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Pharmaceutical products (PPs) belong to emerging contaminants that may accumulate along with other chemical pollutants in wastewaters (WWs) entering industrial and/or urban wastewater treatment plants (WWTPs). In the present study, the technique of ultra-high-performance liquid chromatography coupled to Orbitrap high-resolution mass spectrometry (Orbitrap-HRMS) was applied for the analysis of 24 multi-class PPs in WW samples collected at different technological stages of Daugavgriva WWTP located in Riga, Latvia. Caffeine and acetaminophen levels in the range of 7,570-11,403 ng/L and 810-1,883 ng/L, respectively, were the predominant compounds among 19 PPs determined in the WW. The results indicate that aerobic digestion in biological ponds was insufficiently effective to degrade most of the PPs (reduction efficiency <0-50.0%) with the exception of four PPs that showed degradation efficiency varying from 55.0 to 99.9%. Tests of short-term chemical and enzymatic hydrolysis for PP degradation in WW samples were performed, and the results reflected the complexity of different degradation mechanisms and physicochemical transformations of PPs. The toxicological studies of WW impact on Daphnia magna indicated gradual reduction of the total toxicity through the treatment stages at the WWTP. [ABSTRACT FROM AUTHOR]

Grape processing generates large amounts of by-products, including seeds rich in hydrophilic and lipophilic antioxidants. This study demonstrates, for the first time, that subjecting grape seeds to a single ultrasound-assisted extraction (UAE) with aqueous ethanolic solutions yields both flavan-3-ols and tocochromanols in the final extract. Notably, the water content in ethanol significantly influences the extractability of tocochromanols more than flavan-3-ols. Solid-to-solvent ratios of 1:50 to 1:2 were tested for both analytical and industrial applications. A sustainable analytical approach for recovering flavan-3-ols and tocochromanols using 60% and 96.4% ethanol extractions was validated and employed to profile nineteen genotypes of lesser-studied interspecific grape crosses (Vitis spp.). Different genotypes showed a wide range of concentrations of tocopherols (1.6-6.3 mg/100 g), tocotrienols (1.0-17.4 mg/100 g), and flavan-3-ols (861-9994 mg/100 g). This indicated that the genetic background and maturity of the plant material are crucial factors from an industrial perspective due to the initial concentration of bioactive compounds. Finally, the study also discussed the fundamental aspects of hydrophobic antioxidant extractability from the lipid matrix with aqueous ethanol solutions and the limitations of the workflow, such as the non-extractable tocochromanols and their esters and the losses of these lipophilic antioxidants during extraction., Competing Interests: Declaration of competing Interest All other authors declare no conflict of interest., (Copyright © 2024. Published by Elsevier Ltd.)

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.

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.

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.

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 .

Wastewater-based epidemiology (WBE) was applied to evaluate seasonal variations of the consumption of pharmaceuticals (i.e. antibiotics, NSAIDs, antiepileptics, antihypertensives and others), caffeine, alcohol and nicotine in Latvia throughout 2021. In addition, weekly variation of caffeine, nicotine and alcohol consumption was investigated. Pronounced seasonality was observed in the consumption of antibiotics and decongestants, as well as caffeine, nicotine and alcohol. Correlation with COVID-19 statistics was observed in the case of macrolide antibiotics and antiasthmatic salbutamol. Comparison of the estimated consumption values obtained using the WBE approach and the statistics revealed that the majority of compounds data are in good agreement except angiotensin II receptor blocker group antihypertensives where the most overestimated consumption values were observed., (Copyright © 2022 Elsevier Ltd. All rights reserved.)

The COVID-19 pandemic has become an unprecedented public health emergency causing immense societal and socio-economic consequences. Multiple studies have outlined that interventions to curb the spread of the virus are likely to have an effect on substance use patterns. In this study, we explored the presence of psychoactive pharmaceuticals, illicit drugs and related human metabolites in 24-h composite wastewater samples that were collected weekly in 2021 from the central WWTP of Riga, Latvia. The analysis was performed via suspect screening approach using three separate high-resolution mass spectrometry (HRMS) workflows, which relied on reversed-phase liquid chromatography (RPLC), hydrophilic interaction liquid chromatography (HILIC) and direct infusion HRMS. In total, 39 out of 149 substances were detected throughout the sampling period. These include pharmaceuticals (mainly antiepileptics, antidepressants and antipsychotics), illicit drugs (e.g., MDMA, MDEA, cocaine, etc.) and new psychoactive substances (alpha-PVP). The results were evaluated in relation to COVID-19 incidence rate and the severity of containment and closure policies. For some compounds we observed temporal changes that may be potentially linked to the state of the pandemic. For instance, higher detection rates were observed for several illicit drugs during periods, when restrictions on public events were relaxed. Meanwhile, some psychoactive pharmaceuticals and drugs used to treat upper respiratory tract infections displayed increased prevalence in weeks when the national COVID-19 incidence rates were higher. However, without baseline reference data from previous years, it is difficult to discern how much of the relationships seen are linked to pandemic progression and seasonal variability., Competing Interests: The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (© 2022 Elsevier Ltd. All rights reserved.)

Wastewater-based epidemiology (WBE) is a promising biomonitoring approach with the potential to provide direct information on human intake and exposure to food contaminants and environmental chemicals. The aim of this study was to apply WBE while employing the normalization method for exploring human exposure to selected mycotoxins according to population biomarker 5-hydroxyindoleacetic acid (5-HIAA). This type of normalization technique has been previously used to detect various other compounds. However, to the best of our knowledge, this is the first study tracking human exposure to mycotoxins. A sensitive analytical methodology was developed to achieve reliable quantification of deoxynivalenol, enniatins, and beauvericin in wastewater (WW) samples. The applicability of the method was evaluated by testing 29 WW samples collected at WW treatment plants in Latvia. With frequency of detection greater than 86%, enniatins B, B1, A, and A1 were revealed in WW samples. The estimated total daily intake for enniatins was in the range of 1.8-27.6 µg/day per person. Free deoxynivalenol (DON) was determined in all analysed WW samples. Based on the average 5-HIAA excretion level and the determined 5-HIAA content in the samples, the intake of DON by the human population of Riga was estimated at 325 ng/kg b.w. day.

The biomarkers used in wastewater-based epidemiology studies have a wide range of physicochemical properties, making simultaneous analysis extremely challenging or even impossible. So far, the majority of analytical procedures employed in this field have focused on specific classes or a limited number of analytes. The heart-cutting two-dimensional liquid chromatography tandem mass spectrometry technique (2D-LC-MS/MS) has enabled the incorporation of compounds with significantly different polarities in a single analytical method. In this study, a 2D-LC-MS/MS method has been developed and optimized for the simultaneous analysis of various biomarkers in wastewater, providing relevant information about lifestyle habits (the usage of alcohol, tobacco, and caffeine), health and well-being (pharmaceuticals), and a population size biomarker (5-HIAA) that is useful for correct calculation of human population during wastewater-based epidemiology studies. A single-laboratory validation procedure showed satisfactory analytical performance, with the mean trueness for most compounds falling in the range of 80÷110 % and the mean repeatability being less than 20 %. The applicability of the method was evaluated by testing 28 wastewater samples collected at different wastewater treatment plants in Latvia. The obtained results revealed the occurrence of 44 out of 62 selected biomarkers, with the lowest quantified concentration at 1.1 ng L -1 in the case of xylometazoline and up to 148 μg L -1 in the case of metformin and 156 μg L -1 for caffeine., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2021 Elsevier B.V. All rights reserved.)

Glyphosate and other polar and acidic pesticides have been particularly studied due to the concerns over widespread and intensive use. The chemical properties of these compounds necessitate use of customised methods, such as derivatisation or ion exchange chromatography. These approaches present a compatibility problem with ESI-MS due to presence of salts and non-volatile compounds. For that reason, a simple procedure has been developed for the extraction, pre-column derivatisation with dansyl chloride (5-(dimethylamino)naphthalene-1-sulfonyl chloride), and mass spectrometric detection of glyphosate, AMPA, and glufosinate after the separation on a C 18 stationary phase. The dansyl derivatives were characterised with ESI-MS and their separation from derivatisation reagent byproducts was demonstrated with UV absorption detection. Reagent byproducts eluted before the analytes and were separated from the analytes completely, thus the proposed procedure did not contaminate the mass spectrometers. The proposed procedure was evaluated with respect to the matrix effects and extraction efficiency, and was validated with different mass spectrometers for milk, cucumber, honey, porridge formula, bovine kidney and liver matrix. The LOQ was 10 μg kg -1 for AMPA and glufosinate, and 10-25 μg kg -1 for glyphosate, depending on matrix. Measurement uncertainties ranged from 4 to 44%. Method performance was compared to the QuPPe (Quick Polar Pesticides) procedure in combination with a diethylamino-based column from Waters™. In the case of Orbitrap™ detection, the proposed procedure had a comparable performance to the QuPPe procedure. Although, improved peak shape, higher absolute peak intensity, and lower standard deviation of the calibration curve slope was observed with the proposed procedure. This could be explained by the superior electrospray stability and lower extent of ion suppression., (Copyright © 2021 Elsevier B.V. All rights reserved.)

Twenty-seven mycotoxins in unprocessed cereals ( n = 110) and pulses ( n = 23) harvested in Latvia were analysed by nanoflow liquid chromatography combined with Orbitrap high-resolution mass spectrometry. One or more mycotoxins were found in 99% of the cereals and 78% of the pulses. Deoxynivalenol, zearalenone and T-2 and HT-2 toxins were prevalent in 9 to 86% of the cereals, mostly below their maximum levels as set by the European regulations. Non-regulated type A and B trichothecenes were prevalent in 5 to 87% of the cereals, at concentrations of 0.27-83 µg kg -1 and 1.7-4,781 µg kg -1 , respectively. Quantification of emerging mycotoxins was also provided. Enniatins were detected in 94% of the cereals (3.5-2,073 µg kg -1 ) and 13% of the pulses (4.4-17 µg kg -1 ). Alternaria toxins were prevalent in 94% of the cereals at concentrations of 0.72-307 µg kg -1 and in 39% of the pulses at 0.69-10 µg kg -1 .

During plant-based drinks production a significant amount of valuable by-products (BPs) is obtained. The valorization of BPs is beneficial for both the environment and the food industry. The direct incorporation of the fermented and/or ultrasonicated almond, coconut, and oat drinks production BPs in other food products, such as wheat bread (WB) could lead to the better nutritional value as well as quality of WB. Therefore, in this study, various quantities (5, 10, 15, and 20%) of differently treated [ultrasonicated (37 kHz) or fermented with Lacticaseibacillus casei LUHS210] almond, coconut, and oat drinks preparation BPs were used in wheat bread (WB) formulations. Microbiological and other quality parameters (acidity, color, specific volume, porosity, moisture content, overall acceptability) as well as bread texture hardness during the storage and acrylamide content in the WB were evaluated. Among the fermented samples, 12-h-fermented almond and oat, as well as 24-h-fermented coconut drinks preparation BPs (pH values of 2.94, 2.41, and 4.50, respectively; total enterobacteria and mold/yeast were not found) were selected for WB production. In most cases, the dough and bread quality parameters were significantly ( p ≤ 0.05) influenced by the BPs used, the treatment of the BPs, and the quantity of the BPs. The highest overall acceptability of the WB prepared with 20% fermented almond drink preparation by-product (AP), 15% fermented oat drink preparation by-product (OP), and 15% ultrasonicated OP was established. After 96 h of storage, the lowest hardness (on average, 1.2 mJ) of the breads prepared with 5% fermented AP, coconut drink preparation by-product (CP), and OP and ultrasonicated CP was found. The lowest content of acrylamide in the WB prepared with OP was found (on average, 14.7 μg/kg). Finally, 15% fermented OP could be safely used for WB preparation because the prepared bread showed high overall acceptability, as well as low acrylamide content., Competing Interests: The authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest., (Copyright © 2021 Bartkiene, Bartkevics, Pugajeva, Borisova, Zokaityte, Lele, Starkute, Zavistanaviciute, Klupsaite, Zadeike and Juodeikiene.)

Processed wheat bran (W) is of great importance for food and feed. Consequently, the biosafety of W should be evaluated and improved with valorisation strategies. This study tested a design combining extrusion (at temperature of 115 and 130 °C; screw speeds of 16, 20, and 25 rpm) and fermentation with Lactobacillus plantarum and L. uvarum strains for the valorisation of W to provide safer food and feed stock. The influence of different treatments on biogenic amine formation, mycotoxin content, and free amino acids, as well as acidity, microbiological parameters, and sugar concentration, were analysed. This research showed that a combination of extrusion and fermentation with selected strains can change several aspects of W characteristics. There was a significant effect of applied treatments on acidity and the microbiological parameters of W, as well as biogenic amines content. The lowest total mycotoxin concentration (29.8 µg/kg) was found in extruded (130 °C; 25 rpm) and fermented with L. uvarum sample. Finally, the combination of the abovementioned treatments can be confirmed as a prospective innovative pre-treatment for W, capable of potentially enhancing their safety characteristics and composition.

The aim of this study was to apply a combination of the microbial starters Lactobacillus uvarum LUHS245, Lactobacillus casei LUHS210, Pediococcus acidilactici LUHS29, and Pediococcus pentosaceus LUHS183 for feed fermentation and to evaluate the influence of fermentation on feed acidity and microbiological characteristics, as well as on the piglet feces microbiota, health, and growth performance. Additionally, mycotoxin biotransformation was analyzed, including masked mycotoxins, in feed and piglet feces samples. The 36-day experiment was conducted using 25-day-old Large White/Norwegian Landrace (LW/NL) piglets with an initial body weight of 6.9-7.0 kg, which were randomly distributed into two groups (in each 100 piglets): control group, fed with basal diet (based on barley, wheat, potato protein, soybean protein concentrate, and whey powder), and treated group, fed with fermented feed at 500 g kg -1 of total feed. Compared to a commercially available lactic acid bacteria (LAB) combination, the novel LAB mixture effectively reduced feed pH (on average pH 3.65), produced a 2-fold higher content of L(+) lactic acid, increased viable LAB count [on average 8.8 log 10 colony-forming units (CFU) g -1 ], and led to stable feed fermentation during the entire test period (36 days). Fecal microbiota analysis showed an increased number of probiotic bacteria in the treated group, particularly Lactobacillus , when compared with the control group at the end of experiment. This finding indicates that fermented feed can modify microbial profile change in the gut of pigs. In treated piglets' blood (at day 61), the serum high-density lipoprotein (HDL) cholesterol and triglycerides (TG) were significantly higher, but the levels of T4, glucose, K, alkaline phosphatase (AP), and urea were significantly decreased ( p ≤ 0.05) compared with the control group. Mycotoxin analysis showed that alternariol monomethyl ether (AME) and altenuene were found in 61-day-old control piglets' feces and in fermented feed samples. However, AME was not found in treated piglets' feces. Feed fermentation with the novel LAB combination is a promising means to modulate piglets' microbiota, which is essential to improve nutrient absorption, growth performance, and health parameters. The new LAB composition suggests a novel dietary strategy to positively manipulate fermented feed chemicals and bio-safety and the piglet gut microbial ecology to reduce antimicrobials use in pig production and increase local feed stock uses and economical effectiveness of the process., (Copyright © 2020 Vadopalas, Ruzauskas, Lele, Starkute, Zavistanaviciute, Zokaityte, Bartkevics, Pugajeva, Reinolds, Badaras, Klupsaite, Mozuriene, Dauksiene, Gruzauskas and Bartkiene.)

In this paper, a study of fungal and multi-mycotoxin contamination in 140 Camellia sinensis and 26 herbal teas marketed in Latvia is discussed. The analysis was performed using two-dimensional liquid chromatography with time-of-flight mass spectrometry (2D-LC-TOF-MS) and MALDI-TOF-MS. In total, 87% of the tea samples tested positive for 32 fungal species belonging to 17 genera, with the total enumeration of moulds ranging between 1.00 × 10 1 and 9.00 × 10 4 CFU g -1 . Moreover, 42% of the teas ( n = 70) were contaminated by 1 to 16 mycotoxins, and 37% of these samples were positive for aflatoxins at concentrations ranging between 0.22 and 41.7 µg kg -1 . Deoxynivalenol (DON) and its derivatives co-occurred in 63% of the tea samples, with their summary concentrations reaching 81.1 to 17,360 µg kg -1 . Ochratoxin A (OTA), enniatins, and two Alternaria toxins were found in 10-37% of the teas at low concentrations. The dietary exposure assessment based on the assumption of a probable full transfer of determined mycotoxins into infusions indicated that the analysed teas are safe for consumers: the probable maximum daily exposure levels to OTA and the combined DON mycotoxins were only 0.88 to 2.05% and 2.50 to 78.9% of the tolerable daily intake levels.

In this study, the presence of antibiotics (ANB) residues was evaluated in poultry meat purchased from German and Lithuanian markets. In addition, the antimicrobial activity of 13 lactic acid bacteria (LAB) strains, 2 essential oils (EO) (Thymus vulgaris and Origanum vulgare L.), and their compositions were tested for the purpose of inhibiting antibiotic-resistant Salmonella spp. ANB residues were found in 3 out of the 20 analyzed poultry meat samples: sample no. 8 contained enrofloxacin (0.46 μg/kg), sample no. 14 contained both enrofloxacin and doxycycline (0.05 and 16.8 μg/kg, respectively), and sample no. 18 contained enrofloxacin (2.06 μg/kg). The maximum residue limits (MRLs) for the sum of enrofloxacin and ciprofloxacin and for doxycycline in the poultry muscle are 100 μg/kg. Finally, none of the tested poultry meat samples exceeded the suggested MRLs; however, the issue of ANB residues still requires monitoring of the poultry industry in Germany, Poland, and Lithuania, despite the currently established low ANB concentrations. These findings can be explained by the increased use of alternatives to ANB in the poultry industry. Our results showed that an effective alternative to ANB, which can help to reduce the occurrence of antibiotic-resistant salmonella, is a composition containing 1.0% of thyme EO and the following LAB strains: Lactobacillus plantrum LUHS122, Enteroccocus pseudoavium LUHS242, Lactobacillus casei LUHS210, Lactobacillus paracasei LUHS244, Lactobacillus plantarum LUHS135, Lactobacillus coryniformins LUHS71, and Lactobacillus uvarum LUHS245, which can be recommended for poultry industry as components of feed or for the treatment of surfaces, to control the contamination with Salmonella strains. However, it should be mentioned that most of the tested LAB strains were inhibited by thyme EO at the concentrations of 0.5 and 1.0%, except for LUHS122, LUHS210, and LUHS245. Finally, it can be noted that the agents responsible for the inhibitory effect on Salmonella are not the viable LAB strains but rather their metabolites, and further studies are needed to identify which metabolites are the most important., (Copyright © 2020. Published by Elsevier Inc.)

In order to promote the efficient use of byproducts from the production of plant-based beverages, which still contain a large amount of nutritional and functional compounds, microbiological and chemical safety characteristics should be evaluated and, if needed, improved. Many challenges are associated with byproducts valorization, and the most important ones, which should be taken into account at the further steps of valorization, are biological and chemical safety. For safety improving, several technological treatments (biological, physical etc.) can be used. In this study, the influence of low-frequency ultrasonication (US) and fermentation with Lactobacillus casei LUHS210 strain, as physical and biotechnological treatments, on the safety characteristics of the byproducts (BYs) from the processing of rice, soy, almond, coconut, and oat drinks was compared. Ultrasonication, as well as fermentation, effectively improved the microbiological safety of BYs. Ultrasonication and fermentation reduced the concentration of deoxynivalenol, on average, by 24% only in soy BYs. After fermentation, 15-acetyldeoxynivalenol was formed in all samples (<12 µg kg -1 ), except for soy BYs. The lowest total biogenic amines content was found in fermented rice BYs and ultrasonicated coconut BYs. When comparing untreated and fermented BYs, significant changes in macro- and micro-elements content were found. Ultrasonication at 37 kHz did not significantly influence the concentrations of macro- and micro-elements, while fermentation affected most of the essential micro-elements. Consequently, while ultrasonication and fermentation can enhance the safety of BYs, the specific effects must be taken into account on biogenic amines, mycotoxins, and micro and macro elements.

The occurrence and dietary exposure assessment of 16 mycotoxins, 6 biogenic amines (BAs), and 13 metallic elements in blue-veined cheeses ( n = 46) is reported. Co-occurrence of mycophenolic acid (≤599 µg·kg -1 ) with roquefortine C (≤5454 µg·kg -1 ) was observed in 63% of the tested cheeses, while BAs were frequently present at concentrations between 0.2 and 717 mg kg -1 . The concentrations of heavy metals in cheeses were very low. Chronic/acute exposure assessment based on consumption data from different European populations indicated that the levels of mycotoxins and heavy metals are safe to consumers, whereas, rather high hazard indexes (HI up to 0.77) were determined for BAs according to the worst-case scenario based on high consumption and 95th percentile occurrence. A more detailed acute dietary intake study indicated that histamine and tyramine were predominant among these BAs, reaching 27 and 41% of the acute oral intake reference doses.

Pesticide residues in bee products is still a major issue. However, the relations to botanical source and land use characteristics are not clear. The large variability of residues detected questions the suitability of bee-collected- and other hive materials as indicators for environmental contamination. The aim of our study was to clarify whether different beehive matrices contain similar pesticide residues, and how these are correlated with forage preferences and land use types in foraging areas. We tested bee-collected pollen, beebread, honey, nurse bees and honey bee larvae for the presence of concurrently used agricultural pesticides in Estonia. Samples were collected at the end of May and mid-July to include the main crop in northern region - winter and spring oilseed rape (Brassica napus). We saw that different beehive matrices contained various types of pesticide residues in different proportions: pollen and beebread tended to contain more insecticides and fungicides, whereas herbicides represented the primary contaminant in honey. The variations were related to collection year and time but were not related to crops as basic forage resource nor the land use type. We found few positive correlations between amount of pesticides and proportion of pollen from any particular plant family. None of these correlations were related to any land-use type. We conclude that pesticide residues in different honey bee colony components vary largely in amount and composition. The occurrence rate of pesticide residues was not linked to any particular crop., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

This research effort aimed at isolating and phenotypically characterizing lactic acid bacteria (LAB) isolates from a spontaneous rye sourdough manufactured following traditional protocols, as well as at evaluating their antimicrobial and antifungal properties as key features for future industrial applications. Thirteen LAB strains of potential industrial interest were isolated and identified to species-level via PCR. Most of the sourdough isolates showed versatile carbohydrate metabolisms. The Leuconostoc mesenteroides No. 242 and Lactobacillus brevis No. 173 demonstrated to be gas producers; thus, revealing their heterofermenter or facultative homofermenter features. Viable counts higher than 7.0 log 10 (CFU/mL) were observed for Lactobacillus paracasei No. 244, Lactobacillus casei No. 210, L. brevis No. 173, Lactobacillus farraginis No. 206, Pediococcus pentosaceus No. 183, Lactobacillus uvarum No. 245 and Lactobacillus plantarum No. 135 strains, after exposure at pH 2.5 for 2 h. Moreover, L. plantarum No. 122, L. casei No. 210, Lactobacillus curvatus No. 51, L. paracasei No. 244, and L. coryniformins No. 71 showed growth inhibition properties against all the tested fifteen pathogenic strains. Finally, all LAB isolates showed antifungal activities against Aspergillus nidulans , Penicillium funiculosum , and Fusarium poae . These results unveiled the exceptionality of spontaneous sourdough as a source of LAB with effective potential to be considered in the design of novel commercial microbial single/mixed starter cultures, intended for application in a wide range of agri-food industries, where the antimicrobial and antifungal properties are often sought and necessary. In addition, metabolites therefrom may also be considered as important functional and bioactive compounds with high potential to be employed in food and feed, as well as cosmetic and pharmaceutical applications.

Ion chromatography coupled with mass spectrometry is an established technique for determination of ionic analytes, however, sophisticated buffer removal equipment is required to eliminate inorganic compounds from the eluate before introduction into the ion source of mass spectrometer. A standard high-performance liquid chromatography coupled with tandem mass spectrometry setup using an ion exchange column (Metrosep® A Supp 5) is proposed as an alternative approach. For that reason, some buffers including non-volatile carboxylic acid based solutions have been evaluated for simultaneous trace determination of ionic and acidic pesticides including glyphosate in the same extract without a need for sophisticated buffer removal equipment. Two differently designed ionisation sources were compared qualitatively for the application of non-volatile buffers. The study revealed that the choice of buffers had a strong influence on matrix effects in case of spiked extract injections. Finally, pesticides with very different physicochemical properties (logP < 0, logP ≥ 0) and structures (containing carboxylate, phosphonate, azolide, azanide, phenolate, bromate, and chlorate moieties) were quantified in spiked beer and oat extracts with acceptable recoveries (80-110%) using tandem mass spectrometry detection with AB SCIEX QTRAP 5500 instrument after separation using edetate buffer., (© 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

In this study various coatings from apple press cake (AP) with immobilized antifungal bacterial cells were used for bread surface treatment to increase anti-moulding effect. The antifungal effect and technological properties of newly isolated Lactobacillus coryniformis LUHS71, L. curvatus LUHS51, L. farraginis LUHS206 and Leuconostoc mesenteroides LUHS225 strains. Then, the  lactobacilli were tested for the effects of incorporation of  sourdough on acrylamide formation in bread and antifungal effect against moulds commonly associated with bread spoilage. The addition of 15-20% of sourdoughs significantly ( p  = 0.0001) improved bread volume and crumb porosity depending on LAB strain, and reduced acrylamide formation on average by 23% (for LUHS51 and LUHS206) by 54% (for LUHS71 and LUHS225) compared to control bread. Additionally, the use of AP-LAB coatings prolonged shelf life from 3 to 6 days for control bread, and up to 9 days for sourdough breads. The combination of antifungal LAB sourdough and the AP-LAB coating leads to produce high quality bread with extended shelf life and would be a new and promising environmentally-friendly technological alternative.

Development of a new comprehensive method based on one-step liquid-liquid extraction (LLE) combined with ultra-high-performance liquid chromatography-Orbitrap high resolution mass spectrometry (UHPLC-Orbitrap-HRMS) for the determination of eight phenolic compounds in dark chocolate is demonstrated. The study focuses on the optimization of sample preparation, chromatographic separation and Orbitrap-HRMS detection parameters to adjust selectivity and sensitivity of the method. The LLE mixture of formic acid-water-acetonitrile (2:58:40, v/v) and hexane at the component ratio of 1:1 (v/v) was applied for sample preparation. The inter-day and intra-day precision expressed from the relative standard deviations (RSDs) ranged between 5.50-14.2% and 5.60-16.2%. The quantification limits of the target analytes were between 0.1 and 1.0 mg/kg. The method was applied for the analysis of twenty-six samples of dark chocolate with various cocoa solid contents (30-77%) collected from the markets in Latvia. The total levels of the phenolic contents ranged between 330 and 2631 mg/kg. The study demonstrates advantages of the Orbitrap-HRMS method for the study of phenolic compounds in dark chocolate., (© The Author(s) 2019. Published by Oxford University Press. All rights reserved. For Permissions, please email: journals.permissions@oup.com.)

A new sensitive and selective multi-residue method based on liquid chromatography - Orbitrap high resolution mass spectrometry (LC-Orbitrap-HRMS) was developed and validated for the determination of 17 anticoccidials in poultry and eggs. Instrumental parameters were optimized by the means of statistical experimental designs to improve the sensitivity, precision, and repeatability of the method. Further optimization of auto-tuned MS parameters led to an increase of signal intensity by 10% to 99% for 16 out of 17 analytes. The sample preparation procedure included extraction from muscle tissue and egg samples with acetonitrile, followed by preconcentration, reconstitution, and filtration. Validation was performed according to the Commission Decision 2002/657/EC. The occurrence of anticoccidials in eggs and poultry was assessed by using the developed analytical procedure within the Latvian national monitoring program, revealing quantifiable residues for 6 analytes (marker residue of nicarbazin - 4,4'-dinitrocarbanilide (DNC), salinomycin, narasin, toltrazuril, and its two metabolites)., (Copyright © 2018 Elsevier B.V. All rights reserved.)

This article covers recent trends of carbonaceous nanomaterial supported solid phase extraction for the liquid and gas chromatography analysis of pesticides in food samples. Several advanced carbonaceous nanosorbents have been reported over the previous decade for pesticide extraction, such as graphene derivatives modified by combination with silica, amines, polymers, and/or magnetic nanoparticles. The advances in this field have opened possibilities for using neat or modified carbon nanotubes or graphene-type sorbents for the pre-concentration of polar or nonpolar pesticides by solid phase extraction (SPE) or micro-SPE methods or to apply such nanomaterials for the removal of matrix components by dispersive SPE during sample clean-up. The applications of such nanosorbents should increase in the next few years, considering the expected improvements of their properties, including time and resource economy, selectivity, and reusability.

A sensitive LC-MS/MS method for the determination of glyphosate in beer has been developed, validated, and applied to analyse 100 beer samples from 24 different producers and distributors in Latvia. The selected samples represented most beer brands and varieties sold in local supermarkets. Different procedures for sample preparation and chromatographic separation were compared. The final version of the method consisted of solid phase extraction, chromatographic separation on aminopropyl stationary phase, and detection using tandem mass spectrometry. The concentration of glyphosate in beer varied from below the LOD of 0.2 μg kg -1 up to 150 μg kg -1 , higher than previously reported. Significantly higher (p < 0.01) content of glyphosate was observed in beers that did not have the country of production disclosed on the label and were sold in local supermarkets by distributors from Latvia (1.8 μg kg -1 median concentration in locally produced beer, 6.7 μg kg -1 in beer of undisclosed origin).

The aim of this study was to evaluate the influence of ultrasonication, fermentation with Lactobacillus plantarum LUHS135 and Lactobacillus paracasei LUHS244, and different methods of dehydration on the chemical composition of bovine colostrum (BC), including the fatty acid and free amino acid profile and the content of micro- and macroelements. In addition, we analyzed the changes in lactic acid bacteria count, microbial contamination (aerobic mesophilic spore-forming bacteria, enterobacteria including Escherichia coli, and fungi/yeasts), the abundance of biogenic amines, and the concentration of nucleotide monophosphates. Significant effects of different treatments on the free amino acid profile were established, and an increase of lysine concentration by 1.2 to 95.9% was observed in treated BC. All of the treatments reduced the concentration of cadaverine, histamine, and tyramine in BC. The concentrations of macro- and microelements in BC followed the following order Ca > Na > K > Mg and Zn > Fe > Sr > Ba > Mn > Cu > Al > Se > Mo > Cr > Ni > Sn > Co > Pb > Cd. By combining the fermentation with Lactobacillus plantarum strain LUHS135 and vacuum drying, it was possible to increase the abundance of nucleotide monophosphates by more than 100%. All of the treatments reduced the microbial contamination of BC. Thus, the combination of ultrasonication, fermentation, and dehydration can be used for improving the properties and safety of BC., (The Authors. Published by FASS Inc. and Elsevier Inc. on behalf of the American Dairy Science Association®. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/3.0/).)

An analytical method based on liquid chromatography with quadrupole time-of-flight mass spectrometry has been developed for the simultaneous determination of six aminoglycoside antibiotics in honey. The sample pretreatment included extraction with aqueous trichloroacetic acid followed by solid-phase extraction on Strata-X polymeric reversed phase cartridges. Liquid chromatography separation was performed on an Obelisc R zwitterionic type mixed-mode column. An ionBooster™ heated electrospray source was used and showed enhanced ionization efficiency in comparison to a conventional electrospray source. The observed signal enhancement ranged from 3- (neomycin) to 16-fold (gentamicin C1). A data-dependent mass spectrometry acquisition approach was employed, in which the full mass spectrometry dataset provided quantification and a scheduled precursor list was used to trigger an alternating data-dependent acquisition of MS 2 spectra for confirmation purposes. The described method was validated in accordance to CD 2002/657/EC. Decision limit values were in the range 11.2-33.6 ng/g, and satisfactory performance characteristics were obtained for recovery (65-76%), repeatability (3.8-7.3%), and linearity (≥0.995). The method was applied to the analysis of 49 real honey samples from the country of Georgia. Streptomycin was detected in two samples at 117 and 35 ng/g, and gentamicin C1 was detected in one sample at 32 ng/g., (© 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

This work reports data on the occurrence of nine mycotoxins and two food processing contaminants - acrylamide and furan - in a total of 100 beers produced in Latvia. Mycotoxins were detected by high-performance liquid chromatography (HPLC) coupled with time-of-flight mass spectrometry, acrylamide by HPLC coupled with quadrupole-Orbitrap mass spectrometry, and furan by headspace gas chromatography-mass spectrometry. The most frequently occurring mycotoxins were HT-2 and deoxynivalenol (DON), which were detected in 52% and 51% of the analysed samples. The highest content was observed for DON, reaching the maximum of 248 µg kg -1 . Furan was ubiquitous, and 74% of the samples contained acrylamide. In terms of the estimated exposure, the biggest potential risk was identified for HT-2 representing more than 11% of tolerable weekly intake. The margin of exposure approach indicated the exposure to furan through beer as significant, this parameter being close to the critical limit.

An ultra-sensitive mass spectrometric confirmation and quantification method for the determination of selected fluoroquinolones-enrofloxacin and its main metabolite ciprofloxacin-was developed and validated in poultry meat samples. The achieved limits of quantification were 1 ng kg -1 for enrofloxacin and 10 ng kg -1 for ciprofloxacin. The analysis of 40 retail poultry samples originating from Estonia, Latvia, Lithuania, Poland and France revealed that 93% of samples contained residues of enrofloxacin in the range from 3.3 to 1126 ng kg -1 . Previous studies have shown high levels of antimicrobial resistance to fluoroquinolones, particularly in Campylobacter spp. and various faecal indicators isolated from broiler meat. Consequently, the revealed widespread usage of fluoroquinolones in the poultry industry may result in the further emergence of antimicrobial resistance of Campylobacter in the food chain.

The aim of this study was to investigate the influence of additives such as plants belonging to Lamiaceae family (Thymus vulgaris, Carum carvi, Origanum vulgare, Ocimum basilicum, and Coriandrum sativum), scalded flour (SF) or scalded flour fermented with Lactobacillus plantarum LUHS135 (SFFLp) on the quality and acrylamide formation in wheat bread. The formation of acrylamide and bread quality significantly depended on the king of plants used and the amount of SF and SFFLp used. The additives of T. vulgaris and SF increased the content of acrylamide by 3.4-fold in comparison with bread prepared without SF, whereas the addition of SFFLp significantly reduced the content of acrylamide in bread, especially using 5% of SFFLp supplemented with O. vulgare and 15% of SFFLp supplemented with C. sativum (respectively by 40% and 29.4%) therefore could be recommended for safer bread production., Practical Application: The addition of 5% (from total wheat flour content) of scalded wheat flour fermented with Lactobacillus plantarum LUHS135 strain (SFFLp) with Origanum vulgare addition, and 5% or 10% of SFFLp prepared with Ocimum basilicum, and 15% of SFFLp prepared with Coriandrum sativum significantly reduce the content of acrylamide in wheat bread, therefore could be recommended for safer bread production., (© 2018 Institute of Food Technologists®.)

Pesticide treatments before and during the flowering of honey bee forage crops may lead to residues in honey. In northern regions oilseed rape belongs to the main forage crops that is mostly cultivated by means of intensive agriculture, including several pesticide treatments. However, in addition to the focal forage crops, pesticides from non-forage crops can spread to wild flowers around fields, and thus the residues in honey would reflect the whole range of pesticides used in the agricultural landscape. The aim of our study was to clarify which currently used pesticides are present in honey gathered from heterogeneous agricultural landscapes after the end of flowering of oilseed crops. Honey samples (N = 33) were collected from beehives of Estonia during 2013 and 2014, and analysed for residues of 47 currently used agricultural pesticides using the multiresidue method with HPLC-MS/MS and GC-MS and a single residue method for glyphosate, aminopyralid and clopyralid. Residues of eight different active ingredients with representatives from all three basic pesticide classes were determined. Although no correlation was detected between the cumulative amount of pesticide residues and percent of oilseed crops in the foraging territory, most of the residues are those allowed for oilseed rape treatments. Among all pesticides, herbicide residues prevailed in 2013 but not in 2014. Despite the relatively small agricultural impact of Estonia, the detected levels of pesticide residues sometimes exceeded maximum residue level; however, these concentrations do not pose a health risk to consumers, also acute toxicity to honey bees would be very unlikely., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

Different lactic acid bacteria (LAB) from spontaneous wheat sourdough were isolated, identified, and characterized by their growth, acidification rate, and carbohydrate metabolism. The combinations of isolated LAB (Pediococcus pentosaceus LUHS183 and Leuconostoc mesenteroides LUHS242, P. pentosaceus LUHS183 and Lactobacillus brevis LUHS173, P. pentosaceus LUHS183 and Enterococcus pseudoavium LUHS 234, P. pentosaceus LUHS183 and Lactobacillus curvatus LUHS51, Lactobacillus plantarum LUHS135 and L. curvatus LUHS51, L. plantarum LUHS135 and P. pentosaceus LUHS183) were used for wheat sourdough production, and the effects of LAB fermentation in sourdoughs on wheat bread quality parameters and acrylamide formation were evaluated. All of the tested strains (except E. pseudoavium LUHS 234) were able to ferment l-arabinose, d-ribose, d-galactose, d-fructose, and d-maltose and showed high tolerance to acidic conditions. The highest overall acceptability (135.8 ± 5.5 mm) was found in the bread produced with L. plantarum and P. pentosaceus sourdough. This group of bread also showed the highest shape coefficient (2.59 ± 0.02), the highest specific volume (3.40 ± 0.03 cm 3 /g), the highest porosity (76.6 ± 0.3%), and the highest moisture content (33.7%). Selected sourdoughs reduced acrylamide content in bread samples by 29.5% (sourdough prepared with P. pentosaceus and L. mesenteroides) to 67.2% (sourdough prepared with P. pentosaceus and L. curvatus). These cultures potentially can be used to reduce acrylamide in breads., Practical Application: The data of this study have practical applications. L. plantarum and P. pentosaceus sourdoughs increases overall acceptability, specific volume, and porosity of wheat bread. Besides the fact that sourdoughs produced by using combinations of selected LAB strains improved the quality parameters of bread, fermentation with prepared sourdoughs also reduced the acrylamide content in wheat bread samples by 29.5% (sourdough prepared with P. pentosaceus and L. mesenteroides) to 67.2% (sourdough prepared with P. pentosaceus and L. curvatus)., (© 2017 Institute of Food Technologists®.)