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In this study, five plant matrices (pea, mung bean, lentils, soy and sunflower) were fermented using Bacillus subtilis var. natto. Then the process influence on the content of fatty acids and proteins was evaluated, depending on the fermentation length. Fermentation was conducted for 144 hours in controlled conditions of temperature and relative humidity (37°C, 75%). Samples for tests were collected every 24 hours. Gas chromatography coupled with triple quadrupole tandem mass spectrometry (GC-MS/MS) was used to evaluate fatty acids content in fermented seeds. Their composition was expressed as a percentage of the total quantity of fatty acids. The protein content in plant matrices was analysed with the modified Bradford protein assay, using the TECAN apparatus with the i-Control software, of the wave length of ʎ=595 nm. Studies showed that the prolonged fermentation time influenced an increase of polyunsaturated fatty acids (PUFA) content in all studied seeds. Promising results were obtained for soy, sunflower, and lentil seeds, amounting to 3.6%; 68.7% and 67.7%, respectively. This proves that the process of seed fermentation can be effectively used to increase their nutritional value.

In this study, 10 different plant materials (seeds/beans) were fermented by Bacillus subtilis var. natto. The influence of the process on vitamin K2 MK-7 content during different fermentation periods was assessed. Fermented plant samples were analyzed by the procedure using HPLC UV/DAD. The fermented sunflower seeds, mung beans and peas appeared to be the most promising plants, reaching values of K2 of 1080.18±55.11 µg/100g, 806.45±60.95 µg/100g and 636.92±59.86 µg/100g, respectively. The experiments showed that extending of the fermentation time to 5–6 days was favorable for the menaquinone-7 yield. The results show that almost all fermented seeds/beans, apart from soybean, can be good source of vitamin K2 MK-7 and represent a new perspective, especially in terms of lower the phytoestrogen content.

Although yerba mate has been known and used for hundreds of years, not all of its properties have been fully understood yet. Yerba mate is a source of many desirable substances, but it may also contain toxic metals and other substances that are harmful to health. Fifteen samples of yerba mate tea from three South American countries were analyzed. The content of Cr, Ni, and Cd was determined using the AAS technique, while the PHA's content was determined with the gas chromatography method. Our studies show that some of the analyzed substances present in Ilex paraguariensis may exceed their acceptable levels specified in European standards established for the given substances. All analyzed samples contained the determined metals, where the concentrations of individual elements ranged from 1.92 ± 0.38 to 0.12 ± 0.05 µg/g (for Cr), from 4.86 ± 0.28 to 1.72 ± 0.14 µg/g (for Ni), and from 0.0008 ± 0.000 to 0.0695 ± 0.0745 µg/g (for Cd). The total PAH content ranged from 0.064 to 0.585 mg/kg. Yerba mate samples from Brazil were characterized by a lower PAH content (0.064-0.254 mg/kg), compared with mate from Argentina and Paraguay (0.084-0.374 and 0.197-0.585 mg/kg, respectively). Pesticide residues were found only in samples from Argentina and Paraguay, while samples from Brazil did not contain those compounds. Only four active substances belonging to the group of herbicides, fungicides, and insecticides were detected, two of them not approved for use in the EU: chlorpyrifos and fenbuconazole. The most frequently detected compounds in yerba mate samples were pendimethalin (in four samples), fluazifop-p-butyl and fenbuconazole (detected in two samples), and chlorpyrifos (in one sample)., Competing Interests: Declarations. Ethical approval: Not applicable. Consent to participate: Not applicable. Consent for publication: Not applicable. Competing interests: The authors declare no competing interests., (© 2024. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

A new analytical approach to the simultaneous identification and quantification of vitamins A and E in three representative matrices (Parmesan, spinach, and almonds) was developed. The analyses were based on high-performance liquid chromatography with UV-VIS/DAD detection. The procedure was optimized by a significant reduction in the weight of the tested products and quantities of reagents added during the saponification and extraction stages. A full method validation study was performed for retinol at two concentration levels (LOQ and 200 × LOQ), which showed satisfactory results, with recoveries ranging from 98.8 to 110.1%, and an average CV of 8.9%. Linearity was tested in the range of 1-500 µg/mL and showed the coefficient of determination R 2 = 0.999. The satisfactory recovery and precision parameters were achieved for α-tocopherol (LOQ and 500 × LOQ) in the range of 70.6-143.2%, with a mean CV equal to 6.5%. The observed linearity for this analyte in the concentration range of 1.06-532.0 µg/mL was R 2 = 0.999. The average extended uncertainties were estimated, using a top-down approach of 15.9% and 17.6% for vitamin E and A, respectively. Finally, the method was successfully applied to determine vitamins in 15 commercial samples.

New analytical approaches to the simultaneous identification and quantification of 94 pesticides and 13 polycyclic aromatic hydrocarbons (PAHs) in five representative matrices (pepper, apple, lettuce, wheat, and soil) were developed. The analyses were based on gas chromatography coupled with triple quadrupole tandem mass spectrometry (GC-MS/MS). The procedure was optimized by changing the solvent used during the extraction, from acetonitrile to the acetone: n -hexane mixture at a volume ratio of 1:4 ( v / v ), as well as the use of a reduced amount of water during the extraction of compounds from cereals. An additional modification was the use of florisil instead of GCB in the sample cleanup step. A full method validation study was performed, at two concentration levels (LOQ and 1000 × LOQ), which showed satisfactory results for all analytes from the PAHs group, with recoveries ranging from 70.7-115.1%, and an average RSD of 3.9%. Linearity was tested in the range of 0.001-1.000 mg/kg and showed coefficients of determination (R 2 ) ≥ 0.99 for all PAHs. Satisfactory recovery and precision parameters (LOQ and 100 × LOQ) were achieved for almost all analytes from the pesticide group in the range of 70.1-119.3% with the mean RSD equal to 5.9%. The observed linearity for all analytes in the concentration range of 0.005-1.44 mg/kg was R 2 ≥ 0.99, with the exception of famoxadone, chizalofop-p-ethyl, prothioconazole, spirodiclofen, tefluthrin, and zoxamid. The extended uncertainties were estimated, using a top-down approach of 9.9% (average) and 15.3% (average) for PAHs and pesticides samples, respectively (the coverage factor k = 2, the 95% confidence level). Ultimately, the method was successfully applied to determine pesticide residues in commercial samples of fruit, vegetables and grain, and soil samples for PAHs, which were collected from selected places in the Podkarpacie region. A total of 38 real samples were tested, in which 10 pesticides and 13 PAHs were determined. Proposed changes allow us to shorten the sample preparation time (by 20%) and to reduce the consumption of organic solvents (by 17%). The use of florisil for sample cleanup, instead of GCB, improves the recovery of compounds with flat particles.

In plant protection, biological preparations are used alternately with chemical pesticides. The applied microorganism can influence the concentration of chemical substances. Laboratory and field studies were conducted to assess the influence of Bacillus subtilis and Trichoderma harzianum on the penthiopyrad concentration. In laboratory studies, the effectiveness of penthiopyrad degradation by B. subtilis was approximately 5% during 14 days of the experiment. For penthiopyrad treated with T. harzianum strains, the degradation effectiveness ranged from 34.2% on Day 3 to 56.9% on Day 14. In experiments testing the effects of mixed culture of microorganisms, the effectiveness of penthiopyrad degradation ranged from 23.7% on Day 3 to 29.1% on Day 14. After treatment of apple trees of Gala and Golden Delicious varieties with a biological preparation, a maximum degradation of penthiopyrad of 20% was found in both varieties. Samples of apples were prepared by the quick, easy, cheap, effective, rugged and safe (QuEChERS) method, and penthiopyrad was analyzed by gas chromatography with a mass detector. A determined value of the chronic exposure to penthiopirad was 1.02% of the acceptable daily intake, both for children and for adults. The acute exposure amounted to 7.2% and 1.9% of the acute reference dose for children and adults, respectively. These values were considered to be acceptable and not threatening to health.

Biological crop protection is recommended to be applied alternately or together with chemical one, to protect human health from the excessive use of toxic pesticides. Presence of microorganisms can influence the concentration of chemical pollutants in soil. The aim of this study is to estimate the influence of a commercial biological fungicide containing Trichoderma harzianum Rifai T-22 on dissipation kinetics and degradation of five herbicides belonging to different chemical classes: clomazone, fluazifop-P-butyl, metribuzin, pendimethalin, and propyzamide, in two types of soil. Results of the study revealed that T. harzianum T-22 influences pesticide degradation and dissipation kinetics of the non-persistent herbicides: clomazone, fluazifop-P-butyl, and metribuzin. In soil with a higher content of nitrogen, phosphorus, and organic matter, degradation increased by up to 24.2%, 24.8%, and 23.5% for clomazone, fluazifop-P-butyl, and metribuzin, respectively. In soil with lower organic content, degradation was on a low level, of 16.1%, 17.7%, and 16.3% for clomazone, fluazifop-P-butyl, and metribuzin, respectively. In our study, the addition of the biological preparation shortened herbicide dissipation half-lives, from 0.3 days (2.9%) for fluazifop-P-butyl, to 18.4 days (25.1%) for clomazone. During the degradation study, no significant differences were noticed for pendimethalin, belonging to persistent substances. Biological protection of crops can modify pesticide concentrations and dissipation rates. On one hand, this may result in the reduced effectiveness of herbicide treatments, while on the other, it can become a tool for achieving cleaner environment.

The study concerned dissipation of metazachlor and clomazone, herbicides widely used in rapeseed (Brassica napus L. subsp. napus) protection, applied to the clay soil under field and laboratory conditions. Furthermore, the uptake of these pesticide from soil by rapeseed plants was investigated under field conditions. An additional aim of this work was to modify the QuEChERS method for the determination of metazachlor and clomazone in the plant material. Analytical procedures for metazachlor and clomazone qualification and quantification in rapeseed plants and soil were developed, using gas chromatography with an micro electron capture detector (GC-μECD) and a mass detector (GC-MS/MS QqQ) as confirmation. Dissipation kinetics of herbicide residues in soil were described as first-order equations. The analytical performance was very satisfactory and confirmed that the methods meet the requirements of the European Commission. In the conducted field experiments it was found that dissipation of clomazone and metazachlor in clay soil follows first-order kinetics (R 2 between 0.964 and 0.978), and half-lives were 9.5 days and 10.2 days for clomazone and metazachlor, respectively. Under laboratory conditions, dissipation of clomazone and metazachlor in soil also follows first-order kinetics (R 2 between 0.937 and 0.938), and half-lives were 8.8 days and 5.7 days for clomazone and metazachlor, respectively. Residues of both herbicides in rape plants 22 days after application of herbicides were below the maximum residue levels for Brassica plants. Metazachlor and clomazone dissipate very fast in clay soil and their uptake by rape plants is very low.

In this study, various food processing techniques, including high-temperature processes (pasteurization/sterilization and boiling), low-temperature processes (freezing), mechanical processing (peeling and juicing), and water-based processes (washing with tap water and ultrasonic washing) were used to identify the most effective way to remove contamination of 5 fungicides (cyprodinil, difenoconazole, fluopyram, tebuconazole, and fludioxonil). The most effective processes were juicing and freezing in the range between 63 and 100% and from 52 to almost 100%, respectively. Ultrasonic washing and boiling also significantly removed pesticide residues ranging from 79 to 84% and from 72 to 78%, respectively. The same trend was observed by peeling process where maximum reduction of 80% was achieved almost for all fungicides. Washing with tap water decreased the concentration levels in the range of 35-38%. This study demonstrated that the least effective and unpredictable method of decontamination of pesticides was sterilization and pasteurization, due to the large variation in pesticide levels during the process.

Salvia officinalis L. is a popular herb widely used in culinary, cosmetic, and medicinal preparations, and also as an ornamental plant. Sage crops are threatened by many diseases, such as gray mold, powdery mildew, and leaf spot, by weeds, and by pests, such as aphids. Use of crop protection products may lead to presence of pesticide residues in this herb. The aim of this work was to study presence of pesticide residues in the herb, S. officinalis L., available on the retail market in Poland, to verify their compliance with the maximum residue levels (MRLs) and to assess the chronic and acute risks associated with consumption of this herb and infusions prepared from contaminated sage plants. Ninety active substances of pesticides were analyzed, including all active substances registered in Poland for protection of the sage. Five active substances were found, one fungicide - boscalid and four insecticides: chlorpyrifos, pp'-DDT, dimethoate (residue levels above MRL) and indoxacarb. The chronic and acute exposure to pesticide residues consumed with sage did not exceed 0.02% of the acceptable daily intake (ADI) and 0.1% of the acute reference dose (ARfD), respectively.

Dissipations of three insecticides: chlorantraniliprole, chlorpyrifos-methyl and indoxacarb in apples were studied following their foliar application on apples intended for production of baby food. The apples were sprayed with formulations for control of codling moth (Cydia Pomonella L.) and leafrollers (Tortricidae). Six experiments were conducted; each insecticide was applied individually on dessert apples. A validated gas chromatography-based method with simultaneous electron capture and nitrogen-phosphorus detection (GC-ECD/NPD) was used for the residue analysis. The analytical performance of the method was satisfactory, with expanded uncertainties ≤36% (a coverage factor, k = 2, and a confidence level of 95%). The dissipations of insecticides were studied in pseudo-first-order kinetic models (for which the coefficient of determination, R 2 , ranged between 0.9188 and 0.9897). Residues of studied insecticides were below their maximum residue limits of 0.5 mg/kg at an early stage of growth of the fruit. The half-lives of chlorantraniliprole, chlorpyrifos-methyl and indoxacarb were 16-17, 4-6 and 20-24 days, respectively. The initial residue levels declined gradually and reached the level of 0.01 mg/kg in 1 month for chlorpyrifos-methyl, 2 months for chlorantraniliprole and 2.5 months for indoxacarb. To obtain the insecticide residue levels below 0.01 mg/kg, which is the default MRL for food intended for infants and young children, the application of the studied insecticides should be carried out at recommended doses not later then: 1 month before harvest for chlorpyrifos-methyl, 2 months for chlorantraniliprole and 2.5 months for indoxacarb.

Dissipation of simultaneously applied insecticides alpha-cypermethrin and lambda-cyhalothrin was studied in a minor crop, aboveground part of white mustard (Sinapis alba L.). A validated gas chromatographic method (GC-ECD/NPD) was used to determine insecticide residues. Analytical performances were very satisfactory, with expanded uncertainties not higher than 14% (coverage factor k = 2, confidence level 95%). Dissipation of alpha-cypermethrin and lambda-cyhalothrin in white mustard followed first-order kinetics (R(2) between 0.953 and 0.995), with half-lives of 3.1-4.6 and 2.9-3.7 days respectively. Based on the results of this two-year study and the relevant residue regulation, alpha-cypermethrin and lambda-cyhalothrin treatments can be considered safe for crop protection, feeding animals and the environment.

This paper presents the results of official control of pesticide residues in minor crops collected in southeastern Poland in 2013-2014. Compliance of used pesticides with applicable law was also verified, and determined residues were compared to maximum residue levels (MRLs) provided for in Regulation (EC) No. 395/2005. A total of 583 samples of 25 different types of fresh fruit and vegetables were analyzed for pesticide residues. Pesticide residues were detected in 158 samples (27.1 % of the analyzed samples). According to the European Commission Health & Consumer Protection Directorate-General (SANCO) guidelines document, MRL violations were understood as cases where a residue level exceeded the MRL after the uncertainty of the method (50 %) was considered. MRL violations were found in four samples. The usage of unauthorized pesticides was detected in 5.8 % of analyzed samples. Substances banned in Poland were found in two samples. Fungicides were the most frequently detected group of pesticides. Pesticide residues were most commonly found in fruit samples (19.4 % of all analyzed samples), mainly in gooseberry, redcurrant, and huckleberry. The majority of samples were compliant with MRLs, which means that they were suitable for trade.

Background: Considering the fact that pesticides are commonly used in agriculture, continuous monitoring of these substances in food products is of great significance. Residues of these substances can be present in crops after harvest., Objective: The aim of this study was to evaluate presence of pesticide residues in fruiting vegetables from production farms in south-eastern region of Poland in 2012–2015., Material and Methods: 138 samples were tested using accredited test methods. The monitoring programme covered determination of 242 pesticides. The tests covered tomato, cucumber and pepper crops. The test results were interpreted in accordance with criteria included in the European Commission recommendations published in the document SANCO/12571/2013 (now superseded by Document SANTE 2015), as well as on a basis of the maximum residue levels in force in the EU Member States., Results: Pesticide residues were found in 47 samples, representing 34% of all tested samples. 17 active substances were found, belonging to fungicides and insecticides. Azoxystrobin (38%), boscalid (28%) and chlorothalonil (21%) were most commonly found in fruiting vegetables testing samples. Non-compliances related to use of plant protection product not authorized for protection of a given crop were observed in 6% of analysed samples. However, pesticide residues of fruiting vegetables in quantities that exceed the maximum residue levels (NDP, ang. MRLs), as well as substances which use for plant protection is forbidden were no found., Conclusions: Crops monitoring is used to determine to what extent such products are contaminated with pesticide residues, and ensures protection of customer health.

Background: The use of pesticide leads to the increase in quantity and quality of yields, but may also result in presence of toxic contaminants in food products., Objective: The aim of this study was to evaluate presence of pesticide residues in raw agricultural products from the south-eastern region of Poland, to verify their compliance with the maximum residue levels' (MRLs) as specified in the EU regulations concerning products present in the market, and to assess the acute risk related to consumption of these products., Material and Methods: Samples of raw agricultural products were obtained from production farms as a part of an official premarket monitoring of pesticide residues conducted on behalf of the Ministry of Agriculture and Rural Development, implemented in cooperation with the regional Inspectorates of Plant Health and Seed Inspection. The scheduled tests covered determination of 243 chemicals included in residue definitions for purposes of pesticide residues monitoring in or on food of plant origin (229 pesticides)., Results: In 2015, a total of 328 samples of raw commodities collected from the south-eastern region of Poland were analysed for the presence of pesticide residues. Pesticide residues were detected in 84 samples (25.6%), while in 7 samples (2.1%) they exceeded MRLs. Violations of MRLs concerned 2 samples of Peking Cabbage, 3 samples of dill, 1 sample of raspberry and 1 sample of spinach. The pesticide residues were most often found in: fruit (38.3% of all fruit samples), herbs (35.3%) and vegetables (20.0%). The assessed acute exposure did not exceed the 100% acute reference dose (ARfD) in any sample., Conclusions: Monitoring of pesticide residues in the agricultural crops prevents penetration of products with MRLs exceeded or containing unacceptable pesticide residues into the market, thus protecting consumers' health., Key Words: pesticide residues, agricultural products, risk assessment, multiresidue method.

A new analytical method employing gas chromatography coupled to electron capture and nitrogen phosphorus detection (GC-ECD/NPD) has been developed and validated for the screening and quantification of 51 pesticides in a matrix of high chlorophyll content - white mustard (Sinapis alba L.). For preparation of the sample extract, the citrate buffered QuEChERS procedure was followed. However certain changes were made to adapt the method to our needs and available laboratory resources. The sample size was reduced to 5 g, 10 mL water was added and exchange of solvent before GC analysis was done. The samples spiked with the target pesticides at the concentration level 0.01 mg/kg and a higher level (depending on the compound) yielded average recoveries in the range of 70-120% with relative standard deviations (RSDs) 0-19% except for HCB, S-metolachlor and teflubenzuron, and displayed very good linearity (R(2)>0.99) for nearly all the analytes. Limit of quantification was 0.01 mg/kg for the majority of the analytes. The expanded measurement uncertainties were estimated employing a "top-down" empirical model as being between 6% and 32% and yielding an average value of 18% (coverage factor k=2, confidence level 95%)., (Copyright © 2014 Elsevier Ltd. All rights reserved.)