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

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

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

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

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

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

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

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

Qualitative fingerprinting of psychoactive pharmaceuticals, illicit drugs, and related human metabolites in wastewater: A year-long study from Riga, Latvia.

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.

Consumption trends of pharmaceuticals and psychoactive drugs in Latvia determined by the analysis of wastewater.

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.

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 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.

Two-dimensional liquid chromatography - mass spectrometry as an effective tool for assessing a wide range of pharmaceuticals and biomarkers in wastewater-based epidemiology studies.

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.

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

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 C18stationary 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-1for 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.

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 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.

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 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.

Combination of Extrusion and Fermentation with Lactobacillus plantarum and L. uvarum Strains for Improving the Safety Characteristics of Wheat Bran.

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.

Combination of Antimicrobial Starters for Feed Fermentation: Influence on Piglet Feces Microbiota and Health and Growth Performance, Including Mycotoxin Biotransformation in vivo.

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 log10 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.

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 × 101 and 9.00 × 104 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.

Study of the antibiotic residues in poultry meat in some of the EU countries and selection of the best compositions of lactic acid bacteria and essential oils against Salmonella enterica.

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.

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 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 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 (≤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 beehive matrices are dependent on collection time and matrix type but independent of proportion of foraged oilseed rape and agricultural land in foraging territory.

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.

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 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.