Search

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]

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

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]

• 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 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]