Rugged Large Volume Injection for Sensitive Capillary LC-MS Environmental Monitoring

A rugged and high throughput capillary column (cLC) LC-MS switching platform using large volume injection and on-line automatic filtration and filter back-flush (AFFL) solid phase extraction (SPE) for analysis of environmental water samples with minimal sample preparation is presented. Although narrow columns and on-line sample preparation are used in the platform, high ruggedness is achieved e.g. injection of 100 non-filtrated water samples would did not result in a pressure rise/clogging of the SPE/capillary columns (inner diameter 300 µm). In addition, satisfactory retention time stability and chromatographic resolution were also features of the system. The potential of the platform for …

Simultaneous screening and quantification of aminoglycoside antibiotics in honey using mixed-mode liquid chromatography with quadrupole time-of-flight mass spectroscopy with heated electrospray ionization

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…

Changes in the free amino acids and the biogenic amine contents during lactic acid fermentation of different lupin species

Summary The aim of the work was to evaluate the profile of free amino acids (FAA) as the possible precursors of biogenic amines (BAs) in different varieties and hybrid lines of Lupinus luteus and Lupinus angustifolius and its changes during fermentation. Lupins have high amounts of FAA, and therefore, significant contents of BAs by the action of bacterial amino acid decarboxylases can be formed. In view of this, the effect of three Pediococcus pentosaceus strains KTU05-8, KTU05-9 and KTU05-10 on BA formation during lupin fermentation was studied. The formation of BAs was monitored during 48-h fermentation at solid-state conditions and compared with that in samples after submerged fermentati…

Mycotoxins in herbal teas marketed in Latvia and dietary exposure assessment

The occurrence of 12 mycotoxins has been analysed by liquid chromatography - time of flight mass spectrometry in the batch of 60 herbal teas purchased from drugstores in Latvia. Among the dry tea samples, 90% were positive for one to eight mycotoxins. Enniatin B and deoxynivalenol (DON) were the most frequently detected mycotoxins in 55% and 45% of the samples, respectively. DON reached the highest level, from 129 µg kg-1 in herbal blend to 5,463 µg kg-1 in wormwood tea. Ochratoxin A (OTA) and aflatoxin B1 (AFB1) were found in 10% and 20% of the samples at the concentrations ranged between 2.99-30.3 µg kg-1 and 3.40-23.7 µg kg-1. Studies of the tea infusion process indicated that 32-100% of…

The occurrence of Dechlorane Plus and related norbornene-based flame retardants in Baltic wild salmon (Salmo salar)

Twenty five Baltic wild salmon (Salmo salar) specimens were analysed for the content of Dechlorane-related compounds (DRCs). Out of the ten analysed DRCs, seven compounds were detected in the muscle tissues of salmon, including Dechlorane (Dec) 602, Dec 603, syn- and anti-stereoisomers of Dechlorane Plus (DP), Dechlorane Plus monoadduct (1,3-DPMA), hexachlorocyclopentadienyl-dibromocyclooctane (DBHCTD), and Mirex. The concentrations of Dec 604 and two DP dechlorinated compounds - decachloropentacyclooctadecadiene (Cl10DP) and undecachloropentacyclooctadecadiene (Cl11DP) - were below the limit of detection in all samples. The aggregated concentrations of DRCs (ΣDRC) were in the range of 551-…

Toxicity assessment and biodegradation potential of water-soluble sludge containing 2,4,6-trinitrotoluen

The water-soluble phase of trinitrotoluene-containing sludge (SLP) was characterized with regard to trinitrotoluene (TNT) concentration, ecotoxicity, and a model biodegradation experiment as evaluation criteria for further development of appropriate treatment technologies. SLP contained 67.8 mg TNT/l. The results of germination and root-elongation tests indicated that SLP had a species-specific phytotoxic effect. The results of a 21 day degradation experiment demonstrated TNT conversion to 4-amino-2,6-DNT and 2-amino-4,6-DNT, with a simultaneous reduction in the total concentration of nitroaromatics. Addition of inoculum stimulated the TNT degradation process. The presence of the sludge sol…

A reliable screening of mycotoxins and pesticide residues in paprika using ultra-high performance liquid chromatography coupled to high resolution Orbitrap mass spectrometry

Abstract In this study, an ultra-high performance liquid chromatography (UHPLC) coupled to a high resolution Orbitrap mass spectrometry (Orbitrap-HRMS) was demonstrated as a promising technique in high-throughput method development for the routine analysis and contamination control of mycotoxins and pesticide residues in spices. The method was applied for the analysis of fifty ground paprika samples containing blends of sweet and hot paprika harvested in Brazil and China. The efficiency and detection sensitivity of the used UHPLC-Orbitrap-HRMS technique were compared to the results obtained using a triple quadrupole tandem mass spectrometric detector (UHPLC-QqQ-MS/MS). The values of recover…

Effect of lactic acid fermentation of lupine wholemeal on acrylamide content and quality characteristics of wheat-lupine bread

The effect of supplementing wheat flour at a level of 15% with lupine (Lupinus angustifolius L.) wholemeal fermented by different lactic acid bacteria on acrylamide content in bread crumb as well as on bread texture and sensory characteristics was analysed. The use of fermented lupine resulted in a lower specific volume and crumb porosity of bread on an average by 14.1% and 10.5%, respectively, while untreated lupine lowered the latter parameters at a higher level (30.8% and 20.7%, respectively). The addition of lupine resulted in a higher by 43.3% acrylamide content compared to wheat bread (19.4 µg/kg dry weight (d.w.)). Results showed that acrylamide was significantly reduced using proteo…

Recent applications of carbonaceous nanosorbents for the analysis of mycotoxins in food by liquid chromatography: a short review

Carbonaceous nanomaterials (multi-walled carbon nanotubes (MWCNTs), graphene, and graphene oxide (GO)) have attracted attention over the last decade as adsorbents suitable for the analysis of organic and inorganic pollutants. In the present paper we review methods of mycotoxin analysis that involve sample extraction with carbonaceous nanosorbents, reported from 2011 onwards. Recent studies have highlighted the advantages of magnetically modified MWCNTs and GO in mycotoxin analysis, which may enable sample isolation through magnetic separation, reduce the interaction of nanoparticles, and enhance the recovery of analytes. The papers covered in this review point to promising applications of …

The application of phospholipid removal columns and ultra-high performance liquid chromatography-tandem quadrupole mass spectrometry for quantification of multi-class antibiotics in aquaculture samples.

In this study a robust and sensitive method based on a proposed sample purification procedure, using zirconia-coated Phree™ columns and analysis by ultra-high performance liquid chromatography with triple quadrupole tandem mass spectrometry are presented for the assessment of multi-class antibiotics in farmed fish species. The sample preparation procedure benefited from combined precipitation of proteins and selective removal of phospholipids by Phree™ columns, resulting in a high sensitivity of the method (LOQ 0.3-9mgkg(-1)). The in-house validation results (precision, repeatability, decision limit CCα, detection capability CCβ, etc.) indicate that the elaborated method is fully suitable f…

Effect of fermented Helianthus tuberosus L. tubers on acrylamide formation and quality properties of wheat bread

Abstract The main focus in this study was to investigate the effects on wheat bread safety and quality due to addition of Helianthus tuberosus L. (JA) tubers, fermented by different lactic acid bacteria (LAB) strains (Pediococcus acidilactici KTU05-7, Pediococcus pentosaceus KTU05-8, P. pentosaceus KTU05-9, Lactobacillus sakei KTU05-6, P. pentosaceus KTU05-10). We found experimentally that JA tubers fermented with LAB contained more L(+) than D(−) lactic acid, which resulted in safer products than by spontaneous treatment. The concentrations of biogenic amines in all analysed fermented JA products were far below levels causing a health risk, while the products fermented with LAB contained l…

LC-MS/MS characterisation and determination of dansyl chloride derivatised glyphosate, aminomethylphosphonic acid (AMPA), and glufosinate in foods of plant and animal origin.

Abstract 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 C18 stationary phase. The dansyl d…

The role of nutrients in the biodegradation of 2,4,6-trinitrotoluene in liquid and soil.

The widely used explosive 2,4,6-trinitrotoluene (TNT) has residues that are potentially explosive, toxic, and mutagenic. TNT and other explosives can be degraded by microorganisms; however, biostimulation is needed for process efficiency. To investigate the effectiveness of using biostimulation to degrade TNT, we added varying concentrations of a nutrient amendment consisting of inorganic salts, plant extracts, and molasses to soil and liquid media. For the inoculum we used a consortium of bacteria AM 06 that had exhibited the ability to degrade TNT and which had been previously isolated from explosives-contaminated soils. Phylogenetically, the clones clustered into seven different genera: …

Ultra high performance liquid chromatography-time-of-flight high resolution mass spectrometry in the analysis of hexabromocyclododecane diastereomers: method development and comparative evaluation versus ultra high performance liquid chromatography coupled to Orbitrap high resolution mass spectrometry and triple quadrupole tandem mass spectrometry.

An efficient ultra high performance liquid chromatography (UHPLC)-time-of-flight high resolution mass spectrometry (TOF-HRMS) method was elaborated for the determination of hexabromocyclododecane (HBCD) diastereomers in fish samples and compared against UHPLC-Orbitrap-HRMS and UHPLC-triple quadrupole (QqQ) tandem MS (MS/MS) techniques. The TOF-HRMS analyzer was operated at high resolution (>10000 full width at half maximum (FWHM)) with scanning the m/z range from 600 to 700, to achieve picogram quantitation limits. The effects of various operational parameters on the instrumental response were systematically investigated. Evaluation of the influence of sample clean-up procedure steps on sig…

Improved sensitivity of ochratoxin A analysis in coffee using high-performance liquid chromatography with hybrid triple quadrupole-linear ion trap mass spectrometry (LC-QqQLIT-MS/MS)

A novel and sensitive method utilising high-performance liquid chromatography coupled to triple quadrupole-linear ion trap mass spectrometry (LC-QqQLIT-MS/MS) was developed in order to analyse the content of ochratoxin A (OTA) in coffee samples. The introduction of the triple-stage MS scanning mode (MS(3)) has been shown to increase greatly sensitivity and selectivity by eliminating the high chromatographic baseline caused by interference of complex coffee matrices. The analysis included the sample preparation procedure involving extraction of OTA using a methanol-water mixture and clean-up by immunoaffinity columns and detection using the MS(3) scanning mode of LC-QqQLIT-MS/MS. The propose…

Effect of heating method on the microbial levels and acrylamide in corn grits and subsequent use as functional ingredient for bread making

Abstract Cereal by-products represent abundant and low-cost resources of nutrients. The study is dedicated to the development of a rapid method for the treatment of corn grits to obtain value added ingredients for breadmaking. The infrared irradiation (IR) at 76 °C and 90 °C and vacuum microwave (VM) heating at 60 °C have been applied for stabilization of corn grits. The corn grit particles were fractionated by size and it was found that the particle size fraction significantly (p

Parameters of rye, wheat, barley, and oat sourdoughs fermented withLactobacillus plantarumLUHS135 that influence the quality of mixed rye-wheat bread, including acrylamide formation

A Lactobacillus plantarum strain was used for the production of rye, wheat, barley, and oat sourdoughs, and the influence of different sourdoughs on mixed rye–wheat bread quality parameters and acrylamide formation was evaluated. L. plantarum LUHS135 demonstrated versatile carbohydrate metabolism, good growth and acidification rates, and the ability to excrete amylolytic and proteolytic enzymes in various cereal sourdoughs. The same starter and different cereal substrates allow to produce sourdoughs showing different characteristics. The type of sourdough and its quantity had significant influence on acrylamide content in bread (P ≤ 0.0001), and using 5% or 10% of wheat sourdough, 5%, 15%, …

Evaluation of analytical performance of gas chromatography coupled with atmospheric pressure chemical ionization Fourier transform ion cyclotron resonance mass spectrometry (GC-APCI-FT-ICR-MS) in the target and non-targeted analysis of brominated and chlorinated flame retardants in food.

Abstract A new analytical method was established and validated for the analysis of eighteen halogenated flame retardants (HFRs)in food products. Gas chromatography (GC) coupled to Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) employing atmospheric pressure chemical ionization (APCI) was used for the identification and quantitation of contaminants. Intra-laboratory validation of the method was performed with respect to recovery, repeatability, linear calibration ranges, instrumental and method limits of quantitation (i-LOQ and m-LOQ), and trueness was verified where possible by analysis of reference materials (RMs). The validation results indicated recoveries of ana…

Removal of pharmaceuticals from municipal wastewaters at laboratory scale by treatment with activated sludge and biostimulation.

Abstract Municipal wastewater containing 21 pharmaceutical compounds, as well as activated sludge obtained from the aeration tank of the same wastewater treatment plant were used in lab-scale biodegradation experiments. The concentrations of pharmaceutical compounds were determined by high-performance liquid chromatography coupled to Orbitrap high-resolution mass spectrometry and ranged from 13.2 ng/L to 51.8 μg/L. Activated sludge was characterized in the terms of phylogenetic and catabolic diversity of microbial community, as well as its morphology. Proteobacteria (24.0%) represented the most abundant phylum, followed by Bacteroidetes (19.8%) and Firmicutes (13.2%). Bioaugmentation of was…

Mycotoxins in cereals and pulses harvested in Latvia by nanoLC-Orbitrap MS

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 th…

The contribution of P. acidilactici, L. plantarum, and L. curvatus starters and L-(+)-lactic acid to the acrylamide content and quality parameters of mixed rye - Wheat bread

Abstract Lactic acid bacteria (LAB) from spontaneous rye sourdough were isolated, identified, and characterized by their growth, acidification rate, and carbohydrate metabolism. The isolated LAB were used for production of rye sourdough, and the influence of sourdough on mixed rye - wheat bread quality and acrylamide formation was evaluated. In addition, comparative studies by using acidification with L-(+)-lactic acid for mixed rye – wheat bread production were performed. Isolated LAB (P. acidilactici, L. plantarum, L. curvatus) demonstrated versatile carbohydrate metabolism, grown at 30 °C and 37 °C, and acidic tolerance. When the isolated strains were used for rye sourdough production, t…

Determination of pharmaceutical residues and assessment of their removal efficiency at the Daugavgriva municipal wastewater treatment plant in Riga, Latvia

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 i…

The development and validation of a rapid method for the determination of antimicrobial agent residues in milk and meat using ultra performance liquid chromatography coupled to quadrupole – Orbitrap mass spectrometry

Abstract A new multi-class method has been developed for the identification and quantification of the residues of 26 antibiotics from different classes (sulfonamides, macrolides, tetracyclines, penicillins, and quinolones) in milk and meat by ultra performance liquid chromatography coupled to hybrid quadrupole – high resolution Orbitrap mass spectrometry (UPLC–qOrbitrap). The sample preparation included extraction of two analytical portions with acetonitrile and 5% trichloroacetic acid, respectively, followed by centrifugation and filtration. The method was validated over three days at 50% of MRL (maximum residue limit) set in the European Union. Experiments on spiked meat and milk samples …

Occurrence of Brominated Persistent Organic Pollutants (PBDD/DFs, PXDD/DFs, and PBDEs) in Baltic Wild Salmon (Salmo salar) and Correlation with PCDD/DFs and PCBs

The contamination profiles of polybrominated dibenzo-p-dioxins (PBDDs), dibenzofurans (PBDFs), diphenyl ethers (PBDEs), and mixed monobromo/chloro dibenzo-p-dioxins (PXDDs) and dibenzofurans (PXDFs) were determined in the tissue of Baltic wild salmon and compared with those of polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs), and biphenyls (PCBs). Out of the analyzed PXDD/DFs, only the 3-B-2,7,8-triCDF was detected (in the concentration range of 0.039-0.075 pg g(-1) fresh weight (f.w.)). The toxic equivalents (TEQs) for analyzed PBDD/DFs (0.074-0.142 pg TEQ g(-1) f.w.) were found to contribute on average 2.1% to the total PCDD/DF-PBDD/DF-TEQ. The total concentrations of 27 P…

Multi-analyte method for the analysis of legacy and alternative brominated and chlorinated flame retardants in food products of animal origin using gas chromatography - magnetic sector high resolution mass spectrometry

Abstract An analytical method was developed and validated for the analysis of 32 halogenated flame retardants (HFRs), including 13 polybrominated diphenyl ethers (PBDEs), 9 dechlorane-related compounds (DRCs) and 10 of the so-called alternative BFRs in food samples of animal origin. Gas chromatography (GC) coupled with magnetic sector high resolution mass spectrometry (HRMS) was used for the instrumental analysis. Intralaboratory validation of the developed method was performed in terms of recovery, repeatability, linear calibration ranges, instrumental and method limits of quantitation (i-LOQ and m-LOQ). Where possible, trueness was verified by the analysis of reference materials (RMs). Fo…

Antifungal activity of lactic acid bacteria and their application for Fusarium mycotoxin reduction in malting wheat grains

Abstract This study mainly focuses on finding a strategy for reduction of Fusarium mycotoxin in malting wheat grains, predominantly used in the production of beverages and certain baked goods. The effect of treatment with lactic acid bacteria (LAB) on deoxynivalenol (DON), zearalenone (ZEN), T-2 and HT-2 toxins contained in malting wheat grains was studied. Additionally, the impact of bio-treatment with bio-products based on cheese whey permeate previously fermented with LAB on microbial contamination and germination capacity of grains was studied. Treatment with Lactobacillus sakei KTU05-6, Pediococcus acidilactici KTU05-7, and Pediococcus pentosaceus KTU05-8, KTU05-09, and KTU05-10 strain…

Application of hydrolases and probiotic Pediococcus acidilactici BaltBio01 strain for cereal by-products conversion to bioproduct for food/feed

The aim of this study was to apply the enzymatic treatment and fermentation by Pediococcus acidilactici BaltBio01 strain for industrial cereal by-products conversion to food/feed bioproducts with high amount of probiotic lactic acid bacteria (LAB). LAB propagated in potato media and spray-dried remained viable during 12months (7.0 log10 cfu/g) of storage and was used as a starter for cereal by-products fermentation. The changes of microbial profile, biogenic amines (BAs), mycotoxins, lactic acid (Lþ/D), lignans and alkylresorcinols (ARs) contents in fermented cereal by-product were analysed. Cereal by-products enzymatic hydrolysis before fermentation allows to obtain a higher count of LAB d…

Application of Wastewater-Based Epidemiology for Tracking Human Exposure to Deoxynivalenol and Enniatins

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 deoxyniv…

New perspectives on diastereoselective determination of hexabromocyclododecane traces in fish by ultra high performance liquid chromatography-high resolution orbitrap mass spectrometry.

a b s t r a c t A new analytical method is presented for diastereoisomer-specific identification and quantitation of hexabromocyclododecanes (HBCD) in fish samples. The method is based on extraction of the target analytes from samples with a mixture of organic solvents, with further three-stage clean-up includ- ing destructive removal of matrix components with sulphuric acid and acid-impregnated silica gel, and Florisil adsorption column chromatography. Ultra high performance liquid chromatography (UPLC) cou- pled with high resolution (HR) Orbitrap mass spectrometry featuring heated electrospray ionization (HESI-II) interface operated in negative ion mode was employed for the identification…

Plant-based proteinaceous snacks: Effect of fermentation and ultrasonication on end-product characteristics

Abstract The study aimed at the development of a sufficient technology to improve sensory, textural, physical, and microbiological properties of peas snacks (Ps) using solid‐state fermentation (SSF) and submerged fermentation (SMF) with two different lactic acid bacteria (LAB) strains (Lactobacillus casei LUHS210 and Lactobacillus uvarum LUHS245) for 24 hr and ultrasonication (10, 20, and 30 min). To ensure safety of the used technologies, microbiological characteristics and biogenic amines (BAs) content in treated Ps were analyzed. Additionally, a different salt content (3.6 and 1.0 g/100 g) was used for snacks preparation. The obtained results revealed that used treatments reduced enterob…

Determination of pharmaceutical residues in wastewater using high performance liquid chromatography coupled to quadrupole-Orbitrap mass spectrometry

Abstract A multi-class method for the determination of 24 emerging pharmaceutical residues has been developed and validated. The method is based on solid-phase extraction of wastewater samples using Strata-X cartridges followed by high performance liquid chromatography coupled to hybrid quadrupole − Orbitrap high resolution mass spectrometry (HPLC-Q-Orbitrap-HRMS). A single-laboratory validation procedure showed satisfactory analytical performance. The analysis of 21 samples collected at the wastewater treatment plant in Riga revealed the occurrence of 20 compounds of different therapeutic classes. The highest concentration was found for the central nervous system stimulator caffeine − up t…

Lactic Acid Bacteria Isolation from Spontaneous Sourdough and Their Characterization Including Antimicrobial and Antifungal Properties Evaluation

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

Brominated flame retardants and toxic elements in the meat and liver of red deer (Cervus elaphus), wild boar (Sus scrofa), and moose (Alces alces) from Latvian wildlife.

In order to evaluate the contamination status of terrestrial biota in Latvia, muscle and liver tissues of red deer (Cervus elaphus), wild boar (Sus scrofa), and moose (Alces alces) were analyzed for the content of polybrominated diphenyl ethers (PBDE), hexabromocyclododecane (HBCD), tetrabromobisphenol A (TBBPA), as well as cadmium and lead. The highest mean concentrations of PBDEs (46.6pgg-1 wet weight (w.w.)), cadmium (0.95mgkg-1 w.w.), and lead (0.22mgkg-1 w.w.) were observed in the tissues of moose, while the wild boar samples contained the highest levels of HBCD, with the mean concentration equal to 264pgg-1 w.w. in muscle tissues. Generally low mean concentrations of TBBPA from 0.52 t…

Modulation of the nutritional value of lupine wholemeal and protein isolates using submerged and solid-state fermentation with Pediococcus pentosaceus strains

The influence of different factors (submerged and/or solid‐state fermentation, pediococci strain, lupine variety and protein isolation process) on the protein digestibility, total phenolic compounds (TPC) content and radical scavenging activity of Lupinus luteus and angustifolius wholemeal and protein isolates was evaluated. As safety factor, biogenic amines (Bas) formation was analysed. The Pediococcus pentosaceus strains No. 8, No. 9 and No. 10 are suitable starters for lupine wholemeal fermentation and both applied processes (fermentation and protein isolation) increase protein digestibility (by 10%). Higher TPC content in fermented wholemeal can be obtained, compare to isolates. In SMF …

Non-target and suspected-target screening for potentially hazardous chemicals in food contact materials: investigation of paper straws

A non-target screening strategy was developed for the safety evaluation of potentially hazardous chemicals in paper food contact materials (FCMs). A tentative list of suspect analytes was generated using publicly available FCM substance inventories, the presence of contaminants in paper straws was confirmed by high-resolution Orbitrap mass spectrometry. Data-independent and data-dependent MS and MS/MS results for candidate compounds were processed using a workflow including peak detection by deconvolution, blank subtraction, retention time alignment, formula assignment and fragmentation spectra search against spectral libraries followed by

Occurrence of glyphosate in beer from the Latvian market.

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. Significan…

Occurrence and risk assessment of mycotoxins, acrylamide, and furan in Latvian beer.

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 acrylamid…

Potential of an exploitation of acid-tolerant antimicrobial microorganisms evolving enzyme systems for the utilization of dairy by-products and lignocellulosic biomass to lactic acid

Introduction Bioproduction of optically pure lactic acid (LA) has roused interest in the recent years due to its potential application in a wide range of fields, and there is a significant interest to further development of sustainable and cost-effective process. However, the efficient utilization of agro-industrial wastes for LA production still causes considerable challenges. The biotechnological LA production within the targeted cost still required the development of high-performance LA-producing microorganisms and the lowering of the costs of raw materials and fermentation process. Cheap biomass, such as starchy and cellulosic agricultural residues or by-products from the food industry,…

Two-dimensional liquid chromatography - high resolution mass spectrometry method for simultaneous monitoring of 70 regulated and emerging mycotoxins in Pu-erh tea

Macro and Trace Elements in Barley (Hordeum vulgare L.) Breeds in Latvia Depending on Variety, Environment, and Agricultural Practice

Abstract The aim of the study was to determine concentrations of 13 macro and trace elements in different barley genotypes depending on the year of growth (2011, 2012, and 2013) and agricultural practice (conventional/organic). Cd, Pb, Cr, Ni, and Al concentrations were determined by electrothermal atomic absorption spectrometry and K, Na, Zn, Cu, Ca, Mg, Mn, and Fe concentrations by flame atomic absorption spectrometry. Statistically different concentrations of Cr, Cu, and Zn occurred among genotypes; for Ca, Mn, and Fe concentrations between barley grains, grown conventionally and organically; for Cr and Ni concentrations between hulled and hull-less grain and for Cd, Cr, Ni, Cu, Zn, Al, …

Lactic Acid Bacteria Combinations for Wheat Sourdough Preparation and Their Influence on Wheat Bread Quality and Acrylamide Formation

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 a…

Influence of the addition ofHelianthus tuberosusL. fermented with different lactobacilli on acrylamide content in biscuits

Summary The aim of the study was to investigate the effect of the addition of Helianthus tuberosus L. fermented with different lactobacilli (Lactobacillus sakei KTU05-6, Pediococcus acidilactici KTU05-7 and Pediococcus pentosaceus KTU05-9) on acrylamide content in biscuits. Results of study indicated that submerged fermented Helianthus tuberosus L. tubers had the significantly (P ≤ 0.05) lower pH, higher total titratable acidity and from 1.2 to 1.3 times higher protease and from 1.2 to 2.0 higher alpha-amylase activities compared with treated by solid-state fermentation. The acrylamide content in all biscuit samples enriched with submerged fermented Helianthus tuberosus L. was measured lowe…

Influence of the Fermented Feed and Vaccination and Their Interaction on Parameters of Large White/Norwegian Landrace Piglets

The aim of this study was to evaluate the influence of fermented with a newly isolated lactic acid bacteria (LAB) strains combination (Lactobacillus plantarum LUHS122, Lactobacillus casei LUHS210, Lactobacillus farraginis LUHS206, Pediococcus acidilactici LUHS29, Lactobacillus plantarum LUHS135 and Lactobacillus uvarum LUHS245) feed on non-vaccinated (NV) and vaccinated with Circovac porcine circovirus type 2 vaccine (QI09AA07, CEVA-PHYLAXIA Co. Ltd. Sz&aacute

Occurrence of selected per- and polyfluorinated alkyl substances (PFASs) in food available on the European market - A review on levels and human exposure assessment.

Abstract Per- and polyfluorinated alkyl substances (PFASs) are considered emerging persistent organic pollutants, which are chemically, thermally, and biologically stable, or degrade to persistent end products. Dietary intake is considered as one of the main human exposure pathways of these chemicals and, having entered the human body, PFASs are not metabolised and accumulate in tissues, while their toxicological properties may cause various health problems. Several studies on the occurrence of PFASs in various food types have been conducted, including the assessment of dietary exposure. The most important sources were fish, meat, eggs, fruits, and vegetables. Fruits and vegetables recently…

The impact of lactic acid bacteria with antimicrobial properties on biodegradation of polycyclic aromatic hydrocarbons and biogenic amines in cold smoked pork sausages

The influence of surface treatment with lactic acid bacteria (LAB), previously cultivated in an alternative substrate, on the formation of polycyclic aromatic hydrocarbons (PAHs) and biogenic amines (BAs) in cold smoked pork meat sausages was investigated. Moreover, sausages treatment with LAB after the smoking on PAHs content changes was evaluated. Additionally, the inhibitory effects of LAB metabolites on food spoilage bacteria was determined using the agar well diffusion assay method. The metabolites of Pediococcus acidilactici KTU05-7, Pediococcus pentosaceus KTU05-9 and Lactobacillus sakei KTU05-6 strains showed good inhibitory properties against tested pathogenic and food spoilage bac…

The quality of wheat bread with ultrasonicated and fermented by-products from plant drinks production

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…

Rapid determination of pharmaceuticals in wastewater by direct infusion HRMS using target and suspect screening analysis

Abstract A wide-scope screening of active pharmaceutical ingredients (APIs) and their transformation products (TPs) in wastewater can yield valuable insights and pinpoint emerging contaminants that have not been previously reported. Such information is relevant to investigate their occurrence and fate in various environmental compartments. In this study, we explored the applicability of direct infusion high resolution mass spectrometry (DI-HRMS) for comprehensive and rapid detection of APIs and their TPs in wastewater samples. The method was developed using a Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) system and incorporated both wide-scope suspect screening and…

The safety, technological, nutritional, and sensory challenges associated with lacto-fermentation of meat and meat products by using pure lactic acid bacteria strains and plant-lactic acid bacteria bioproducts

Introduction. Lactic acid bacteria (LAB) are the most popular microbial cultures used in the preparation of fermented foods (Bintsis, 2018). Due to their wide range of antimicrobial activity, LAB have been shown to improve safety, nutritional and sensory characteristics, control fermentation by microflora and speed maturation, as well as increase the shelf life of products (Des et al., 2018). Recently, as a new approach for the application of technological starters, great interest has been concentrated on their biodegradation and/or absorption properties of non-desirable chemical compounds, and it was reported that LAB can reduce polycyclic aromatic hydrocarbons (PAHs) and heterocyclic arom…

Emerging brominated flame retardants and dechlorane-related compounds in European eels (Anguilla anguilla) from Latvian lakes

Abstract Fifteen halogenated flame retardants (HFRs) including seven emerging brominated flame retardants (EBFRs) and eight dechlorane-related compounds (DRCs) were analyzed in eels (Anguilla anguilla) sampled from five Latvian lakes. Out of the seven EBFRs, hexabromocyclododecane (HBCD) and decabromodiphenyl ethane (DBDPE) were found in eels in quantifiable concentrations, up to 6.58 and 33.0 ng g−1 lipid weight (l.w.), respectively. The mean total concentration of DRCs (∑DRC) in the samples was 0.62 ng g−1 l.w. and the geographical distribution of DRC contamination was nearly uniform among the selected lakes. Dechlorane 602 (Dec 602) was the predominant component, whereas the composition …

Application of Pediococcus acidilactici LUHS29 immobilized in apple pomace matrix for high value wheat-barley sourdough bread

The aim of this study was to evaluate the potential use of Pediococcus acidilactici LUHS29 immobilized in apple pomace in case to apply in barley sourdough fermentation for functional bread production. The strain was phenotypically characterized by the growth and acidification rate, carbohydrate metabolism and resistance to acidic conditions. The effect of immobilized bacterial cells on antioxidant properties of barley sourdough and on the acrylamide content in wheat-barley bread was analyzed. The phenotypic and molecular testing indicates the P. acidilactici having a versatile carbohydrate metabolism and acid resistance, showing 42.7% of viable cells surviving after incubation at low pH as…

The effects of woodchip- and straw-derived biochars on the persistence of the herbicide 4-chloro-2-methylphenoxyacetic acid (MCPA) in soils

Sorption and degradation are the primary processes controlling the efficacy and runoff contamination risk of agrochemicals. This study assessed the influence of two biochars, made from woodchips and straw at a pyrolysis temperature of 725°C and applied to a loamy sand and a sandy soil in the concentration of 5.3 g 100 g(-1) sandy soil and 4.1 g 100 g(-1) loamy sand soil, or 53 t ha(-1) for both soil types, on degradation of the herbicide 4-chloro-2-methylphenoxyacetic acid (MCPA). Soils were spiked with 50 mg MCPA kg(-1) soil. In the sandy soil, significantly more MCPA remained after 100 days if amended with straw-derived biochar in comparison to wood-derived biochar. Both biochars types si…

A rapid and sensitive method for the control of selected regulated and emerging mycotoxins in beer

A fast method using automated online solid-phase extraction (SPE) coupled to liquid-chromatography/high resolution mass spectrometric (LC-HRMS) detection for the determination of 12 mycotoxins in beer was developed and fully validated according to the performance criteria set in the European Union (EU) guidelines. Mycotoxin detection was achieved by full-scan HRMS with electrospray ionisation in positive ion mode within 13 min. No significant matrix interferences were observed. The lowest limits of detection (LODs) were achieved for emerging mycotoxins (beauvericin and enniatins) and ochratoxin A at levels between 0.01 and 0.02 μg/l, while the overall LODs were in the range of 0.01-0.30 μg…

The effect of Pediococcus acidilactici and Lactobacillus sakei on biogenic amines formation and free amino acid profile in different lupin during fermentation

Abstract The effect of Pediococcus acidilactici and Lactobacillus sakei strains on biogenic amines (BAs) formation during submerged and solid state fermentation of Lupinus luteus and Lupinus angustifolius was analysed. The composition of lupin seeds was evaluated and the influence of fermentation on free amino acid (FAA) profile was investigated. The highest protein and carbohydrate contents were found in L. luteus var. ‘Vilciai’, the highest carbohydrate contents – in L. angustifolius hybrid lines No. 1701 and No. 1800, and fat – in L. angustifolius hybrid lines No. 1700, No. 1703 and No. 1734. The interaction between the fermentation method, the bacterial strains used and lupin varieties …

The effects of ultrasonication, fermentation with Lactobacillus sp., and dehydration on the chemical composition and microbial contamination of bovine colostrum.

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 …

The application of headspace gas chromatography coupled to tandem quadrupole mass spectrometry for the analysis of furan in baby food samples.

Abstract Selective methodology employing a tandem quadrupole mass spectrometer coupled to a gas chromatograph with headspace autosampler (HS-GC–MS/MS) was elaborated in this study. Application of the elaborated procedure resulted in a limit of detection of 0.021 μg kg −1 and a limit of quantification of 0.071 μg kg −1 . The mean recoveries during in-house validation ranged from 89% to 109%, and coefficients of variation for repeatability ranged from 4% to 11%. The proposed analytical method was applied for monitoring the furan content of 30 commercial baby food samples available on the Latvian retail market. The level of furan found in these samples varied from 0.45 to 81.9 μg kg −1 , indic…

Challenges of Lactobacillus fermentation in combination with acoustic screening for deoxynivalenol and deoxynivalenol conjugates reduction in contaminated wheat - based products

Abstract This study was dedicated to apply biological treatment using Lactobacillus (LAB) fermentation separately or in combination with an acoustic screening method for the prevention of mycotoxins in Fusarium spp. contaminated wheat-based products. Wheat samples of different contamination were treated separately using antimicrobial LAB strains (L. casei, L. plantarum, L. paracasei, and L. uvarum) and the changes on the level of deoxynivalenol (DON) and its conjugates such as 3-acetyldeoxynivalenol (3-ADON), 15-acetyldeoxynivalenol (15-ADON), and DON-3-β-D-glucoside (D3G)) were evaluated using UHPLC-QqQ-MS/MS and UHPLC-Orbitrap-HRMS. Additionally, an acoustic device was used to analyse DON…

Challenges Associated with Byproducts Valorization—Comparison Study of Safety Parameters of Ultrasonicated and Fermented Plant-Based Byproducts

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 phys…

Brominated, chlorinated and mixed brominated/chlorinated persistent organic pollutants in European eels (Anquilla anquilla) from Latvian lakes

Fifty-eight European eel (Anquilla anquilla) specimens collected from five Latvian lakes were investigated for six groups of persistent organic pollutants (POPs), including polychlorinated, polybrominated and mixed bromo-chloro dibenzo-p-dioxins and dibenzofurans (PCDD/DFs, PBDD/DFs and PXDD/DFs), polychlorinated and mixed bromo-chloro biphenyls (PCBs and PXBs) and polybrominated diphenyl ethers (PBDEs). PCDD/DFs and PCBs were found to occur in the range 0.85–15.8 pg Total-WHO2005-TEQ g−1 f.w., and concentrations in most of the samples were below the maximum levels specified in European Commission Regulation (EU) No. 1259/2011. The summed concentrations of 27 PBDEs (∑PBDE) and 16 non-dioxin…

Lactobacillus plantarum LUHS135 and paracasei LUHS244 as functional starter cultures for the food fermentation industry: Characterisation, mycotoxin-reducing properties, optimisation of biomass growth and sustainable encapsulation by using dairy by-products

Abstract Lactobacillus plantarum LUHS135 and Lactobacillus paracasei LUHS244 from fermented cereals were isolated and their properties (carbohydrate metabolism, gas production, ability to survive at a low pH values, growth performance at different temperatures, antimicrobial properties against Pseudomonas aeruginosa, Staphylococcus aureus, Escherichia coli, Salmonella enterica, Corynebacter spp, Klebsiella pneomoniae, Enterococcus faecalis, Bacillus cereus, Proteus mirabilis, Clostridium spp., Streptococcus spp., resistance to antibiotics, and reducing properties for aflatoxin B1, ochratoxin A, HT-2 toxin, T-2 toxin, zearalenone) were evaluated. Also, the possibilities to use dairy by-produ…

Application of Dopant-Assisted Atmospheric Pressure Photoionisation HPLC–MS Method for the Sensitive Determination of Polycyclic Aromatic Hydrocarbons in Dark Chocolate

Multiple food research studies have shown that the polycyclic aromatic hydrocarbon (PAHs) are frequently found in processed cocoa products and chocolate. In a present study a method based on dopant-assisted atmospheric pressure photoionisation (DA-APPI) combined with a liquid chromatography/high-resolution mass spectrometer (HPLC-HRMS) for high-sensitivity analysis of four EU marker PAHs in dark chocolate samples was developed and fully validated according to the performance criteria set in EU guidelines. PAHs detection was achieved by HRMS in positive electrospray ionization mode with toluene used as a dopant to enhance the ionization efficiency of non-polar PAHs. The on-column instrument …

Evaluation of Glyphosate Ecotoxicity and Biodegradability in the Municipal Wastewaters

Glyphosate (G) is a broad-spectrum systemic organophosphate herbicide being widely used to control weeds in agricultural fields and urban areas. Its safety for both human health and aquatic biomes is a subject of wide debate. This study was aimed at evaluating the removal efficiency and ecotoxicity of G based herbicide (GBH) Klinik® (Nufarm, Austria) added to the raw municipal wastewater (WW) in a lab-scale model column system. The effect of oxide ceramics as a filtering medium (treatment „B”), as well as activated sludge and nutrients (treatment „C”) was compared with the control columns, which contained only WW (treatment „A”). After 72h treatment of WW spiked with 100 mg/L G, the lowest …

Determination of Fungi and Multi-Class Mycotoxins in Camelia sinensis and Herbal Teas and Dietary Exposure Assessment

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 &times

Nutraceuticals in gummy candies form prepared from lacto-fermented lupine protein concentrates, as high-quality protein source, incorporated withCitrus paradiseL. essential oil and xylitol

The Influence of Scalded Flour, Fermentation, and Plants Belonging to Lamiaceae Family on the Wheat Bread Quality and Acrylamide Content

The aim of this study was to investigate the influence of additives such as plants belonging to Lamiaceaefamily (Thymus vulgaris, Carum carvi, Origanum vulgare, Ocimum basilicum, and Coriandrum sativum), scalded flour (SF) or scalded flour fermented with Lactobacillus plantarumLUHS135 (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. vulgarisand 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,…

Phenolic profiles of raw mono- and polyfloral honeys from Latvia

Abstract The phenolic compound profiles of 393 raw mono- and polyfloral Latvian honey samples were investigated using a targeted ultra-high performance liquid chromatography-high resolution mass spectrometry (UHPLC-HRMS) method. This strategy allowed simultaneous determination of the content of 11 phenolic acids, 18 flavonoids, 2 plant hormones, and 3 water-soluble vitamins in honey samples of botanically diverse origin, including buckwheat (Fagopyrum esculentum), heather (Calluna vulgaris), linden (Tilia cordata), and rapeseed (Brassica napus). Honey samples were collected directly from the beekeepers and were analyzed in their natural, raw form. A selective high-throughput analysis was im…

Development of a Rapid Method for the Determination of Phenolic Antioxidants in Dark Chocolate Using Ultra Performance Liquid Chromatography Coupled to Orbitrap Mass Spectrometry

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 stand…

Occurrence of polybrominated diphenyl ethers, perfluorinated compounds, and nonsteroidal anti-inflammatory drugs in freshwater mussels from Latvia.

Abstract The occurrence of polybrominated diphenyl ethers (PBDE), perfluorinated compounds (PFC), and nonsteroidal anti-inflammatory drugs (NSAID) in Latvian freshwater ecosystems was evaluated by using filter-feeding mussels as bioindicators. Twenty four samples of mussels were collected from freshwater bodies throughout the territory of Latvia during the summer of 2017. PBDE contamination was ubiquitous, reaching the highest total concentration of 193.2 pg g−1 w.w. BDE-209 was the most abundant compound, followed by penta-BDE components BDE-49, -100, −99, −153, −154, and −47 in decreasing order. The levels of PFCs in Latvian mussels were generally lower than those reported from other regi…

Perspectives of lupine wholemeal protein and protein isolates biodegradation

Lupine (Lupinus angustifolius L.) protein (in wholemeal and protein isolates) was biodegraded using Pediococcus acidilactici in submerged and solid‐state fermentation conditions. The changes in the molecular weight of lupine protein fractions, amino acid (AA) profile, biogenic amine formation, antimicrobial and antioxidant properties, and protein digestibility in vitro and in vivo (in Wistar rats) were evaluated. After biotreatment, lower molecular weight peptides (from 10 to 20 kDa) were established, and the free AA content increased. Biodegradation improved the antioxidant properties, modulated the antimicrobial properties, and led to higher in vitro and in vivo digestibility and function…

Changes of bioactive compounds in barley industry by‐products during submerged and solid state fermentation with antimicrobial Pediococcus acidilactici strain LUHS29

Abstract In this study, changes of bioactive compounds (crude protein (CP), crude fat (CF), dietary fiber (DF), fatty acids (FAs), free amino acids (FAAs), phenolic compounds (PCs), biogenic amines (BAs), lignans, and alkylresorcinols) in barley industry by‐products (BB) during submerged and solid state fermentation (SSF) with Pediococcus acidilactici were analyzed. It was established that both fermentation conditions reduce the CP and CF content in BB (by 25.8% and 35.9%, respectively) and increase DF content (on average by 25.0%). Fermentation increases the oleic, arachidic, eicosadienoic, behenic, and lignoceric FA in BB samples. The highest total BA content was found in untreated sample…

MICROBIAL COMMUNITY CHANGES IN TNT SPIKED SOIL BIOREMEDIATION TRIAL USING BIOSTIMULATION, PHYTOREMEDIATION AND BIOAUGMENTATION

Trinitrotoluene (TNT), a commonly used explosive for military and industrial applications, can cause serious environmental pollution. 28-day laboratory pot experiment was carried out applying bioaugmentation using laboratory selected bacterial strains as inoculum, biostimulation with molasses and cabbage leaf extract, and phytoremediation using rye and blue fenugreek to study the effect of these treatments on TNT removal and changes in soil microbial community responsible for contaminant degradation. Chemical analyses revealed significant decreases in TNT concentrations, including reduction of some of the TNT to its amino derivates during the 28-day tests. The combination of bioaugmentation…

Development and optimization of confirmatory liquid chromatography—Orbitrap mass spectrometry method for the determination of 17 anticoccidials in poultry and eggs

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. Val…

Analytical capabilities of high performance liquid chromatography – Atmospheric pressure photoionization – Orbitrap mass spectrometry (HPLC-APPI-Orbitrap-MS) for the trace determination of novel and emerging flame retardants in fish

A new analytical method was established and validated for the analysis of 27 brominated flame retardants (BFRs), including so called "emerging" and "novel" BFRs (EBFRs and NBFRs) in fish samples. High performance liquid chromatography (HPLC) coupled to Orbitrap mass spectrometry (Orbitrap-MS) employing atmospheric pressure photoionization (APPI) interface operated in negative mode was used for the identification/quantitation of contaminants. HPLC-Orbitrap-MS analysis provided a fast separation of selected analytes within 14 min, thus demonstrating a high throughput processing of samples. The developed methodology was tested by intralaboratory validation in terms of recovery, repeatability, …

A concept of mould spoilage prevention and acrylamide reduction in wheat bread: application of lactobacilli in combination with a cranberry coating

In this study, a concept for wheat bread moulding prevention and acrylamide reduction has been developed. It includes various lactic acid bacteria (LAB), selected according to their technological, antifungal and acrylamide-lowering properties, in combination with an antifungal cranberry coating for wheat bread surface treatment. All the tested strains (Pediococcus pentosaceus LUHS183, Pediococcus acidilactici LUHS29, Lactobacillus paracasei LUHS244, Lactobacillus brevis LUHS173, Lactobacillus plantarum LUHS135 and Leuconostoc mesenteroides LUHS242) showed antifungal activities against Aspergillus nidulans, Penicillium funiculosum and Fusarium poae. However, L. brevis LUHS173 and Leu. mesent…

Study on the reduction of acrylamide in mixed rye bread by fermentation with bacteriocin-like inhibitory substances producing lactic acid bacteria in combination with Aspergillus niger glucoamylase

Abstract This study mainly focuses on a strategy for reducing of acrylamide in cereal products, predominantly in bakery products. The effect of mesophilic lactic acid bacteria (LAB) strains as well as a novel fermentation media on the bases of extruded rye wholemeal on the acrylamide formation in mixed rye bread of different weight of loaf was studied. The LC–MS/MS method for acrylamide determination in bread crumb has been applied. Addition of 15% low pH (pH 3.4–4.3) fermented product to bread dough, which were produced by using commercial strain Lactobacillus casei and bacteriocin-like inhibitory substances (BLIS) producing strains Lactobacillus sakei KTU05-6 , Pediococcus acidilactici KT…

The effects of ibuprofen on activated sludge: Shift in bacterial community structure and resistance to ciprofloxacin

Abstract Ibuprofen (IBP) is ranked at the 4th place among 57 pharmaceutical compounds according to the number of citations in prioritization documents. The response of microbial community of activated sludge to IBP was studied at the concentrations of 50–5000 mg/L. Batch incubation was performed in an OxiTop® device for 21 days. The reduction of biological oxygen demand depended on the IBP concentration and varied in the range from 321 to 107 mg O 2 /L. Massive DNA sequencing analysis of the activated sludge revealed that Proteobacteria became more dominant when grown in the presence of IBP. Microbial diversity was reduced in the presence of 500–1000 mg/L IBP, but increased again in the pre…

Efficacy of Ozonation Treatments of Smoked Fish for Reducing Its Benzo[a]pyrene Concentration and Toxicity

Ozone is widely used in food processing, for example, to decompose mycotoxins or pesticide residues, to extend the shelf life of products, and for sanitation. The objective of this study was to assess the possibility of expanding the application of ozone for oxidative degradation of polycyclic aromatic hydrocarbons (PAHs). The evaluation was conducted by ozonation of a benzo[a]pyrene (BaP) standard solution and smoked fish (sprats) contaminated with PAHs. The effect of ozonation was immediate in the BaP solution; 89% of this toxic compound was decomposed after only 1 min of treatment. However, the impact of ozonation on the smoked sprats was less pronounced, even after prolonged treatment. …

The Occurrence and Dietary Exposure Assessment of Mycotoxins, Biogenic Amines, and Heavy Metals in Mould-Ripened Blue Cheeses

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 (&le

Macro and trace elements in oat cultivars bred in Latvia

The expedient application of microbial fermentation after whole-wheat milling and fractionation to mitigate mycotoxins in wheat-based products

Abstract The effect of whole milling and fractionation of wheat grains from the 2017 and 2018 harvests on the mycotoxin transfer into milling products and the influence of microbial fermentation of such products on mycotoxin levels were analysed. Additionally, the identification and occurrence of fungal contamination in grains with different mycotoxin contamination levels was evaluated. The mycotoxin contents were determined by chromatography (HPLC-TOF-HRMS). The distribution of mycotoxins in wheat wholemeal fractions depended on wheat kernel contamination level. The flour fractions contained zearalenone (ZEN) from 59 to 92%, and deoxynivalenol (DON) and deoxynivalenol-3-glucoside (D3G) at …

Recent Applications of Carbonaceous Nanosorbents in Solid Phase Extraction for the Determination of Pesticides in Food Samples

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 compon…

Evaluation of selected buffers for simultaneous determination of ionic and acidic pesticides including glyphosate using anion exchange chromatography with mass spectrometric detection

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 …

Development of a sensitive method for the determination of acrylamide in coffee using high-performance liquid chromatography coupled to a hybrid quadrupole Orbitrap mass spectrometer

The emerging trend towards high-resolution mass spectrometry (MS) alternatives was evaluated by the application of Orbitrap MS for the determination of acrylamide in coffee samples. The high resolving power of the Orbitrap MS provided the high selectivity and sensitivity that enabled quantitative analysis of acrylamide in complex matrices, such as coffee. Several sample preparation methods and scanning modes of the MS (full MS, t-SIM, t-MS2) were assessed in order to optimise parameters of the analytical method. The final procedure involved the extraction of acrylamide with acetonitrile, solid-phase extraction with dispersive primary secondary amine (PSA) and amino columns, and the detectio…

Advanced analytical techniques based on high-resolution mass spectrometry for the detection of micropollutants and their toxicity in aquatic environments

Abstract An abundance of micropollutants (MPs) in treated wastewater (WW) and occasionally even in drinking water represents a global threat from the environmental and public health risk standpoint. Along with the development of innovative WW treatment technologies, advanced analytical techniques, such as chromatography hyphenated to high-resolution mass spectrometry, are required for ensuring the detectability of target and nontarget MPs. Further studies on the chronic toxicity of MPs are needed to improve the regulation of hazardous substances in WWs. This article provides an up-to-date overview of the latest methodological developments related to the screening and quantification of MPs, …

Modeling the mobility of glyphosate from two contrasting agricultural soils in laboratory column experiments

Glyphosate (GLP) currently is one of the most widely used herbicides worldwide. The persistence of GLP and its major metabolite, aminomethylphosphonic acid (AMPA) in the environment has been described by other authors. This study was aimed at comparing the GLP and AMPA behavior in sandy and loamy sand soils after spiking with enhanced (445 µg g−1) concentrations of GLP in herbicide KLINIK® (Nufarm, Austria) and bioaugmentation followed by 40 days weathering and a consistent three-stage leaching in a laboratory column experiment. Soil samples were obtained from mineral topsoil (0–10 cm) within former agricultural lands where soil parent material was formed by glacigenic deposits. The total a…

Method development for the simultaneous determination of polybrominated, polychlorinated, mixed polybrominated/chlorinated dibenzo-p-dioxins and dibenzofurans, polychlorinated biphenyls and polybrominated diphenyl ethers in fish.

An analytical methodology was developed for simultaneous determination of five groups of persistent organic pollutants (POPs) including polybrominated, polychlorinated and mixed brominated-chlorinated dibenzo-p-dioxins and dibenzofurans (PBDD/DFs, PCDD/DFs and PXDD/DFs, respectively), polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs) in fish samples. The presented analytical approach was based on well established and robust method for determination of PCDD/DFs and PCBs, which was augmented with gas chromatography coupled to high resolution mass spectrometry (GC-HRMS) to include PBDEs, as well as poorly investigated PBDD/DFs and PXDD/DFs at toxicologically significa…

Content of polychlorinated dibenzo-p-dioxins, dibenzofurans and dioxin-like polychlorinated biphenyls in fish from Latvian lakes

Seventeen polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/PCDFs) of the highest priority as well as twelve dioxin-like polychlorinated biphenyls (dl-PCBs) were analyzed in the muscle tissues of the following freshwater fish species sampled from eleven Latvian freshwater lakes: perch (Perca flavescens), carp (Cyprinus carpio), eel (Anguilla rostrata), bream (Abramis brama), chub (Leuciscus cephalus), pike (Esox lucius), sheatfish (Silurus glanis) and roach (Rutilus). To analyze the selected persistent organic pollutants in fish matrices, an optimization of EPA-1613 and EPA-1668A clean-up procedures was carried out, followed by validation of the analytical procedure …

Reducing of acrylamide formation in wheat biscuits supplemented with flaxseed and lupine

Abstract The use of pseudo-cereals for wheat products making is to fortify the deficiency of nutritional value in wheat flour. However rich in proteins plant additives could increase acrylamide content in baked products. The present study was focused on acrylamide reduction in wheat flour biscuits supplemented with lupine and defatted flaxseed flour treated by solid state (SSF) and submerged (SMF) fermentations by Lactobacillus sakei , Pediococcus pentosaceus and Pediococcus acidilactici strains. After fermentation the decrease in asparagine was on average of 67.6 and 80.6%, and reducing sugar contents were reduced by 18 and 79.4% in flaxseed and lupine, respectively. The most effective acr…

Distinguishing the roles of carrier and biofilm in filtering media for the removal of pharmaceutical compounds from wastewater

Abstract Pharmaceutical compounds (PCs) represent a large group of micropollutants in wastewaters (WW) worldwide. Many PCs are resistant to conventional WW treatment. Moreover, for some PCs the removal process is reversible. The aim of this study was to test three newly developed ceramic carriers for biofilm formation and PCs removal. The testing of untreated WW samples by liquid chromatography coupled to Orbitrap mass spectrometry allowed to detect the occurrence of 18 PCs in the range from 26 ng/L to 20,688 ng/L, with the highest concentrations found for caffeine. Besides, among PCs with concentrations above 1,000 ng/L, ibuprofen (19,234 ng/L), naproxen (1,405 ng/L), xylazine (1,366 ng/L)…

Non-target and suspected-target screening for potentially hazardous chemicals in food contact materials: investigation of paper straws

A non-target screening strategy was developed for the safety evaluation of potentially hazardous chemicals in paper food contact materials (FCMs). A tentative list of suspect analytes was generated using publicly available FCM substance inventories, the presence of contaminants in paper straws was confirmed by high-resolution Orbitrap mass spectrometry. Data-independent and data-dependent MS and MS/MS results for candidate compounds were processed using a workflow including peak detection by deconvolution, blank subtraction, retention time alignment, formula assignment and fragmentation spectra search against spectral libraries followed by in silico generated spectra annotation. This workfl…