved biological value of lentils; still, the quantity of BA needs to be considered. Further investigations into the P. acidilactici metabolism of certain compounds (such as phenolic and antinutritional compounds) in lentils during fermentation ought to be carried out.

Mycotoxins and pyrrolizidine alkaloids in herbal dietary supplements.

The market demand for herbal dietary supplements is rapidly growing and such products are becoming more common and accessible to consumers. However, the knowledge about their safety remains incomplete. Herbal dietary supplements are one of the food groups that can contribute significantly to human health concerns arising from chronic exposure to pyrrolizidine alkaloids and mycotoxins. This study aimed to simultaneously determine 79 natural contaminants, including mycotoxins, as well as pyrrolizidine and tropane alkaloids in herbal dietary supplements in one analytical run. Exposure assessment and human health risks were assessed for all compounds included in this study. The total concentration of naturally occurring contaminants in herbal dietary supplements reached 5.3 mg kg-1 and the most frequently detected mycotoxins were tentoxin and alternariol monomethyl ether. The latter was detected with the highest frequency, reaching concentrations up to 2.5 mg kg-1. The obtained results indicate a potential risk to public health related to herbal dietary supplement consumption.

Pharmaceutical and Recreational Drug Usage Patterns during and Post COVID-19 Determined by Wastewater-Based Epidemiology.

Wastewater-based epidemiology (WBE) was applied to evaluate the consumption trends of pharmaceuticals (i.e., antibiotics, non-steroidal anti-inflammatory drugs, antiepileptics, antihypertensives, and others), as well as recreational drugs (caffeine, alcohol, and nicotine), in Latvia from December 2020 to July 2023. The time period covers both the COVID-19 pandemic and the post-pandemic periods; therefore, the impact of the implemented restrictions and the consequences of the illness in terms of the usage of pharmaceuticals thereon were investigated. Additionally, the seasonality and impact of the seasonal flu and other acute upper respiratory infections were studied. The results revealed that the pandemic impacted the consumption of alcohol, nicotine, and caffeine, as well as several pharmaceuticals, such as antihypertensives, antidepressants, psychiatric drugs, and the painkiller ibuprofen. The findings suggest that the imposed restrictions during the pandemic may have had a negative effect on the population's health and mental well-being. Distinct seasonal trends were discovered in the consumption patterns of caffeine and alcohol, where lower use was observed during the summer. The seasonal consumption trends of pharmaceuticals were discovered in the case of antibiotics, the antiasthmatic drug salbutamol, and the decongestant xylometazoline, where higher consumption occurred during colder seasons.

An Occurrence Study of Mycotoxins in Plant-Based Beverages Using Liquid Chromatography-Mass Spectrometry.

Mycotoxins are toxic mold metabolites that can adversely affect human and animal health. More than 400 mycotoxins have been identified so far. Cereals and nuts are the predominant mycotoxin-contaminated foodstuffs. Plant-based drinks produced from cereals, nuts, and legumes have grown in popularity. The mycotoxins accumulated in these crops may transfer to these beverages. A liquid chromatography-tandem mass spectrometry method was developed and optimized for the assessment of 22 mycotoxins in commercially available plant-based drinks in Latvia and Lithuania. A total of 64% of the seventy-two analyzed beverages were positive for one to sixteen mycotoxins, with deoxynivalenol, beauvericin, and enniatins A, B, B1, T-2, and HT-2 toxins detected most frequently. The European Commission has not yet set guidelines for the maximum mycotoxin concentrations in plant-based beverages, nor has the European Food Safety Authority conducted a risk assessment. Therefore, acute exposure studies were provided for the Latvian population based on the assumed replacement of dairy milk with plant-based beverages to ascertain the safety of plant-based milk substitutes. Based on the observed levels of mycotoxin prevalence and contamination levels and assumed exposure, it can be concluded that tested plant-based beverages may be relatively safe. However, exposure to emerging mycotoxins should be considered.

The Effect of Ustilago maydis and Delayed Harvesting on A- and B-Type Trichothecene Concentrations in Maize Grain.

The aim of this study was to investigate whether, in the context of a higher incidence of Ustilago maydis and Fusarium spp. at optimal and delayed harvest times, a higher incidence of mycotoxin contamination in maize grains could be expected. The field experiment was carried out at the Lithuanian Research Centre for Agriculture and Forestry experimental fields over three consecutive years (2020-2022). Two maize hybrids (Duxxbury and Lapriora) with different FAO numbers were used. The experimental design in the field was a randomized complete block design. Harvesting took place at three different times: first at physiological maturity, and then 10 (±2) and 20 (±2) days after the first harvest. Each hybrid had four repetitions at different harvest times. The U. maydis infection was only detected in 2021 and after the first harvest cobs were further divided into four different groups with four repetitions: healthy cobs, cobs visually infected with Fusarium spp., cobs visually infected with common smut, and cobs visually infected with both pathogens. No U. maydis-damaged maize cobs were found in 2020 and 2022. The levels of Fusarium microscopic fungi in maize grains were also from 4 to 16 times higher in 2021 than in 2020 and 2022. Harvest delays in 2020 led to a significant deoxynivalenol concentration increase in the Duxxbury hybrid and an HT-2 concentration increase in the Lapriora hybrid. In 2021, deoxynivalenol, 3-acetyl-deoxynivalenol, 15-acetyl-deoxynivalenol, and HT-2 concentrations significantly rose in both hybrids, but the T-2 concentration significantly increased only in the Lapriora hybrid. Deoxynivalenol concentrations were, respectively, 110 and 14.6 times higher than in cobs only infected with Fusarium spp. or U. maydis. Concentrations of 15-acetyl-deoxynivalenol were, respectively, 60, 67, and 43 times higher than in asymptomatic cobs and cobs only infected with Fusarium spp. or U. maydis. Cobs contaminated with both pathogens also had higher concentrations of 3-acetyl-deoxynivalenol. T-2 and HT-2 were detected in maize grains harvested from cobs infected only with Fusarium spp. The presence of U. maydis and Fusarium fungi in maize cobs, along with harvest delays, led to significant increases in mycotoxin concentrations, highlighting the importance of timely harvesting and pathogen management to mitigate mycotoxin contamination in maize grains.

Diversity of Mycotoxins Produced by Fusarium Strains Infecting Weeds.

Although Fusarium is mainly known as an agricultural pathogen that affects monocotyledonous plants, it can also infect different species of weeds in the agricultural environment, thereby contributing to the production of mycotoxins in cereals. In this study, we present new developmental data on the diversity of mycotoxins produced by Fusarium graminearum and Fusarium avenaceum strains from weeds under field conditions. Regarding the potential for the strain dependence of mycotoxin production, this study demonstrated that all F. graminearum strains isolated from weeds and spring wheat showed high potential for deoxynivalenol (DON), 3-acetyl-deoxynivalenol (3-ADON), 15-acetyl-deoxynivalenol (15-ADON), and nivalenol (NIV) production in spring wheat under field conditions. It was determined that F. graminearum is a typical producer of B-type trichothecenes. All strains of F. avenaceum isolated from spring wheat and weeds have the potential to produce enniatins and moniliformin in spring wheat. Each type of weed can host different Fusarium species and strains that produce completely different mycotoxins. Therefore, the distribution of mycotoxins in spring wheat grain may depend more on the Fusarium species or strains that infect the weeds than on the pathogen's host plant species. The predominance of specific mycotoxins in cereals depends on the year's weather conditions and the diversity of Fusarium species present in the field.

A diabetes-like biochemical and behavioural phenotype of Drosophila induced by predator stress.

Predation can have both lethal and non-lethal effects on prey. The non-lethal effects of predation can instil changes in prey life history, behaviour, morphology and physiology, causing adaptive evolution. The chronic stress caused by sustained predation on prey is comparable to chronic stress conditions in humans. Conditions like anxiety, depression, and post-traumatic stress syndrome have also been implicated in the development of metabolic disorders such as obesity and diabetes. In this study, we found that predator stress induced during larval development in fruit flies Drosophila melanogaster impairs carbohydrate metabolism by systemic inhibition of Akt protein kinase, which is a central regulator of glucose uptake. However, Drosophila grown with predators survived better under direct spider predation in the adult phase. Administration of metformin and 5-hydroxytryptophan (5-HTP), a precursor of the neurotransmitter serotonin, reversed these effects. Our results demonstrate a direct link between predator stress and metabolic impairment, suggesting that a diabetes-like biochemical phenotype may be adaptive in terms of survival and reproductive success. We provide a novel animal model to explore the mechanisms responsible for the onset of these metabolic disorders, which are highly prevalent in human populations.

Influence of different lactic acid bacteria strains and milling process on the solid-state fermented green and red lentils (Lens culinaris L.) properties including gamma-aminobutyric acid formation.

The aim of this study was to evaluate the influence of lactic acid bacteria (LAB) strains (Lactiplantibacillus plantarum No.122 and Lacticaseibacillus casei No.210) and milling process on the solid-state fermented (for 24 h, at 30°C) green and red lentils (Lens culinaris L.) properties, chiefly pH, LAB viable counts, color coordinates, free amino acid (FAA) profile, γ-aminobutyric acid (GABA) and biogenic amine (BA) concentrations, fatty acid (FA) and volatile compound (VC) profiles. Results showed that both of the tested LAB strains are suitable for the fermentation of lentils: pH of fermented lentils was <4.5 and LAB viable counts >8.0 log10 colony-forming units (CFU)/g. A very strong negative correlation was found (r = -0.973, p ≤ 0.0001) between LAB counts and pH of the samples. Also, fermentation and milling process were significant factors toward color coordinates of the lentils. In most of the cases, solid-state fermentation (SSF) increased essential FAA content in lentils; however, some of the non-essential FAA content was reduced. SSF significantly increased GABA concentration in lentils and milling process was a significant factor on GABA content of the samples (p ≤ 0.05). The main BA in lentils was spermidine, and SSF decreased their total BA content (34.8% on average in red lentils and 39.9% on average in green lentils). The main FA in lentils were linoleic and oleic. The main VC in lentils were hexanal, 1-hexanol, hexanoic acid, D-limonene and (E)-2-nonen-1-ol. Furthermore, most of the VC showed significant correlations with pH of lentil samples, LAB counts and FA content. Finally, the LAB strain used for fermentation and the milling process of lentils are significant factors for most of the analyzed parameters in lentil. Moreover, despite the higher GABA concentration found in green non-milled SSF lentils, application of combined milling and SSF is recommended because they showed the lowest BA content in addition to higher essential FAA and GABA concentrations.

Dilute-and-shoot approach for determination of several biomarkers and pharmaceuticals in wastewater using nanoflow liquid chromatography - Orbitrap mass spectrometry.

A new method for quantitative analysis of several biomarkers and pharmaceutical compounds in wastewater has been developed employing nanoflow liquid chromatography with Orbitrap mass spectrometry. An easy dilute-and-shoot approach has been used for sample preparation with a dilution factor of 5. Improved retention of ionic and highly polar compounds has been achieved by the addition of tetrabutylammonium bromide as an ion pair reagent into the final diluted sample. The new nanoflow liquid chromatography method has demonstrated low matrix effects (70%-111%), high sensitivity in terms of limits of quantification (0.005 to 0.3 µg/L), low injection volume (70 nl) and solvent consumption, and the ability to analyze diverse polar and ionic analytes within one run using a single reversed-phase nanoflow liquid chromatography column. Wastewater samples (n = 116) from the wastewater treatment plants of different cities in Latvia were analyzed using the developed method. The observed concentrations of biomarkers were in line with the literature data.

The metabolic processes of selected pesticides and their influence on plant metabolism. A case study of two field-cultivated wheat varieties.

Pesticides that are absorbed by plants undergo biotransformation and might affect plant metabolic processes. The metabolisms of two cultivated wheat varieties, Fidelius and Tobak, treated with commercially available fungicides (fluodioxonil, fluxapyroxad, and triticonazole) and herbicides (diflufenican, florasulam, and penoxsulam) were studied under field conditions. The results provide novel insights regarding the effects of these pesticides on plant metabolic processes. Plants (roots and shoots) were sampled six times during the six-week experiment. Pesticides and pesticide metabolites were identified using GC-MS/MS, LC-MS/MS, and LC-HRMS, while root and shoot metabolic fingerprints were determined using non-targeted analysis. Fungicide dissipation kinetics were analyzed according to the quadratic mechanism (R2: 0.8522-0.9164) for Fidelius roots, and zero-order for Tobak roots (R2: 0.8455-0.9194); shoot dissipation kinetics were analyzed according to first-order (R2: 0.9593-0.9807) and quadratic (R2: 0.8415-0.9487) mechanisms for Fidelius and Tobak, respectively. The fungicide degradation kinetics were different compared to reported literature values, most likely due to differences in pesticide application methods. The following metabolites were respectively identified in shoot extracts of both wheat varieties for fluxapyroxad, triticonazole, and penoxsulam: 3-(difluoromethyl)-N-(3',4',5'-trifluorobiphenyl-2-yl)-1H pyrazole-4-carboxamide, 2-chloro-5-{(E)-[2-hydroxy-3,3-dimethyl-2-(1H-1,2,4-triazol-1-ylmethyl)-cyclopentylidene]-methyl}phenol, and N-(5,8-dimethoxy[1,2,4]triazolo[1,5-c]pyrimidin-2-yl)-2,4-dihydroxy-6 (trifluoromethyl)benzene sulfonamide. Metabolite dissipation kinetics varied depending on the wheat variety. These compounds were more persistent than parent compounds. Despite having the same cultivation conditions, the two wheat varieties varied in their metabolic fingerprints. The study revealed that pesticide metabolism has a greater dependence on plant variety and method of administration compared to the physicochemical properties of the active substance. This highlights the necessity of conducting research on pesticide metabolism under field conditions.

Application of nano-LC - nano-ESI - Orbitrap-MS for trace determination of four priority PFAS in food products considering recently established tolerable weekly intake (TWI) limits.

An analytical method was developed and validated for the analysis of four priority perfluoroalkyl substances (PFAS), namely, perfluorooctanoic acid (PFOA), perfluorononanoic acid (PFNA), perfluorohexanesulfonic acid (PFHxS), and perfluorooctanesulfonate (PFOS) in food products using nanoscale liquid chromatography (nano-LC) coupled with nanoscale electrospray ionization (nano-ESI) and Orbitrap mass spectrometry (Orbitrap-MS) detection. The efficiency of two different nano-LC setups for chromatographic separation of selected PFAS was evaluated. The optimal LC separation of analytes was achieved using a reversed phase C18 (RP-C18) nano bore column with an integrated emitter. The effect of matrix concentration factor on signal suppression/enhancement was evaluated for different matrices. The method validation indicated analyte recoveries in the range 83-118% and within-laboratory reproducibility from 7 to 18%, while reanalysis of the materials from proficiency tests (PTs) showed that the accuracy of the obtained concentrations ranged from 85 to 124% of the provided consensus values. The method limits of quantification (m-LOQs) were set as first validation levels ranging from 0.001 to 0.3 ng g-1 sample depending on the type of the food group. The observed method performance characteristics met the criteria stated in Commission Regulation (EU) 2022/1428, Commission Recommendation (EU) 2022/1431, as well as Guidance Document on Analytical Parameters for the Determination of Per- and Polyfluoroalkyl Substances (PFAS) in Food and Feed with regards to the compliance testing of PFAS maximum levels (MLs) and monitoring purposes. The elaborated method was applied for the analysis of selected priority PFAS in different food groups collected from the Latvian retail market.

Influence of Biotreatment on Hordeum vulgare L. Cereal Wholemeal Contamination and Enzymatic Activities.

Crop contamination with mycotoxins is a global problem with a negative impact on human and animal health as well as causing economical losses in food and feed chains. This study was focused on the evaluation of the effect of lactic acid bacteria (LAB) strain (Levilactobacillus brevis-LUHS173, Liquorilactobacillus uvarum-LUHS245, Lactiplantibacillus plantarum-LUHS135, Lacticaseibacillus paracasei-LUHS244 and Lacticaseibacillus casei-LUHS210) fermentation on the changes in the level of deoxynivalenol (DON) and its conjugates in Fusarium spp.-contaminated barley wholemeal (BWP). Samples, with different contamination of DON and its conjugates, were treated separately (for 48 h). In addition to mycotoxin content, enzymatic activities (amylolytic, xylanolytic, and proteolytic) of BWP (before and after fermentation) were evaluated. It was established that the effect of decontamination depends on the LAB strain used, and a significant reduction in DON and the concentration of its conjugates in Lc. casei fermented samples was achieved: the amount of DON decreased on average by 47%, and the amount of D3G, 15-ADON and 3-ADON decreased by 82.4, 46.1, and 55.0%, respectively. Lc. casei also showed viability in the contaminated fermentation medium and an effective production of organic acids was obtained. Additionally, it was found that enzymes are involved to the detoxification mechanism of DON and its conjugates in BWP. These findings indicate that fermentation with selected LAB strains could be applied for contaminated barley treatment in order to significantly reduce Fusarium spp. mycotoxin levels in BWP and improve the sustainability of grain production.

Bio-Converted Spirulina for Nutraceutical Chewing Candy Formulations Rich in L-Glutamic and Gamma-Aminobutyric Acids.

This study aimed at evaluating changes of microalgae Spirulina during its fermentation with Lactiplantibacillus plantarum No. 122 strain, and further at incorporating Spirulina bio-converted for nutraceuticals rich in L-glutamic (L-Glu) and gamma-aminobutyric acids (GABA) into sucrose-free chewing candy (gummy) preparations. Fermented Spirulina had higher b* (yellowness) coordinates than untreated (non-fermented), and fermentation duration (24 and 48 h) had a statistically significant effect on colour coordinates. The highest contents of L-glutamic and gamma-aminobutyric acids (4062 and 228.6 mg/kg, respectively) were found in 24 and 48 h-fermented Spirulina, respectively. Fermentation increased the content of saturated fatty acids and omega-3 in Spirulina, while monounsaturated fatty acids and omega-6 were reduced. The addition of fermented Spirulina (FSp) significantly affected hardness, decreased lightness and yellowness, and increased the greenness of chewing candies. All chewing candy samples (with xylitol) prepared with 3 and 5 g of FSp and 0.2 µL of Citrus paradise essential oil received the highest scores for overall acceptability, and the highest intensity (0.052) of emotion "happy" was elicited by the sample group containing xylitol, agar, ascorbic acid, 3 g of FSp, and 0.1 µL of Mentha spicata essential oil. As an outcome of this research, one may conclude that fermented Spirulina has significant potential as an innovative ingredient in the production of healthier sucrose-free nutraceutical chewing candies.

Submerged and Solid-State Fermentation of Spirulina with Lactic Acid Bacteria Strains: Antimicrobial Properties and the Formation of Bioactive Compounds of Protein Origin.

The aim of this study was to investigate the changes in bioactive compounds (L-glutamic acid (L-Glu), gamma-aminobutyric acid (GABA) and biogenic amines (BAs)) during the submerged (SMF) and solid-state (SSF) fermentation of Spirulina with lactobacilli strains (Lacticaseibacillus paracasei No. 244; Levilactobacillus brevis No. 173; Leuconostoc mesenteroides No. 225; Liquorilactobacillus uvarum No. 245). The antimicrobial properties of the untreated and fermented Spirulina against a variety of pathogenic and opportunistic strains were tested. The highest concentrations of L-Glu (3841 mg/kg) and GABA (2396 mg/kg) were found after 48 h of SSF with No. 173 and No. 244 strains, respectively. The LAB strain used for biotreatment and the process conditions, as well as the interaction of these factors, had statistically significant effects on the GABA concentration in Spirulina (p ≤ 0.001, p = 0.019 and p = 0.011, respectively). In all cases, the SSF of Spirulina had a higher total BA content than SMF. Most of the fermented Spirulina showed exceptional antimicrobial activity against Staphylococcus aureus but not against the other pathogenic bacteria. The ratios of BA/GABA and BA/L-Glu ranged from 0.5 to 62 and from 0.31 to 10.7, respectively. The GABA content was correlated with putrescine, cadaverine, histamine, tyramine, spermidine and spermine contents. The L-glutamic acid concentration showed positive moderate correlations with tryptamine, putrescine, spermidine and spermine. To summarize, while high concentrations of desirable compounds are formed during fermentation, the formation of non-desirable compounds (BAs) must also be considered due to the similar mechanism of their synthesis as well as the possibility of obtaining high concentrations in the end products.

Application of Baltic Pine (Pinus sylvestris) Needle Extract as a Gut Microbiota-Modulating Feed Supplement for Domestic Chickens (Gallus gallus).

The valorization of wood industry residues is very desirable from a circular economy perspective. Pine needle extracts are known for their health-promoting properties and therefore can be used as herbal remedies and nutritional supplements. Since the withdrawal of antibiotics as growth promoters in the European Union, natural feed additives that improve poultry health and production are needed. It was proposed that pine needle extract could be a good alternative to antibiotic usage at sub-therapeutic concentrations. The results relevant to our assumption could be obtained by using domestic chickens as an in vivo model for the evaluation of gut microbiota-altering properties of pine needle extract as an herbal supplement. We tested the antimicrobial effects of Baltic pine (Pinus sylvestris) needle extract. Then, we used chicken (Gallus gallus) that received feed supplemented with two different concentrations of the extract for 40 days to evaluate the changes in gut microbiota using 16S rRNA gene sequencing. This preliminary study demonstrated trends toward dose-dependent desirable changes in broiler microbiome, such as a reduction in the relative abundance of Campylobacter.

Changes in Spirulina's Physical and Chemical Properties during Submerged and Solid-State Lacto-Fermentation.

The aim of this study was to select a lactic acid bacteria (LAB) strain for bio-conversion of Spirulina, a cyanobacteria ("blue-green algae"), into an ingredient with a high concentration of gamma-aminobutyric acid (GABA) for human and animal nutrition. For this purpose, ten different LAB strains and two different fermentation conditions (SMF (submerged) and SSF (solid state fermentation)) were tested. In addition, the concentrations of fatty acids (FA) and biogenic amines (BA) in Spirulina samples were evaluated. It was established that Spirulina is a suitable substrate for fermentation, and the lowest pH value (4.10) was obtained in the 48 h SSF with Levilactobacillus brevis. The main FA in Spirulina were methyl palmitate, methyl linoleate and gamma-linolenic acid methyl ester. Fermentation conditions were a key factor toward glutamic acid concentration in Spirulina, and the highest concentration of GABA (2395.9 mg/kg) was found in 48 h SSF with Lacticaseibacillus paracasei samples. However, a significant correlation was found between BA and GABA concentrations, and the main BA in fermented Spirulina samples were putrescine and spermidine. Finally, the samples in which the highest GABA concentrations were found also displayed the highest content of BA. For this reason, not only the concentration of functional compounds in the end-product must be controlled, but also non-desirable substances, because both of these compounds are produced through similar metabolic pathways of the decarboxylation of amino acids.

Recent Applications of Nano-Liquid Chromatography in Food Safety and Environmental Monitoring: A Review.

In recent years, a trend toward instrument miniaturization has led to the development of new and sophisticated analytical systems, such as nano-liquid chromatography (nano-LC), which has enabled improvements of sensitivity, as well as chromatographic resolution. The growing interest in nano-LC methodology has resulted in a variety of innovative and promising applications. In this article, we review the applications of nano-LC separation methods coupled with mass spectrometry in the analysis of food and environmental samples. An assessment of sample preparation methods and analytical performance are provided, along with comparison to other, more established analytical techniques. Three main groups of compounds that are crucial for food safety assessment are considered in this review: pharmaceuticals (including antibiotics), pesticides, and mycotoxins. Recent practical applications of the nano-LC method in the determination of these compounds are discussed. Furthermore, we also focus on methods for the determination of various environmental contaminants using nano-LC methods. Future perspectives for the development of nano-LC methods are discussed.

Targeted and non-targeted analysis for the investigation of pesticides influence on wheat cultivated under field conditions.

A comprehensive approach was applied to evaluate the effects of pesticides on the metabolism of wheat (Triticum aestivum L). The application of commercially available pesticide formulations under field cultivation conditions provided a source of metabolic data unlimited by model conditions, representing a novel approach to study the effects of pesticides on edible plants. Gas and liquid chromatography coupled to tandem mass spectrometry were employed for targeted and non-targeted analysis of wheat roots and shoots sampled six times during the six-week experiment. The applied pesticides: prothioconazole, tebuconazole, fluoxastrobin, diflufenican, florasulam, and penoxulam were found at concentrations ranging 0.0070-25.20 mg/kg and 0.0020-2.2 mg/kg in the wheat roots and shoots, respectively. The following pesticide metabolites were identified in shoots: prothioconazole-desthio (prothioconazole metabolite), 5-(4-chlorophenyl)-2,2-dimethyl-3-(1,2,4-triazol-1-ylmethyl)pentane-1,3-diol (tebuconazole metabolite), and N-(5,8-dimethoxy[1,2,4]triazolo[1,5-c]pyrimidin-2-yl)-2,4-dihydroxy-6-(trifluoromethyl)benzene sulphonamide (penoxulam metabolite). The metabolic fingerprints and profiles changed during the experiment, reflecting the cumulative response of wheat to both its growth environment and pesticides, as well as their metabolites. Approximately 15 days after the herbicide treatment no further changes in the plant metabolic profiles were observed, despite the presence of pesticide and their metabolites in both roots and shoots. This is the first study to combine the determination of pesticides and their metabolites plant tissues with the evaluation of plant metabolic responses under field conditions. This exhaustive approach contributes to broadening the knowledge of pesticide effects on edible plants, relevant to food safety.

Changes in the physicochemical parameters and microbial community of a new cultivar blue wheat cereal wholemeal during sourdough production.

Changes in the characteristics of a new cultivar (DS8472-5) of blue wheat during wholemeal fermentation with Pediococcus acidilactici (LUHS29), Liquorilactobacillus uvarum (LUHS245), and Lactiplantibacillus plantarum (LUHS122), including acidity, microbiological and chromaticity parameters, free amino acid (FAA), gamma-aminobutyric acid (GABA), and biogenic amine (BA) contents, macro- and micro-element concentrations and fatty acid (FA) and volatile compounds (VC), were evaluated. In addition, a metagenomic analysis was performed. The lactic acid bacteria (LAB) strains used for fermentation was a significant factor in wholemeal fermentation sample pH, redness (a*) and LAB counts (p ≤ 0.05). In most of the samples, fermentation increased the FAA content in wheat wholemeal, and the highest concentration of GABA was found in DS8472-5 LUHS122 samples. Phenylethylamine (PHE) was found in all wheat wholemeal samples; however, spermidine was only detected in fermented samples and cadaverine only in DS8472-5 LUHS122. Fermented samples showed higher omega-3 and omega-6 contents and a higher number and variety of VC. Analysis of the microbial profile showed that LAB as part of the natural microbiota present in cereal grains also actively participates in fermentation processes induced by industrial bacterial cultures. Finally, all the tested LAB were suitable for DS8472-5 wheat wholemeal fermentation, and the DS8472-5 LUHS122 samples showed the lowest pH and the highest LAB viable counts (3.94, 5.80°N, and 8.92 log10 CFU/g, respectively).