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The profile of secondary metabolites present in the apple cuticular layer is not only characteristic of a particular apple cultivar; it also dynamically reflects various external factors in the growing environment. In this study, the possibility of authenticating apple samples by analyzing their cuticular layer extracts was investigated. Ultra-high-performance liquid chromatography coupled with high-resolution tandem mass spectrometry (UHPLC-HRMS/MS) was employed for obtaining metabolomic fingerprints. A total of 274 authentic apple samples from four cultivars harvested in the Czech Republic and Poland between 2020 and 2022 were analyzed. The complex data generated, processed using univariate and multivariate statistical methods, enabled the building of classification models to distinguish apple cultivars as well as their geographical origin. The models showed very good performance in discriminating Czech and Polish samples for three out of four cultivars: "Gala", "Golden Delicious" and "Idared". Moreover, the validity of the models was tested over several harvest seasons. In addition to metabolites of the triterpene biosynthetic pathway, the diagnostic markers were mainly wax esters. "Jonagold", which is known to be susceptible to mutations, was the only cultivar for which an unambiguous classification of geographical origin was not possible. [ABSTRACT FROM AUTHOR]

In 2022, Poland and Germany experienced a prolonged and extensive mass fish kill in the Odra River. During the period from the end of July to the beginning of September 2022, a high level of incidental disease and mortality was observed in various fish species (dozens of different species were found dead). The fish mortality affected five Polish provinces (Silesia, Opole, Lower Silesia, Lubuskie, and Western Pomerania) and involved reservoir systems covering most of the river (the Odra River is 854 km long, of which 742 km are in Poland). Fatal cases were investigated using toxicological, anatomopathological, and histopathological tests. Water samples were collected to determine nutrient status in the water column, phytoplankton biomass, and community composition. High nutrient concentrations indicated high phytoplankton productivity, with favorable conditions for golden algal blooms. The harmful toxins (prymnesins secreted by Prymnesium parvum habitats) had not been found in Poland before, but it was only a matter of time, especially in the Odra River, whose waters are permanently saline and still used for navigation. The observed fish mortality resulted in a 50% decrease in the fish population in the river and affected mainly cold-blooded species. Histopathological examinations of fish showed acute damage to the most perfused organs (gills, spleen, kidneys). The disruption to hematopoietic processes and damage to the gills were due to the action of hemolytic toxins (prymnesins). An evaluation of the collected hydrological, meteorological, biological, and physico-chemical data on the observed spatio-temporal course of the catastrophe, as well as the detection of three compounds from the group of B-type prymnesins in the analyzed material (the presence of prymnesins was confirmed using an analysis of the fragmentation spectrum and the accurate tandem mass spectrometry (MS/MS) measurement, in combination with high-performance liquid chromatography-tandem mass spectrometry (LC-MS/MS), allowed the formulation and subsequent testing of the hypothesis for a direct link between the observed fish mortality and the presence of prymnesins in the Odra River. This article systematizes what is known about the causes of the fish kill in the Odra River in 2022, based on official government reports (one Polish and one German) and the EU technical report by the Joint Research Centre. A review and critical analysis of government findings (Polish and German) on this disaster were conducted in the context of what is known to date about similar cases of mass fish kills. [ABSTRACT FROM AUTHOR]

Beta vulgaris L. is an important source of bioactive saponins -- a group of secondary metabolites -- that have spurred a growing interest due to their health-promoting properties. This study aimed to gain information on triterpene saponin profile of the peel and flesh of white, yellow and red beet of six cultivars -- Snow Ball, Boldor, Ceryl, Chrobry, Forono and Tytus -- harvested in Poland, in the same region. Twenty four saponins with oleanolic acid, hederagenin, akebonoic acid and gypsogenin as aglycons were identified and quantified by liquid chromatography/tandem mass spectrometry (LC-ESI-MS/MS). Among them, betavulgaroside I, II, III and IV were the major compounds, but the quantitative profile of saponins was found to be dependent on beet cultivar and root part, respectively. The highest content of saponins was found in the peel of yellow B. vulgaris Boldor (20812 mg/kg fresh weight, fw), while the lowest saponin content was determined in the flesh of white B. vulgaris Snow Ball (497 mg/kg fw). In addition, the total saponin content in peel and flesh in yellow beet (26054 mg/kg fw) was much higher than the total content in peel and flesh in red beet Tytus (8364 mg/kg fw) and white beet Snow Ball (1204 mg/kg fw). This is the first report on the profile of saponins in white and yellow beets. [ABSTRACT FROM AUTHOR]

In the past, pigs were commonly fed with acorns, and this was of remarkable economic importance. Currently this habit is continued in some areas, especially for production of prime-quality Iberian ham. Mature acorns, after shedding and during storage in unsuitable conditions, can be quickly infected with spores of many moulds, which cause mummification, blackening, dehydration, and nutrient loss. This study aimed to evaluate the quality of acorns of pedunculate oak (Quercus robur L.). The samples were collected in 2017 in southern Wielkopolska (central part of Poland), as feed material. In mouldy acorns a very high number of fungi was found (2.6 × 106 cfu/g), and 97% of them represented pathogenic Penicillium spp. Liquid chromatography-tandem mass spectrometry (LC-MS/MS) analysis showed in mouldy acorns high concentrations of mycophenolic acid (14580 μg/kg) and patulin (50 μg/kg). The dominant mould species, Penicillium expansum, showed a high cytotoxicity of swine kidney cells using assay based on the conversion of the tetrazolium salt, 3-(4,5, dimethylthiazol-2-yl)-2-5 diphenyltetrazolium (MTT). This raises the question if the pathogenic metabolites of moulds present in acorns can be dangerous for livestock, especially pigs, and people, as acorns are beginning to be seen as an interesting and functional part of their diet. [ABSTRACT FROM AUTHOR]

The present study reports for the first time the occurrence of selected pharmaceuticals and personal care products (PPCPs) in the shallow aquifer underlying the Kraków city. Urban groundwater samples were gathered from 11 wells, which can serve as the emergency water supply wells. Liquid chromatography with tandem mass spectrometry method with the previous pre-concentration of samples using an SPE technique was applied for the determination of the PPCPs selected. There were quantified concentrations of PPCPs from the groups of estrogens (17-α-ethinylestradiol (EE2), 2.6–18.7 ng/L), non-steroidal anti-inflammatory drugs (ketoprofen, 59.5 ng/L in 1 sample), and antimicrobial preservatives used in cosmetic production (methylparaben up to 91.5 ng/L). Triclosan was observed in all analysed water samples in concentrations above the limit of detection. The presence of the PPCPs in the shallow aquifer is an evidence that the sewer network system under the city leaks and then pollutes the urban groundwater. [ABSTRACT FROM AUTHOR]

Summary: The prevalent pesticide carbofuran was banned in the European Union (EU) in 2008; however, the extent of its actual elimination from the environment has been little studied. The presence of this pesticide in the livers of the protected raptors the white-tailed eagle (Haliaeetus albicilla) and the common buzzard (Buteo buteo) was monitored in Poland from 2008 to 2019 using liquid chromatography with tandem mass spectrometry analysis and data from government institutions. Carbofuran residues were detected in the liver samples of the analysed raptors throughout the period studied. In total, carbofuran was detected in the livers of 33% of the eagles and 54% of the buzzards; concentrations were in the ranges of 11–699 and 14–1890 μg kg–1 of dry matter, respectively. Effective measures to eliminate banned pesticides from the market more efficiently are required. [ABSTRACT FROM AUTHOR]

Objectives: We aimed to screen for late‐onset Pompe disease using the dried blood spot (DBS) test in a cohort of patients with limb‐girdle muscle weakness or persistent hyperCKemia. Materials and methods: Patients with limb‐girdle muscle weakness, persistently elevated CK, rigid spine syndrome, dyspnoea, myalgia or sibling of the patient diagnosed with LOPD were included in the study. Acid α‐glucosidase (GAA) activity was measured on DBS by tandem mass spectrometry and followed by genetic testing when required. Study was conducted between June 2014 and May 2017. Results: A total of 337 patients aged 32.2 years (range 2‐80) were included in the study. Late‐onset Pompe disease was diagnosed in 10 patients (3.0% of tested cohort). All were compound heterozygotes with common c.32‐13T>G mutation on one allele and missense or frameshift mutation on the other. Two of the mutations (c.1951delG and c.397T>G) were not reported previously. Seven of the patients started enzyme replacement therapy. Conclusions: DBS test is a reliable method for screening for late‐onset Pompe disease. [ABSTRACT FROM AUTHOR]

Phthalates are a group of widely used chemicals and humans are exposed to them in their daily life. Some phthalates may affect the hormonal balance in both children and adults. The aim of this study was to assess the phthalate exposure and its determinants among children at age of 7 years from the Polish Mother and Child Cohort Study (REPRO_PL). 250 urine samples collected in 2014–2015 were analysed for 21 metabolites of 11 parent phthalates using on-line high performance liquid chromatography coupled to tandem mass spectrometry (HPLC-MS/MS). This represents the most extensive set of phthalate metabolites ever determined for Poland. Ten metabolites were quantifiable in 100% of the samples, another eight in >90%. The highest median concentrations were found for the primary monoester metabolites of di-iso-butyl (MiBP, 72.4 μg/l), di-n-butyl (MnBP, 56.3 μg/l) and diethyl (MEP, 42.0 μg/l) phthalate, followed by the sum of di-2-ethylhexyl (ΣDEHP, 89.3 μg/l) and di-iso-nonyl (ΣDiNP, 21.9 μg/l) phthalate metabolites. Metabolite concentrations were higher in children at 7 years than in the same children at age 2 or in their mothers during pregnancy. Generally, phthalate exposures in this study were much higher than exposures reported in other European populations. Multivariate regression models showed that body mass index, place of residence, breastfeeding duration, socio-economic status and parental education were associated with the metabolite levels in the 7-year old children. Daily intake and hazard index calculations revealed that a small percentage of children (around 3–10%) exceeded the tolerable daily intakes established by international institutions such as EFSA and U.S. EPA indicating that these children might be at risk of anti-androgenic effects from the individual and cumulative exposure to phthalates. Thus, further monitoring of this population, by educational programs and follow-up interventions, is required. Unlabelled Image • Phthalate exposures in children from Poland ranked among the highest. • The most prevalent phthalate metabolites were MEP, MiBP, MnBP, ΣDEHP and ΣDiNP. • BMI, place of residence and breastfeeding are associated with phthalate body burdens. • Exposures in the upper percentiles exceeded levels that cannot be regarded as safe. [ABSTRACT FROM AUTHOR]

The presence of antibiotics and their metabolites in the aquatic environment exerts a negative impact on all organisms. Moreover, the easy migration of these substances to drinking water may also have serious consequences for public health, such as drug resistance. Although antibiotics and their metabolites are detected in surface waters and wastewater, there are still no systemic solutions preventing environmental pollution with these substances. The procedure for quantification of antibiotics usually involves solid-phase extraction (SPE) followed by instrumental analysis typically using liquid chromatography coupled with tandem mass spectrometry (LC–MS/MS), which provides sensitivity, selectivity and reliability of results. Therefore, it is necessary to take decisive steps aimed at the determination of critical concentrations of antibiotics, which will make it possible to maintain safe values that will not exert a negative impact on the natural environment and human health. This work presents the current state of knowledge based on data from 2009 to 2018 (review of ten years of scientific papers) on the presence of antibiotics and their metabolites in the aquatic environment in Poland and Europe and methods used for the determination of antibiotics in different types of water (surface water and wastewater). The main strategies used for the removal of antibiotics during wastewater treatment processes in the context of antibiotics' concentrations were also presented. • Presence of antibiotics in different types of surface water and wastewater in Poland and Europe • Impact on organisms resulting from the presence of antibiotics in the aquatic environment • A literature update of analytical methods for quantification of antibiotics based on data from 2009 until today [ABSTRACT FROM AUTHOR]

Comfrey ( Symphytum officinale L.) has a long tradition of use in the treatment of musculoskeletal disorders. However, due to hepatotoxic pyrrolizidine alkaloids (PAs), the EMA restricts the use of comfrey root (CR) to external use only and for short periods of time. Recent studies indicate a low permeability of PAs across the skin, calling into question the safety of topical application of products containing comfrey preparations. The aim of our work was to develop and validate an HPLC method enabling the separation of isomeric PAs from comfrey and, on this basis, to assess the potential toxicity of CR and comfrey leaf (CL) obtained from various Polish sources. The qualitative and quantitative analysis of PAs via HPLC-MS/MS was performed in MRM mode. The results obtained confirmed a lower content of PAs in CL than in CR and showed a wide variation in the composition of PAs in CR, with a much more stable profile of PAs in CL. Factor analysis confirmed that CRs and CLs differ in PA content, which is influenced by the growth conditions and geographical origin. The determined concentrations of PAs prove that in some CRs available on the Polish herbal market, the content of PAs may exceed the daily dose considered safe.

Antibiotic consumption (e.g. fluoroquinolones (FQs)) and, as a consequence, their presence in the environment, have received a lot of attention in the last several years due to increasing numbers of diseases and infections that are becoming resistant to traditional treatments for both humans and animals. In addition, even though antibiotics are safe for human and veterinary usage, ecosystems may be exposed to these substances. In this study, analytical methods for determining enrofloxacin (ENR), norfloxacin (NOR) and ciprofloxacin (CIP) in water samples and fish tissue based on the LC-MS/MS technique were developed and validated. As there is no data available concerning the risks posed by antibiotics in Poland, the proposed methods were applied for monitoring drug presence in environmental samples collected from two rivers in northern Poland. Evaluations of the ecotoxicity of ENR, NOR and CIP towards four different species of aquatic organisms: marine bacteria (Vibrio fischeri), green algae (Scenedesmus vacuolatus), duckweed (Lemna minor) and crustacean (Daphnia magna), were also carried out. All the investigated compounds were detected at least once in the survey. NOR was found to be the most ubiquitous drug with concentrations of up to 442.8 ng L-1. Moreover, it was established that L. minor is the most sensitive species to the investigated drugs (EC50NOR = 0.13 mg L-1, EC50ENR = 0.22 mg L-1 and EC50CIP = 0.34 mg L-1). The calculated risk quotient (RQ) values confirmed that the concentrations of the investigated FQs in the environmental samples were at a level of moderate environmental risk (1 < RO ≤ 10), however, for CIP they were found to be closer to a level of high environmental risk (RQCIP = 8.1). [ABSTRACT FROM AUTHOR]

Abstract: Concentration levels of 30 pesticide residues were measured in honey samples collected from apiaries in northern part of Poland (Pomerania) using method based on the QuEChERS extraction followed by liquid chromatography–tandem mass spectrometry with electron spray ionization (LC–ESI–MS/MS). In 29% of the samples were found positive for at least some of the target compounds. Concentration of bifenthrin, fenpyroximate, methidathion, spinosad, thiamethoxam, and triazophos exceeded maximum residue levels (MRL) in five samples (11%), the kind of the residues being correlated to agriculture practices in the region. The maximum values of these pesticides were 14.5, 16.3, 25.7, 20.6, 20.2 and 20.3 ng/g respectively. Profenofos was the most abundant at concentration ranged from

Nettle is a common plant that offers many health benefits and is grown all over the world. The content of active compounds in roots, stems, and leaves was determined based on the extraction procedure optimized using the Central Composite Design. Flavonols, phenolic acids, trigonelline, nicotinamide, nicotinic acids, and short-chain organic acids were determined with the use of LC-MS/MS and capillary isotachophoresis. Trigonelline, which was not previously reported in the roots and stems of nettle, was found in all parts of the plant and considerable variations in its content were observed (2.8-108 µg g -1 ). Furthermore, the Principal Component Analysis taking into account more variables demonstrated differences in the content of bioactive components between roots and aerial parts of nettle.

Abstract: Levels of 13 pesticides in 40 honey samples form Poland are reported. A rapid and sensitive method was developed for the LC-ESI-MS/MS determination of multi-class pesticide residues in honey samples. Liquid–liquid extraction (LLE) on a diatomaceous earth support (requiring the use of small amounts of organic solvent), followed by chromatographic separation on a C18 column and gradient elution were employed. The method quantifies over a dynamic linear range from respective MQLs (0.06–1.3 ng/g) to 5 ng/g. Matrix effects were evaluated by comparing the slopes of matrix-matched and solvent-based calibration curves. The mean recoveries obtained for three fortification levels (0.5, 1.0 and 4.0 ng/g) were 63–117% for most compounds, with an expanded uncertainty of <10%. The results for real honey samples collected from five regions of Poland (Pomerania, Wielkopolska, Lublin Region, Lower and Upper Silesia), showed that residue concentrations were <5 ng/g and did not pose a threat to human health. [ABSTRACT FROM AUTHOR]

Abstract: Several freshwater cyanobacteria species have the capability to produce toxic compounds, frequently referred to as cyanotoxins. The most prevalent of these cyanotoxins is microcystin LR. Recognizing the potential health risk, France, Italy, Poland, Australia, Canada, and Brazil have set either standards or guidelines for the amount of microcystin LR permissible in drinking water based on the World Health Organization guideline of one μg/L of microcystin LR. Recently, the United States Environmental Protection Agency has begun to evaluate the occurrence and health effects of cyanotoxins and their susceptibility to water treatment under the Safe Drinking Water Act through the Contaminant Candidate List (CCL). A recent update of the Contaminant Candidate List focuses research and data collection on the cyanotoxins microcystin LR, anatoxin-a, and cylindrospermopsin. Liquid Chromatography/Tandem-Mass Spectrometry (LC/MS/MS) is a powerful tool for the analysis of various analytes in a wide variety of matrices because of its sensitivity and selectivity. The use of smaller column media (sub 2μm particles) was investigated to both improve the speed, sensitivity and resolution, and to quantify the CCL cyanotoxins, in a single analysis, using Ultra-Performance Liquid Chromatography (UPLC®) combined with tandem mass spectrometry. Natural waters and spiked samples were analyzed to show proof-of-performance. The presented method was able to clearly resolve each of the cyanotoxins in less than eight minutes with specificity and high spike recoveries. [Copyright &y& Elsevier]

Objective: To evaluate physical growth, development and nutritional status in adults with previously undiagnosed/ untreated phenylketonuria (PKU). Methods: Four hundred adults (201 females and 199 males) with severe intellectual disability who were born prior to compulsory neonatal screening (before 1976) and who resided in social welfare homes in southeastern Poland were screened for PKU. The screening was performed by blood test using a tandem mass spectrometry method (MS/MS) and was confirmed by analysis of organic acids in urine. Eleven were identified as previously undiagnosed and/or untreated PKU cases. They underwent an assessment of their somatic development/status. Results: Among the 11 PKU patients (4 females and 7 males) the following characteristics were observed: poor physical growth after somatic development (n = 8, 2 females aged 23 and 56 years and 6 males aged 28–59 years); decreased head circumference – microcephaly (n = 5, 1 female aged 56 years and 4 males aged 28–59 years); poor body height (n = 2, 1 female aged 23 years and 1 male aged 59 years); poor thoracic circumference (n = 9, 3 females aged 23–56 years and 6 males aged 28–59 years). Overall, body weight imbalance was noted in 9 (81.8%) patients and irregularity of body proportions in 6 (54.5%) patients. Conclusion: Our data showedthe importance of nutritional surveillance and impact of metabolic imbalance on physical growth and body stature in untreated PKU patients. We therefore recommend an adequate and individually planned introduction of dietary intervention among that group of patients in order to ameliorate its nutritional status, general fitness and health. Copyright © 2009 S. Karger AG, Basel [ABSTRACT FROM AUTHOR]

Obesity rates among children are growing rapidly worldwide, placing massive pressure on healthcare systems. Untargeted metabolomics can expand our understanding of the pathogenesis of obesity and elucidate mechanisms related to its symptoms. However, the metabolic signatures of obesity in children have not been thoroughly investigated. Herein, we explored metabolites associated with obesity development in childhood. Untargeted metabolomic profiling was performed on fasting serum samples from 27 obese Caucasian children and adolescents and 15 sex- and age-matched normal-weight children. Three metabolomic assays were combined and yielded 726 unique identified metabolites: gas chromatography-mass spectrometry (GC-MS), hydrophilic interaction liquid chromatography coupled to mass spectrometry (HILIC LC-MS/MS), and lipidomics. Univariate and multivariate analyses showed clear discrimination between the untargeted metabolomes of obese and normal-weight children, with 162 significantly differentially expressed metabolites between groups. Children with obesity had higher concentrations of branch-chained amino acids and various lipid metabolites, including phosphatidylcholines, cholesteryl esters, triglycerides. Thus, an early manifestation of obesity pathogenesis and its metabolic consequences in the serum metabolome are correlated with altered lipid metabolism. Obesity metabolite patterns in the adult population were very similar to the metabolic signature of childhood obesity. Identified metabolites could be potential biomarkers and used to study obesity pathomechanisms.

The aim was to determine, for the first time, concentrations of 7 neonicotinoids (NEOs) and 5 metabolites in Sus scrofa from hunting areas in north-eastern Poland and assess the risk to consumers eating boar meat. 42 wild boar muscle samples were collected over a one-year period. The concentrations of 12 NEOs were determined by a fully validated LC-ESI-MS/MS protocol based on ultrasonic, freezing and cleanup EMR-lipid sample preparation. NEOs were present in over 83% of samples, 17% had no residue, and one pesticide was present in 36% of samples. Most often found were: clothianidin (35%), acetamiprid and imidacloprid (33%), thiacloprid (31%), thiamethoxam (9%), and the average concentrations were (ng g -1 ): thiacloprid 6.2 > imidacloprid 5.7 > acetamiprid 4.6 > clothianidin 2.2 > thiacloprid 1.6 > thiamethoxam 1.0. Multi-residue samples were found, one with 7 and one with 5 NEOs. Two NEOs were present in 24%; 3 in 39% and 4 in 10% of samples. In the metabolic degradation of acetamiprid, imidacloprid and thiacloprid, it was observed that metabolites account for no more than 8.5% of the measured parent substance. Acetamiprid-n-desmethyl was noted most often (21%). Due to the detection of NEOs in a large proportion of samples, chronic and acute risk assessment were performed. The estimated chronic and acute risk for consumers from NEOs neonicotinoids through the consumption of wild boar was very low and amounted to respectively 0.02% of ADI and 0.86% of ARfD., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

The present work is the first extensive study of large-scale pesticides research in wild animals. The investigation covered three game species: wild boar (n = 42), roe deer (n = 79) and deer (n = 15) collected from north-eastern Poland. To characterize the 480 pesticides in muscle samples, LC-GC-MS/MS techniques were used. A total of 28 compounds were detected: 5 neonicotinoids, 6 organochlorine and 5 other insecticides, 9 fungicides and 4 herbicides, in the range of 0.1-85.3 ng g -1 . Over four hundred detections were done. The highest mean concentrations were as follows: anthraquinone (85.3 ng g -1 ) > DDT-p,p' (4.6 ng g -1 ) > imidacloprid (4.3 ng g -1 ) > permethrin (3.6 ng g -1 ) > thiacloprid (2.8 ng g -1 ). DDT and metabolites were the most frequently detected, followed by acetamiprid, tebuconazole, clothianidin and imidacloprid. Overall, 92% samples with residues were recorded, including 100% of wild boar, 88% of roe deer and 86% of deer. More than one pesticide (up to 9) was found in over 73% of the tested samples. The estimated chronic and acute risk to consumers of venison were very low (below 1% ADI and ARfD). This interdisciplinary study may be helpful for estimating ecological risk to wild animals and risk to consumers of wild animal products, and also as a source of biomonitoring data., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2021 Elsevier B.V. All rights reserved.)

• The use of hormones for anabolic purposes in animals is prohibited in the EU. • The presence of hormone esters in animal serum/hair is evidence of illegal use. • Sensitive and selective methods allow the detection of low hormone levels. • Residue monitoring in Poland does not confirm the abuse of hormones in animals. • Animals tissue testing is designed to ensure the safety of food consumers. Anabolic hormones, which cause muscle growth, have been banned for anabolic purposes in animal husbandry in Europe since the 1980s. Control of hormones from the list of Annex I to Directive 96/23/EC is mandatory in the European Union. The presence of hormones in samples of animal origin may be due to their endogeneous nature or illegal use. One way to distinguish their origin is to study hormones, particularly steroids in the form of ester derivatives. In the body synthetic hormone esters could be only exogenous therefore their detection in animal tissues is the undisputed evidence of illegal administration. The analytical procedure involves the extraction of esters from serum with organic solvents, derivatisation with methoxyamine and detection by liquid chromatography tandem mass spectrometry. The method was approved in accordance with the applicable legislative criteria and its effectiveness was verified in the proficiency test. The research material consisted of bovine serum samples officially taken. During the validation good apparent recovery, precision, decision limits and detection capabilities in the range 0.006–0.012 µg L−1 and 0.010–0.020 µg L−1 respectively were obtained. The developed method met the criteria for confirmation set out in Commission Decision 2002/657/EC. Since the inclusion of serum in 2018 for testing for testosterone esters in the National Residue Control Program, 130 samples have been examined. In none of the serum samples, esters above the decision limits were found. The control of animals and food of animal origin for hormone esters will be continued to ensure the health and safety of consumers. [ABSTRACT FROM AUTHOR]

The article presents the first Polish case of fatal single-substance poisoning with cyclopropylfentanyl, a representative of fentanyl derivatives, whose victim was a 37-year-old man. This opioid was detected in biological material collected during medicolegal autopsy and in the syringe found near the deceased. Blood and urine samples were analyzed using liquid chromatography with mass spectrometry. The concentration of cyclopropylfentanyl was 24 ng/mL in blood and 73 ng/mL in urine.

The purpose of this work was to compare the content of pesticide residues (250) in unprocessed plant products from farms situated in the eastern part of Poland. The content of pesticide residues in the analysed samples was assayed with the use of the QuEChERS (Quick Easy Cheap Effective Rugged Safe) method combined with HPLC-MS/MS (high performance liquid chromatography with tandem mass spectrometry) analysis. The analyses revealed that among 160 analysed samples, pesticide residues were detected in 83 samples (approximately 52%), while in 77 samples (approximately 48%), no presence of those substances was noted. In all the samples in which the presence of the sought compounds was identified, their levels did not exceed the Maximum Residue Levels (MRL). The most often identified ones were azoxystrobin—detected in 36 samples (22.5%), linuron—assayed in 33 samples (20.6%), chlorpyrifos and carbendazim—each detected in 13 samples (8.1%), metalaxyl and metalaxyl M—in 11 samples (6.9%), and acetamiprid—in 7 samples (4.4%). [ABSTRACT FROM AUTHOR]

Sewage sludge, one of the main wastes generated during wastewater treatment, constitutes an important source of emissions of volatile chemical compounds such as volatile aromatic compounds These substances may undergo various changes as a result of operations and unit processes, which affects their concentrations in sewage sludge. An important factor determining the potential hazardousness of volatile organic compounds is the quality of wastewater delivered to wastewater treatment plants and the technical and equipment solutions applied to wastewater. In this study, a rapid and sensitive headspace gas chromatography method, coupled with tandem mass spectrometry using the standard addition method, was developed for the determination of selected volatile aromatic compounds in sewage sludge samples collected at different stages from three wastewater treatment plants located in Poland. This study attempted to assess the relationship between differences in the emissions of representative VACs and the given stage of the technological process within three analysed wastewater treatment plants. Toluene was detected with the highest frequency in analysed samples, at concentrations varying from 0.234 ± 0.035 ng/g of sludge to 28.3*102±3.2*102 ng/g of sludge. The highest concentration levels were determined for p-cresol, with concentrations ranging from 44.0*101±5.6*101 ng/g of sludge (sludge from aerobic chamber, wastewater treatment plant no.2) to 47.7*102±6.9*102 ng/g of sludge (sludge from aerobic chamber, wastewater treatment plant no.1), while the lowest concentration levels were observed for chlorobenzene, with concentrations ranging from 0.1300 ± 0.0030 ng/g of sludge (sludge from anaerobic chamber, wastewater treatment plant no.2), to 0.2606 ± 0.0046 ng/g of sludge (primary sludge, wastewater treatment plant no.1). The repeatability of the method was better than 10%, with accuracy levels in the ranges 89%–108%.Wastewater treatment technologies and residual sludge management in the selected wastewater treatment plantsinfluenced volatile aromatic compounds emission. Furthermore, the diversity of the wastewater quality, depending on the catchment area, is also an important factor determining the differentiation in volatile aromatic compounds emission. The microbial composition of raw wastewater highly influenced not only the treatment effectiveness of wastewater treatment plants but also the production of intermediate products, such as volatile aromatic compounds, which may contribute to odour emissions. Image 1 • Sensitive determination of selected volatile aromatic compounds in sludge samples. • Concentration of toluene, p-cresol and skatole related with type of sewage sludge. • The microbial composition highly influenced the production of p-cresol and skatole. [ABSTRACT FROM AUTHOR]

The triticale grain has high nutritive value and good technological suitability. Triticale flour can be a valuable raw material for bread-making. The aim of this work was to determine the profile of phenolic acids in triticale grain of selected Polish cultivars and its products. Ultra-high-performance liquid chromatography (UPLC-PDA-MS/MS) was applied for separation and identification of these constituents. The grain of the examined triticale cultivars contained 13 phenolic acids, of which ferulic acid was determined in the largest amount and was constituted from 42-44% of the total content of phenolic acids in the grain. In addition, due to the large amounts of ferulic, di-ferulic, and sinapic acids, composition of the phenolic acids fraction in triticale grain of the tested cultivars varied in comparison with that of wheat and rye cultivars. In triticale flour, the number of phenolic acids was nearly 4 times lower than in the grain, as phenolic acids were removed along with bran, in which their proportion was almost 9 times higher than in the grain intended for grinding. The application of bran in the bread recipe resulted in a 3.5-fold increase in the fraction of phenolic acids compared to the bread produced from triticale flour without bran addition.

Background: In some clinical situations (pregnancy, aging, drug resistance, toxicity), measurements of lamotrigine plasma levels may be reliable. Limited studies indicate that saliva and hair could be alternative sources for monitoring lamotrigine therapy. The drug content in hair can also be used to assess the history of drug therapy and to ascertain long-term patient compliance. The aims of this study were to 1) determine the correlations among plasma, saliva, and hair lamotrigine concentrations, 2) evaluate saliva as an alternative matrix for monitoring drug levels and 3) evaluate hair as a source of information on adherence to antiepileptic treatment and on the correlation of hair concentrations with clinical outcomes in patients with epilepsy., Methods: Plasma, saliva, and hair lamotrigine concentrations were measured by liquid chromatography-tandem mass spectrometry in positive ionization mode. The study group (n = 85) was recruited among the epileptic patients at the Institute of Psychiatry and Neurology, Warsaw, Poland., Results: Plasma concentrations were not influenced by sex, age, or the concomitant use of other antiepileptic drugs. Lamotrigine saliva and plasma concentrations were strongly correlated (r = 0.82, p < 0.001). Lamotrigine hair concentrations were correlated with the plasma concentrations (r = 0.53, p < 0.001) and daily dose in mg/kg (r = 0.23, p = 0.024). The analysis revealed no significant correlation between lamotrigine hair levels and the number of seizures in the previous 3 months (r = -0.1, p > 0.05)., Conclusions: The lamotrigine saliva concentration is strongly correlated with its plasma level, and saliva can be used as an alternative matrix to plasma for monitoring. Lamotrigine can also be successfully measured in hair, and the drug levels in hair tend to be correlated with the levels in plasma. However, lamotrigine levels in hair may not correspond to clinical outcomes (i.e., seizure episodes)., (Copyright © 2019 The Canadian Society of Clinical Chemists. Published by Elsevier Inc. All rights reserved.)

The aim of this paper was to analyze selected physicochemical properties and the pro-health potential of wines produced in southeastern Poland, in the Subcarpathian region, and commercial Carlo Rossi wines enhanced with cowslip ( Primula veris L.). This study used ultra-performance reverse-phase liquid chromatography (UPLC)-PDA-MS/MS to perform most of the analysis, including the polyphenolic compounds and saponin content in wines enriched by Primula veris L. The initial anthocyanin content in Subcarpathian (Regional) red wine samples increased four times to the level of 1956.85 mg/L after a 10% addition of Primula veris L. flowers. For white wines, a five-fold increase in flavonol content was found in Subcarpathian (Regional) and wine samples, and an almost 25-fold increase in flavonol content was found in Carlo Rossi (Commercial) wine samples at the lowest (2.5%) Primula veris L. flower addition. Qualitative analysis of the regional white wines with a 10% Primula veris L. flower enhancement demonstrated the highest kaempferol content (197.75 mg/L) and a high quercetin content (31.35 mg/L). Thanks to wine enrichment in triterpenoid saponins and in polyphenolic compounds from Primula veris L. flowers, which are effectively extracted to wine under mild conditions, both white and red wines can constitute a highly pro-health component of diets, which is valuable in preventing chronic heart failure.

Cardiovascular disease (CVD) remains one of the primary causes of death after kidney transplantation (KTX). Cyclosporine (CsA) metabolites may play a role in CVD. Metabolic ratio (MR) may be considered a measure of intra-individual differences of CsA metabolism. The study was aimed at analysis of associations of CVD with indices of CsA metabolism: MRs and dose-adjusted CsA concentrations (C/D and C/D/kg). The study was performed in the Department of Immunology, Transplant Medicine, and Internal Diseases of the Medical University of Warsaw and involved 102 KTX recipients. Whole blood concentrations of cyclosporine A, AM1, AM9, AM4N, demethylcarboxylated (dMC-CsA), dihydroxylated (DiH-CsA), trihydroxylated (TriH-CsA) cyclosporine metabolites were determined by liquid chromatography coupled with tandem mass spectrometry. Lower AM9/CsA were observed in diabetics. Patients with coronary disease and/or myocardial infarction had lower dMC-CsA/CsA and higher AM4N/CsA. Supraventricular arrhythmia (SVA) was associated with higher AM1/CsA and AM4N/CsA. Hypertriglyceridemia (hTG) was associated with lower AM9/CsA, higher C/D and C/D/kg. Decrease of AM9/CsA and AM4N and higher D/C were associated with overweight/obesity. Systolic blood pressure (BP) positively correlated with dMC-CsA/CsA and negatively with C/D/kg. Diastolic BP correlated positively with AM1/CsA, dMC-CsA/CsA, DiH-CsA/CsA and TriH-CsA/CsA. We have demonstrated the association of coronary disease/myocardial infarction, SVA, hTG, overweight/obesity and elevated arterial BP with higher MRs of AM1, AM4N, dMC-CsA, DiH-CsA and TriH-CsA, and lower MRs of AM9, which may indicate deleterious and favourable effects of individual CsA metabolites on cardiovascular system and suggest engagement of specific enzymatic pathways.

The phytochemistry of the genera Androsace , Cortusa , Soldanella, and Vitaliana , belonging to the Primulaceae family is not well studied so far. Hence, in this paper, we present the results of UHPLC-MS/MS analysis of several primrose family members as well as isolation and structure determination of two new saponins from Vitaliana primuliflora subsp. praetutiana . These two nor -triterpenoid saponins were characterized as (23 S )-17α,23-epoxy-29-hydroxy-3β-[( O -β-d-glucopyranosyl-(1→2)- O -α-l-rhamnopyranosyl-(1→2)- O -β-d-glucopyranosyl-(1→2)- O -α-l-arabinopyranosyl-(1→6)-β-d-glucopyranosyl)oxy]-27- nor -lanost-8-en-25-one and (23 S )-17α,23-epoxy-29-hydroxy-3β-[( O -α-l-rhamnopyranosyl-(1→2)- O -β-d-glucopyranosyl-(1→2)- O -α-l-arabinopyranosyl-(1→6)-β-d-glucopyranosyl)oxy]-27- nor -lanost-8-en-25-one, respectively. Their structures were determined by high resolution mass spectrometry (HRMS), tandem mass spectrometry (MS/MS), one- and two-dimensional nuclear magnetic resonance spectroscopy (1D-, and 2D-NMR) analyses. So far, the 27- nor -lanostane monodesmosides were rarely found in dicotyledon plants. Therefore their presence in Vitaliana and also in Androsace species belonging to the Aretia section is unique and reported here for the first time. Additionally, eleven other saponins were determined by HRMS and MS/MS spectra. The isolated lanostane saponins can be considered as chemotaxonomic markers of the family Primulaceae., Competing Interests: The authors declare no conflict of interest. The funders had no role in the design of the study; in the collection, analyses, or interpretation of data; in the writing of the manuscript, or in the decision to publish the results.

In this study, 120 silage samples collected in 2015 from farms in Poland were analysed by a multimycotoxin method based on liquid chromatography coupled with tandem mass spectrometry. The study included toxins which are regulated within the European Union (aflatoxins, deoxynivalenol, fumonisins, T-2/HT-2 toxins, ochratoxin A and zearalenone) and non-regulated mycotoxins (enniatins, beauvericin, 8-ketotrichothecenes, sterigmatocystin, zearalenone derivatives). All silage samples were positive for at least one mycotoxin, and 61% of samples contained five or more mycotoxins simultaneously. The most frequently detected toxins were deoxynivalenol, nivalenol, zearalenone, enniatins and beauvericin, although the levels of these toxins were relatively low. The mean concentration of deoxynivalenol and zearalenon was 406 and 80.6 μg/kg, respectively, and two toxins were positive-correlated. This is the first study that provides information about emerging mycotoxins contaminating silage in Poland.

A quick, easy, cheap, effective, rugged and safe (QuEChERS)-based extraction method has been optimized for the determination of pentachlorophenol, 4-tertoctylphenol and 4-nonylphenol in river sediments. The extraction method was followed by gas chromatography-triple quadrupole tandem mass spectrometry (GC-QqQ-MS/MS) analysis, which ensures the reliable identification of the target compounds. The proposed method has been validated allowing the successful determination of the selected compounds, with recoveries ranging from 72 to 96%, when three concentration levels were evaluated (10, 50 and 100μgkg(-1)) and inter-day and intra-day precision, expressed as relative standard deviation (RSD), were lower than 20%. The method showed limits of detection (LODs) and limits of quantification (LOQs) ranging from 0.1 to 2.0μgkg(-1) and from 0.5 to 5.0μgkg(-1), respectively. Finally, 25 real samples from Poland have been analyzed, and only 4-tertoctylphenol was detected at concentrations up to 8.9μgkg(-1) of soil dry weight., (Copyright © 2016 Elsevier B.V. All rights reserved.)

The aim of this work was to measure illicit drug residues in raw sewage samples collected from nine Polish cities in order to determine trends in illicit drug use in these urban populations. This is the first study involving an analysis of samples from several sewage treatment plants in Poland and covering such a large population. Concentration of illicit drugs was determined using a high performance liquid chromatography-tandem mass spectrometry method. The samples were subjected to a multistep preparation procedure with a solid phase extraction as a main pre-treatment step. Among the selected drugs investigated in the study, amphetamine was found in the greatest amounts in all sewage samples and consequently was the most prevalent drug of abuse. Higher loads of illicit drug residues were found during weekends compared to the weekdays, especially for 3,4-methylenedioxymethamphetamine (ecstasy) and benzoylecgonine, main metabolite of cocaine., (Copyright © 2016 Elsevier Ireland Ltd. All rights reserved.)

Basal serum 17OHP measurement remains the first screening step for nonclassic congenital adrenal hyperplasia (NCCAH) and the accuracy of the test is of high value. The aim of this study was to compare the accuracy of immunoassays to LC-MS/MS in the assessment of serum 17OHP and androgens concentration in women with hyperandrogenism and controls. 17OHP, total testosterone, androstendione and DHEA-S were measured in 39 women with clinically and/or biochemically evident hyperandrogenism and in 29 age-matched controls without clinical hyperandrogenism. 17OHP and androgens were measured by immunoassays and by LC-MS/MS. In patients group median 17OHP level measured by immunoassays was significantly higher compared to LC-MS/MS (5.49 nmol/l-ELISA NovaTec® and 3.57 nmol/l-ELISA DRG® versus 1.56 nmol/l-LC-MS/MS p < 0.0001) as well as in the control group (2.58 nmol/l-ELISA DRG® versus 1.14 nmol/l-LC-MS/MS p < 0.0001). Additional, unnecessary diagnostic procedures explaining elevated 17OHP level were undertaken in 85% of patients when NovaTec® test was used, in 50% when ELISA DRG® and in none when LC-MS/MS method was applied. Total testosterone, androstendione and DHEA-S concentrations in the patients and the controls assessed by the immunoassays were also significantly higher compared to LC-MS/MS. LC-MS/MS is more reliable diagnostic tool in the measurement of serum 17OHP and androgens concentrations compared to immunoassays in women with hyperandrogenism.

Pharmaceuticals consumption in Poland is high. One of the most frequently prescribed is cardiovascular drugs. Due to their relatively high hydrophilic properties, they are not completely eliminated during wastewater treatment processes. In contrast to parent compounds, the presence of cardiovascular metabolites is rarely investigated in surface waters. The goal of this paper was to develop the methodology for detection of metabolites of selected beta-blockers: metoprolol, bisoprolol and propranolol. These metabolites were obtained by the incubation of parent compounds with S9 rat's liver fraction and used for the development and optimization of the low resolution LC-MS/MS method. Accurate mass spectrometry measurements were applied for validation of this method. The incubation of the parent compound with S9 fraction resulted only in propranolol's metabolites generation. However, on the basis of hydroxypropranolol, theoretically transitions for mono- and dihydroxy-metoprolol and bisoprolol derivatives were generated for MRM mode and applied for surface water analysis. The analysis revealed the presence of some of the target metabolites in the Vistula river. This work is the first one proposing the application of biotrasformation in the methodology of low resolution LC-MS-MS analysis of metabolites of cardiovascular drugs in surface water., (Copyright © 2015 Elsevier B.V. All rights reserved.)

5-Methylcytosine is one of the most important epigenetic modifications and has a profound impact on embryonic development. After gamete fusion, there is a widespread and rapid active demethylation process of sperm DNA, which suggests that the paternal epigenome has an important role during embryonic development. To better understand the epigenome of sperm DNA and its possible involvement in a developing embryo, we determined epigenetic marks in human sperm DNA and in surrogate somatic tissue leukocytes; the analyzed epigenetic modifications included 5-methyl-2'-deoxycytidine, 5-hydroxymethyl-2'-deoxycytidine, and 5-hydroxymethyl-2'-deoxyuridine. For absolute determination of the modification, we used liquid chromatography with UV detection and tandem mass spectrometry techniques with isotopically labeled internal standards. Our analyses demonstrated, for the first time to date, that absolute global values of 5-methyl-2'-deoxycytidine, 5-hydroxymethyl-2'-deoxycytidine, and 5-hydroxymethyl-2'-deoxyuridine in sperm are highly statistically different from those observed for leukocyte DNA, with respective mean values of 3.815% versus 4.307%, 0.797 versus 2.945 per 10⁴ deoxynucleosides, and 5.209 versus 0.492 per 10⁶ deoxynucleosides. We hypothesize that an exceptionally high value of 5-hydroxymethyluracil in sperm (>10-fold higher than in leukocytes) may play a not yet recognized regulatory role in the paternal genome., (© 2014 by the Society for the Study of Reproduction, Inc.)

Blood lead levels (BLL) in women of child-bearing age have been decreasing in recent decades, but still remains a concern for long-term effects of child psychomotor development. The aim of the study was to characterize lead exposure among Polish pregnant women and assess the relationship between BLL and selected socio-demographic, economic and lifestyle factors. The study population consisted of 594 pregnant women who had been the subjects of the prospective Polish Mother and Child Cohort Study (REPRO&#95;PL). The women were interviewed three times during pregnancy (once in each trimester. Lead concentration in the blood collected during the second trimester of pregnancy was analyzed using graphite furnace atomic absorption spectrometry (GF-AAS), or inductively coupled plasma mass spectrometry (ICP-MS). Active and passive smoking was analyzed by the cotinine level in saliva using liquid chromatography with tandem mass spectrometry (LC-MS/MS). The lead level in the blood ranged from 0.3 - 5.7 μg/dL, with a geometric mean (GM) of 1.1 μg/dL (GSD ±0.2 μg/dL). Statistically significant associations were found between BLL and factors such as maternal age (β=0.01; p=0.02), education (β=0.08; p=0.04) and prepregnancy BMI (β=0.1; p=0.001). Additionally, BLL increased with increasing cotinine level in saliva (β=0.02; p=0.06) and decreased with the increasing distance from the copper smelter (β=-0.1; p=0.009). Public health interventions, especially in regions with a higher level of exposure to lead, among women with lower SES and among smokers, are still reasonable.

Aims: The aim of the study was to establish whether the addition of some berries and fruits during quince jam processing, improves its colour and enriches it in polyphenol compounds, other than those found in quince fruits., Methods: Phenolic compounds were identified and quantified by LC-MS Q/TOF and HPLC. Antioxidant activity was measured by ABTS, DPPH and FRAP methods. The colour of jams was expressed as L, a*, b* value., Results: The total content of polyphenolic compounds in quince jam was 484.5 mg/100 g. The highest level of phenolic compounds and antioxidant activity (p < 0.05) was observed in samples with the addition of chokeberry > black currant > flowering quince. The colour of examined jams could be due to the type of fruit addition, the nature of the pigments in these fruits., Conclusion: Overall, the results indicated that some mixed jams can represent a good source of antioxidant compounds and can have an attractive colour for the consumer.

Background/purpose: In mice, biotin deficiency is one of the most potent clefting factors. Increased 3-hydroxyisovalerylcarnitine (C5OH) is regarded as a biomarker of biotin deficiency. This retrospective study was undertaken to determine whether increased C5OH in newborns is associated with orofacial clefts., Materials and Methods: Seventy newborns with non-syndromic cleft lip with or without cleft palate and 140 control newborns without congenital anomalies were investigated. Whole-blood C5OH concentrations were measured using tandem mass spectrometry., Results: The median (interquartile range, IQR) concentrations of C5OH in patients with clefts and controls were 0.16 (0.13-0.22)μmoll(-1) and 0.17 (0.13-0.20)μmoll(-1), respectively (p=0.90). The receiver operating characteristic analysis did not find out cut-off values for C5OH discriminating between cases and controls., Conclusion: There appears to be no association between biotin deficiency, as indexed by an increase of C5OH, and orofacial clefts in the investigated group of patients., (Copyright © 2012 Elsevier Ltd. All rights reserved.)

Setting appropriate cutoff values and the use of a highly sensitive analytical method allow for correct classification of the smoking status. Urine-saliva pairs samples of pregnant women in the second and third trimester, and saliva only in the first trimester were collected. Offline SPE and LC-ESI-MS/MS method was developed in the broad concentration range (saliva 0.4-1000 ng/mL, urine 0.8-4000 ng/mL). The mean recoveries were 3.7 ± 7.6% for urine and 99.1 ± 2.6% for saliva. LOD for saliva was 0.12 ng/mL and for urine 0.05 ng/mL; LOQ was 0.4 ng/mL and 0.8 ng/mL, respectively. Intraday and interday precision equaled, respectively, 1.2% and 3.4% for urine, and 2.3% and 6.4% for saliva. There was a strong correlation between salivary cotinine and the uncorrected cotinine concentration in urine in the second and third trimesters of pregnancy. The cutoff values were established for saliva 12.9 ng/mL and urine 42.3 ng/mL or 53.1 μg/g creatinine with the ROC curve analysis. The developed analytical method was successfully applied to quantify cotinine, and a significant correlation between the urinary and salivary cotinine levels was found. The presented cut-off values for salivary and urinary cotinine ensure a categorization of the smoking status among pregnant women that is more accurate than self-reporting.

The purpose of the study was to assess the environmental exposure to 2 commonly used pesticides: 2-methyl-4- chlorophenoxyacetic acid (MCPA) and 2,4-dichlorophenoxyacetic acid (2,4-D) among spouses of farmers, not directly involved in the process of spraying. Exposure to 63 sprayings 24 women in households from the rural area of the Łódż Voivodeship in Poland was assessed. The women were asked to collect 3 biological urine samples: in the morning before spraying (sample A), in the evening after spraying (sample B), and on the morning of the next day (sample C). The determination of pesticides in urine was performed by high performance liquid chromatography, coupled with tandem mass spectrometry and negative electrospray (LC-MS/MS-ESI-). In the case of both active ingredient, the number of urine samples with the level of pesticides above limit of detection (LOD) increased from 30% in samples A to 45% in samples B and C. The average levels of herbicides increased from sample A (2.8 ng/g creatinine) to sample B (6.0 ng/g creatinine). The mean value of the C sample was 4.0 ng/g creatinine. Similar results were obtained when the average was calculated for all measurements, including those below LOD. The outdoor activity of the women during spraying was statistically significant (p=0.023), a predictor of exposure in multivariate analyses. The presented study indicates that farmers' spouses might be exposed to pesticides, even if they do not take part in the spraying.

Coccidiostats are widely used as feed additives to prevent coccidiosis. The off-label use of anticoccidials or feeding non-target animals with cross-contaminated feedingstuffs may result in the occurrence of coccidiostat residues in animal tissues and eggs. In EU countries, food of animal origin is subjected to official control of residues according to Council Directive 96/23/EC. In Poland, within the framework of the National Residue Control Plan, 3718 samples (3533 targeted and 185 suspect) of animal liver, eggs, drinking water and feed were tested for coccidiostats between 2007 and 2010. Violative residues of nicarbazin, lasalocid, maduramicin, salinomycin, semduramicin and robenidine were detected in 77 food samples (53 samples of chicken liver, 23 samples of eggs and 1 sample of turkey liver). A high percentage (31%) of non-compliant feed samples collected during follow-up investigations was observed, which confirms that feed cross-contamination may be the reason of the occurrence of coccidiostat residues in food.

Perfluorochemicals (PFCs) are wide-spread contaminants on a global scale. There is an increasingly growing number of data on environmental occurrence, sources and risk of PFCs to humans and aquatic biota in highly industrialised countries but inadequate information exists for less industrialised regions. In the present study, concentrations and profiles of PFCs were examined in surface waters (rivers, lakes, streams, coastal region of the Baltic Sea) of Poland. PFOS was the dominant compound found in water at most of the sites surveyed and its concentration varied between < 0.5 and 150 ng/L and next was PFHxS with < 0.25 to 110 ng/L, while at much smaller concentration of < 0.5 to 18 ng/L occurred PFOA. The long-chain carboxylates (C11-C16) could be found only in water of a drainage ditch near to the Sarzyna site, i.e., PFUnDA occurred at 0.17 ng/L, PFTeDA of 0.06 ng/L, PFDoDA at 0.1 ng/L and PFHxDA at 0.12 ng/L. PFDA was found at several locations in the Gulf of Gdansk and its concentration varied between < 0.01 and 0.07 ng/L. The profile of PFCs in surface water at several sites of Poland with PFOS as a major compound, followed by PFOA is similar to that reported for other countries in Europe as well as for India, while this is different from that of Korea, Japan and the USA, where PFOA was the predominant contaminant.

An optimized analytical method employing gas chromatography-tandem quadrupole mass spectrometry (GC-MS/MS) has been developed for the simultaneous screening of roughly 150 pesticides in honeybees suspected of poisoning by pesticides during field spraying. In this work, a sample preparation approach based on acetonitrile extraction followed by dispersive solid-phase extraction (d-SPE) cleanup was implemented and validated for pesticides in honeybees for the first time. The procedure involved homogenization of a 2g sample (23 insects on average) with acetonitrile-water mixture followed by salting out with citrate buffer, magnesium sulphate and sodium chloride. An amount of matrix constituents with limited solubility in acetonitrile was reduced in the extract by precipitation at low-temperature (freezing-out cleanup). Hereafter, d-SPE cleanup was carried out using primary secondary amine (PSA), octadecyl (C18) and graphitized carbon black (GCB). This combination of cleanup steps ensured efficient extract purification. Linearity of the calibration curves was studied using matrix-matched standards in the concentration range between 4 and 500 ng mL(-1) (equivalent to 10 and 1250 ng g(-1)), and coefficients of determination (R(2)) were > or =0.99 for approximately 90% of the targeted compounds. The recovery data were obtained by spiking honeybees samples free of pesticides at three concentration levels of 10, 50, and 500 ng g(-1) (approximately 0.9, 4.3, 43.5 ng per bee). At these spiking levels 47, 77 and 92% of the targeted compounds were recovered, respectively. Generally the recoveries were in the range between 70 and 120% with precision values, expressed as relative standard deviation (RSD) < or =20%. The expanded uncertainty was estimated following a "top down" empirical model as being 28% on average (coverage factor k=2, confidence level 95%). Preliminary results from practical application to analysis of real samples are presented. A total of 25 samples of honeybees from suspected pesticides poisoning incidents were analyzed, in which 10 different pesticides were determined.

The objective of the study was to determine the content of acrylamide in randomly selected samples of potato crisps and French fries using GC/MS/MS. The mean content of acrylamide in tested crisps amounted to 998 microg/kg (range from 352 to 3647 microg/kg) and was almost three times higher than in French fries--337 microg/kg (range from 88 to 799 microg/kg). Differences (even ten times) in the level of acrylamid in individual product samples, testifying the impact of raw materials and technological process running conditions on the content of acrylamide in the final product. The results of our study were close to those obtained in other countries.