Dissipation, processing factors and dietary risk assessment of the bioinsecticide abamectin in herbal plants belonging to Lamiaceae family from open field to herbal tea infusion.

Abamectin, the mixture of avermectin B1a and B1b, is widely used as a bioinsecticide and is an alternative to chemical pest control from insects. To our knowledge, its behaviour is not fully recognized, especially in herbs. Thus, the objective of this study was to investigate the environmental fate of abamectin in herbal plants belonging to the Lamiaceae family, its dissipation in open field studies laboratory processing treatments and dietary risk assessment. Three medicinally and culinary important species of herbs: Melissa officinalis L., Mentha × piperita L. and Salvia L. were treated with single and double dose than recommended on the label during their cultivation (BBCH 11-29). Residues were monitored using the QuEChERS method followed by the LC-MS/MS. The dissipation pattern of the sum of avermectin B1a and B1b and their persistence were observed 14 d after spraying. Abamectin decline was very rapid in plants and followed the first-order kinetics model. The half-life (t1/2) was in the range of 0.96-1.08 d (single dose) and 0.93-1.02 d (double dose). The pre-harvest intervals (decrease to the level of 0.01 mg kg-1) were 7.29-7.92 d at single and 7.99-8.64 d at double dose application. Herbal infusion preparation in previously washed and dried mint, lemon balm and sage leaves was the key processing step in the removal of abamectin residues. The reduction of initial deposits after single dose treatment was noted up to 65% (PF = 0.35-0.67) and up to 79% after double dose application (PF = 0.21-0.72) in herbal tea. Acute risk assessment of children and adults for the highest residues in EFSA PRIMo model at single and double dose expressed as hazard quotients (HQ) were <1, indicating no risk to humans via consumption of the herbal products. The data provide a better understanding of abamectin behaviour in herbal plants and can help assure herbs' safety for consumers.

Plants, Microorganisms and Their Metabolites in Supporting Asbestos Detoxification-A Biological Perspective in Asbestos Treatment.

Many countries banned asbestos due to its toxicity, but considering its colossal use, especially in the 1960s and 1970s, disposing of waste containing asbestos is the current problem. Today, many asbestos disposal technologies are known, but they usually involve colossal investment and operating expenses, and the end- and by-products of these methods negatively impact the environment. This paper identifies a unique modern direction in detoxifying asbestos minerals, which involves using microorganisms and plants and their metabolites. The work comprehensively focuses on the interactions between asbestos and plants, bacteria and fungi, including lichens and, for the first time, yeast. Biological treatment is a prospect for in situ land reclamation and under industrial conditions, which can be a viable alternative to landfilling and an environmentally friendly substitute or supplement to thermal, mechanical, and chemical methods, often characterized by high cost intensity. Plant and microbial metabolism products are part of the green chemistry trend, a central strategic pillar of global industrial and environmental development.

Selected Fungicides as Potential EDC Estrogenic Micropollutants in the Environment.

An increasing level of pesticide exposition is being observed as a result of the consumption of large amounts of fruits, vegetables and grain products, which are key components of the vegetarian diet. Fungicides have been classified as endocrine-disrupting compounds, but their mechanisms of action have not yet been clarified. The effect of boscalid (B), cyprodinil (C) and iprodione (I) combined with Tamoxifen (T) and 17ß-estradiol (E2) on cell viability, cell proliferation, reporter gene expression, ROS content, the cell membrane's function, cell morphology and antioxidant enzymes gene expression in MCF-7 and T47D-KBluc cell lines were investigated. The cell lines were chosen due to their response to 17ß -estradiol. The selected fungicides are commonly used in Poland to protect crops against fungi. Our results revealed that the studied fungicides caused significant increases in cell viability and proliferation, and estrogenic activity was present in all studied compounds depending on their concentrations. Oxidative stress activated uncontrolled cancer cell proliferation by inducing ROS production and by inhibiting antioxidant defense. Our findings verify that the studied fungicides could possibly exhibit endocrine-disrupting properties and exposure should be avoided.

Impact of technological processes on tebuconazole reduction in selected cereal species and the primary cereal product, and dietary exposure assessment.

Contamination of cereals with tebuconazole (TEB) can affect the dietary risk assessment. This study investigates, for the first time, how mechanical, thermal, physical-chemical, and biochemical processes affect the TEB level in wheat, rye, and barley. The biochemical process of malting was the most effective for tebuconazole reduction (by 86%) in cereals. Thermal processes were also effective, i.e., boiling (70%) and baking (55%). These processes considerably decreased the concentration of tebuconazole, and Procesing Factors (PFs) were from 0.10 to 0.18 (malting), 0.56 to 0.89 (boiling), and 0.44 to 0.45 (baking), respectively. The concentration of TEB was not reduced after the application of mechanical processing. The risk was estimated in dietary exposure assessment on the basis of the highest reported levels of tebuconazole residues bread. At a high level of rye bread consumption, the potential exposure to tebuconazole reached only 3.5% and 2.7% in children and adults, respectively.

Removal of triazole and pyrethroid pesticides from wheat grain by water treatment and ultrasound-supported processes.

A simple way to reduce pesticides in cereal grains is to use washing methods. The challenge of this study was to evaluate the effectiveness of reduction of 3 triazole fungicides (difenoconazole, tebuconazole, tetraconazole) and 3 pyrethroid insecticides (beta-cyfluthrin, cypermethrin, deltamethrin) commonly used in wheat protection. Four different pre-washing methods (hot and cold water washing, twice water, and ultrasound-supported washing) were evaluated. The processing factor (PF) was calculated based on the concentration of pesticides determined by LC-MS/MS in the samples of cereal grains before and after the washing process. PFs were within the range 0.01-0.97. Time, teperature and ultrasound were factors influencing the efficiency of water treatment. The study showed that ultrasound-supported washing eliminated pesticide residues to a greater extent than ordinary washing. This process significantly affected or completely reduced concentrations of triazoles in wheat grains. The highest reduction of residues (99%) was received for tebuconazole and ultrasound washing with heating temperature of 60 °C for a total of 10 min. In all washing processes, pyrethroids were removed with lower efficiency than triazoles. The lowest residue reduction was obtained for cypermethrin and washing under cold water for 5 min (3%; PF = 0.97). Beta-Cyfluthrin showed only a 6-27% reduction regardless of the process (PF: 0.73-0.95). Using static analysis, the relationship between the properties of pesticides and the reduction of their concentration in cereals was clarified and showed a strong correlation.

High and low temperature processing: Effective tool reducing pesticides in/on apple used in a risk assessment of dietary intake protocol.

Apples play an important role in everyone's diet and may contain pesticide residues that can pose a significant health problem for consumers. Various technological processes are promising methods for minimizing pesticide concentrations in fruit. Therefore, the subject of this comprehensive study was to investigate the effects of high-temperature (baking) and low-temperature (freeze-drying) processes on the change in the levels of nine fungicides in apples with skin and peeled. The investigated compounds belong to the chemical groups of benzimidazole (thiophanate methyl and carbendazim), phtalimide (captan and their metabolite tetrahydrophtalimid (THPI)), strobilurin (pyraclostrobin, trifloxystrobin) and triazole (difenoconazole, tebuconazole, tetraconazole). Processing factors (PF) were calculated for each pesticide-process-product combination. The results show that baking and freeze-drying generally reduced pesticide concentrations, with PFs ranging from 0.31 to 0.81 and 0.26 to 0.68, respectively. Apart from freeze-drying for carbendazim and baking for captan, PFs were above 1. Only for thiophanate-methyl, a complete reduction was observed, which resulted from complete degradation to carbendazim. The study also aimed to assess human risk according to the new strategy for different sub-populations with conversion using the 36 PFs obtained. The highest acute exposure (expressed as %ARfD) was obtained for tebuconazole in raw apples (initial concentration of 1.42 mg/kg; 400% ARfD) for Dutch toddlers. After food processing, this decreased to 284% (0.74 mg/kg, baking) and to 137% (0.37 mg/kg, freeze-drying), but was still above the safety limit. Similarly, for adults and the general French population for tebuconazole, the %ARfD was high as it reached the values of 104% (initial concentration of 0.89 mg/kg) in unprocessed apples, 73.9% after baking (0.73 mg/kg) and 35.6% after freeze-drying (0.35 mg/kg). The results indicate that food processing techniques can potentially be used to minimize the hazardous effects of pesticide residues on human health.

Effect of vermiculite feed additive on the chemical, mineral, and amino acid compositions of quail meat.

Background and Aim: Poultry farming plays a significant role in providing the population with high-quality and cheap meat products. The development and success of this industry depend on the proper use of available feed. As a rule, feed additives should compensate for missing elements in livestock diets. This study investigated the effects of vermiculite feed additives on the chemical, amino acid, and mineral compositions of quail meat. Materials and Methods: Texas Quail meat breed birds were randomly divided into three groups (35 heads each). Group I served as the control group, in which the birds were fed a standard diet without any supplements. The diet of Group II was supplemented with 3% vermiculite feed additive, whereas Group III received 5% vermiculite. The experiment was conducted over 120 days. Results: Quails in the experimental groups contained less moisture, had more ash and protein, and were richer in calories in terms of energy value. In terms of mineral composition, the calcium concentrations were 9.9% and 16.5% higher in the in the Group I and II, respectively. Furthermore, the highest percentages of nonessential and essential amino acids were found in the 5% vermiculite group. In the meat of quails that received 5% vermiculite, cadmium and lead salt levels were 20%-25% lower than those in the control variant. Conclusion: The results of our analyses confirmed that meeting the mineral requirements of quails improves animal productivity and meat product quality. Vermiculite as a feed additive improved the chemical, mineral, and amino acid compositions of quail meat when it was added to up to 5% of the feed dry matter. These results will help to improve the feed base of the poultry industry in the Republic of Kazakhstan.

Chlorpyrifos Occurrence and Toxicological Risk Assessment: A Review.

Chlorpyrifos (CPF) was the most frequently used pesticide in food production in the European Union (EU) until 2020. Unfortunately, this compound is still being applied in other parts of the world. National monitoring of pesticides conducted in various countries indicates the presence of CPF in soil, food, and water, which may have toxic effects on consumers, farmers, and animal health. In addition, CPF may influence changes in the population of fungi, bacteria, and actinomycete in soil and can inhibit nitrogen mineralization. The mechanisms of CPF activity are based on the inhibition of acetylcholinesterase (AChE) activity. This compound also exhibits reproductive toxicity, neurotoxicity, and genotoxicity. The problem seems to be the discrepancy between the actual observations and the final conclusions drawn for the substance's approval in reports presenting the toxic impact of CPF on human health. Therefore, this influence is still a current and important issue that requires continuous monitoring despite its withdrawal from the market in the EU. This review traces the scientific reports describing the effects of CPF resulting in changes occurring in both the environment and at the cellular and tissue level in humans and animals. It also provides an insight into the hazards and risks to human health in food consumer products in which CPF has been detected.

Evaluation of titanium and silicon role in mitigation of fungicides toxicity in wheat expressed at the level of biochemical and antioxidant profile.

Biostimulators are compounds that are gaining attention due to their potential to support plant growth, however, less in known about their impact on plant biochemistry. Therefore, the main goal of this comprehensive study was to evaluate the effect of two inorganic biostimulators (titanium, Ti and silicon, Si) and five fungicides (propiconazole, cyproconazole, spiroxamine, tebuconazole, triadimenol) on biochemical and antioxidant status as well as mycotoxin profile in wheat (Triticum aestivum). Moreover, the half-life of fungicides under the influence of biostimulators was evaluated. Titanium caused most efficient mitigation of fungicide-induced toxicity reflected by greater increase of protein (104.80 mg g-1), carbohydrates (43.70 mg g-1), phenolic compounds (1023.18 µg g-1), and peroxidase activity (0.151 U mg-1) compared to treatment with silicon. The application of spiroketalamine and triazole fungicides with silicon decreased the activity of acid phosphatases (35.70 µM h-1 g-1) while inducing amino acid (861.40 µg kg-1) and catalase activity (1.056 U mg-1). Moreover, silicon was most effective in the reduction of mycotoxin contamination in wheat grain (61.17 µg g-1). This study indicated a shortened dissipation of propiconazole, spiroxamine, tebuconazole and triadimenol under the influence of titanium or silicon (DT50 = 1.85-4.82), which can therefore affect the grace period of wheat. The results of this comprehensive investigation demonstrated that titanium and silicon have a beneficial influence on wheat biochemistry and mitigate fungicide toxicity, which makes them widely suitable for optimizing plant health.

Biochemical compounds and stress markers in lettuce upon exposure to pathogenic Botrytis cinerea and fungicides inhibiting oxidative phosphorylation.

MAIN CONCLUSION: Botrytis cinerea and fungicides interacted and influenced selected biochemical compounds. DPPH and glutathione are the first line of defence against biotic/abiotic stress. Plant metabolites are correlated with fungicides level during dissipation. Botrytis cinerea is an etiological agent of gray mould in leafy vegetables and is combated by fungicides. Fluazinam and azoxystrobin are commonly used fungicides, which inhibit oxidative phosphorylation in fungi. In this study, lettuce was (i) inoculated with B. cinerea; (ii) sprayed with azoxystrobin or fluazinam; (iii) inoculated with B. cinerea and sprayed with fungicides. This investigation confirmed that B. cinerea and fungicides affected lettuce's biochemistry and stress status. B. cinerea influenced the behaviour of fungicides reflected by shortened dissipation of azoxystrobin compared to non-inoculated plants, while prolonged degradation of fluazinam. Stress caused by B. cinerea combined with fungicides reduced level of chlorophylls (53.46%) and carotenoids (75.42%), whereas increased phenolic compounds (81%), ascorbate concentrations (32.4%), and catalase activity (116.1%). Abiotic stress caused by fungicides contributed most to the induction of carotenoids (107.68 µg g-1 on dissipation day 3-1). Diphenyl picrylhydrazyl (DPPH) radical scavenging activity and glutathione concentration peaked from the first hour of fungicides dissipation. For the first time correlation between the status of plant metabolites and fungicides during their dissipation was observed. These results indicate that non-enzymatic antioxidants could be the first-line compounds against stress factors, whereas ascorbate and antioxidant enzymes tend to mitigate stress only secondarily. The findings of this study help better understand plant biochemistry under biotic/abiotic stress conditions.

Effects of agricultural landscape structure, insecticide residues, and pollen diversity on the life-history traits of the red mason bee Osmia bicornis.

Agricultural landscapes have changed substantially in recent decades, shifting from the dominance of small fields (S) with diverse cropping systems toward large-scale monoculture (L), where landscape heterogeneity disappears. In this study, artificial nests of the red mason bee, Osmia bicornis, were placed in S and L landscape types on the perimeter of oilseed rape fields representing different oilseed rape coverages (ORC, % land cover). The local landscape structure around each nest was characterised within a 100, 200, 500, and 1000 m radius using ORC and 14 landscape characteristics, which were then reduced by non-metric multidimensional scaling (nMDS) to two axes: nMDS1 characterised the dataset primarily according to land fragmentation and the main crop, whereas nMDS2 captured the prevalence of more natural areas in the landscape. Pollen diversity and insecticide risk levels in the pollen provisions collected by the bees were analysed, and their dependence on the landscape structure was tested. Thereafter, the effects of pollen diversity, insecticide risk, and landscape structure on the life-history traits of bees and their sensitivity to topically applied Dursban 480 EC were determined. Pollen taxa richness in a single nest ranged from 3 to 12, and 34 pesticides were detected in the pollen at concentrations of up to 320 ng/g for desmedipham. The O. bicornis foraging range was relatively large, indicating that the landscape structure within a radius of ~1000 m around the nest is important for this species. Pollen diversity in the studied areas was of minor importance for bee performance, but the ORC or landscape structure significantly affected the life-history traits of the bees. Contamination of pollen with insecticides affected the bees by decreasing the mass of newly emerged adults but their sensitivity to Dursban 480 EC was not related to environmental variables.

Synthesis, characterization and biological activity of bifunctional ionic liquids based on dodine ion.

BACKGROUND: Development of new plant protection strategies has become an urgent matter in modern agriculture, in view of the evidently proved negative effect of currently used active ingredients of pesticides. In recent years, much effort has been made to eliminate the use of pesticides established to be toxic to pollinators. RESULTS: In this study, we present a group of new bifunctional ionic liquids based on dodine (N-dodecylguanidine) cation whose physical and biological properties have been modified relative to those of the commercially available N-dodecylguanidine acetate. The decreased level of residue of active substances in plant tissues reduces their availability to pollinators, which increases the safety of their use. Moreover, lower environmental impact in combination with high antifungal activity and an additional biological function, that is the systemic acquired resistance induction, are in line with the goals of sustainable agriculture. CONCLUSION: The presented approach shows the possibility of derivatization of commonly used fungicide into the form of bifunctional salts whose physical and biological properties can be easily modified. The paper reports successful design and synthesis of new sustainable and green chemicals for the modern agriculture, being less toxic to the environment and human health but still effective against pathogens. © 2021 Society of Chemical Industry.

The processing factors of canning and pasteurization for the most frequently occurring fungicides and insecticides in apples and their application into dietary risk assessment.

The challenge of the present comprehensive work was to study, from apple orchards to consumer's plate, the influence of high- and low-temperature thermal treatments on the most frequently occurring fungicides (boscalid, captan, pyraclostrobin) and insecticides (acetamiprid, methoxyfenozide) in apples and processing factor (PF) application for more realistic dietary risk assessment in the new EFSA methodology. Dry pasteurization and canning combined with previous preliminary treatment gave PFs = 0.25-1.8 of the five active substances. Acute exposure (expressed as %ARfD) in the raw commodity was demonstrated to be 168.1% for acetamiprid in the worst case (input - highest residue) and 307.9% for boscalid in the most critical case (input - MRL), and after re-calculation for PF, decreased to 139.5% for acetamiprid in canned product and 203.2% for boscalid in pasteurized apples. These novel data may be helpful in estimating new threshold residue levels significant in food safety especially intended for children.

Health risk assessment of exposure to toxic elements resulting from consumption of dried wild-grown mushrooms available for sale.

Mushrooms exhibit a high ability to accumulate potentially toxic elements. The legal regulations in force in the European Union countries do not define the maximum content of elements in dried wild-grown mushrooms. This study presents the content of mercury (Hg), lead (Pb), cadmium (Cd) and arsenic (As) determined in dried wild-grown mushrooms (Boletus edulis and Xerocomus badius) available for sale. Moreover, the health risk associated with their consumption is assessed. The inductively coupled plasma mass spectrometry (Cd, Pb, As) and atomic absorption spectrometry (Hg) were used. The mean Hg, Cd, Pb and As concentration in Boletus edulis was 3.039±1.092, 1.983±1.145, 1.156±1.049 and 0.897±0.469 mg/kg and in Xerocomus badius 0.102±0.020, 1.154±0.596, 0.928±1.810 and 0.278±0.108 mg/kg, respectively. The maximum value of the hazard index (HI) showed that the consumption of a standard portion of dried Boletus edulis may have negative consequences for health and corresponded to 76.2%, 34.1%, 33% and 4.3% of the maximum daily doses of Hg, Cd, Pb and As, respectively. The results indicate that the content of toxic elements in dried wild-grown mushrooms should be monitored. The issue constitutes a legal niche where unfavourable EU regulations may pose a threat to food safety and consumer health.

Impact of broad-spectrum pesticides used in the agricultural and forestry sector on the pesticide profile in wild boar, roe deer and deer and risk assessment for venison consumers.

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.

A global study of pesticides in bees: QuEChERS as a sample preparation methodology for their analysis - Critical review and perspective.

To this day, it remains unknown what the cause of decline of honey bee populations is and how to prevent this phenomenon efficiently. Poisonings with pesticides are assumed to be among the main causes for the decline of the honey bee population. Despite the significant progress observed in analytics over recent years, research aimed at improving methods applied in diagnostics of bee poisoning is still in progress. This is no easy task, since determination of the content of trace amounts (often equal to sublethal doses) of a wide range of compounds with diverse physico-chemical properties in honey bee samples with a complex matrix composition poses a serious challenge to modern analytics. This overview is the first to include a comprehensive critical assessment of analytical methods proposed for quantification of pesticides in honey bees over the last decade. Since the QuEChERS method is currently of great significance to ensuring accurate and reliable results of pesticide quantification in honey bees, the present overview focuses on the major aspects of this method, which will provide a comprehensive reference for scientists. The review focuses on the limitations of methods and on potential future prospects. It also contains information on the detection of pesticides in honey bees between 2010 and 2020 and characterizes the pesticide classes which are most toxic to these insects. This is extremely important, not just in the context of understanding the potential adverse impact of pesticides, manifesting as losses in bee colonies; it is also intended to facilitate decision-making in future research related to this difficult yet very important subject.

Exposure of wild boars (Sus scrofa L) to neonicotinoid insecticides.

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.

Dissipation kinetics and processing behavior of boscalid and pyraclostrobin in greenhouse dill plant (Anethum graveolens L.) and soil.

BACKGROUND: Determining the environmental behavior and fate of chemical compounds during technological processing of plants is a task of great significance nowadays. However, the current knowledge is still incomplete for unique herbal matrices belonging to minor crops. The research in this article presents, for the first time, the dissipation kinetics and processing behavior of carboxamide boscalid (BOS) and stobilurin pyraclostrobin (PYR) fungicides during glasshouse dill (Anethum graveolens L.) cultivation. RESULTS: The half-lives (t1/2 ) of BOS and PYR after application at the recommended and double dosage were in the range: 1.62-2.01 days in plant and 2.08-4.85 days in soil, respectively. The processing behavior in dill was estimated after washing, hot air drying and drying in sunlight without/with pretreatment. Processing factors (PFs) were above 1 after drying (PF = 1.24-1.39 hot air; PF = 1.15-1.28 sunlight) and below this value when the washing step was applied (PF = 0.31-0.42 hot air; PF = 0.21-0.34 sunlight), indicating the highest effectiveness of reduction, up to 73% BOS and 79% PYR. CONCLUSION: BOS/PYR residues at pre-harvest intervals after both doses were below European Union (EU) maximum residue limits (MRLs). The highest effectiveness was noted for drying carried out with the washing step, which has a great influence on the concentration of residues in the final product. The findings can supplement PF databases not set for minor crops and can be used to establish MRLs and determine human exposures more accurately in risk assessment studies. © 2021 Society of Chemical Industry.

Seasonal content of heavy metals in the "soil-feed-milk-manure" system in horse husbandry in Kazakhstan.

BACKGROUND AND AIM: The quality of food, especially animal-based food, is crucial for human health. However, the quality of milk and other animal products has become an acute cause for concern in Kazakhstan. Technogenic dispersion of heavy metals (HMs) causes adverse effects on living organisms and creates unfavorable conditions for the existence of humans, animals, and plants. The purpose of this study was to analyze the content of several HMs in samples of soil, horse feed (hay, mixed feed, and bran), mare's milk, and manure to assess bioaccumulation and possible adverse effects on the bodies of horses. An additional purpose was to identify areas with acceptable conditions for obtaining environmentally safe horse breeding products in the agricultural zones of the Almaty region, Kazakhstan. MATERIALS AND METHODS: Samples were obtained from two farms in the Almaty region in 2020 (spring, summer, and autumn). In total, 72 soil samples were analyzed, which were taken from the upper humus horizon to the depth of the arable layer. Eighty-six samples were taken from the feed of horses. Green feed was represented by perennial and annual grasses (alsike clover, Medicago sativa, sweet yellow clover, as well as pea and oat mix). Barley and wheat bran stored in the warehouses of the farm were sampled for the research as feed supplements. The mixed feed comprised components such as maize and sunflower. In addition, 46 samples of mare's milk and 28 samples of horse manure were collected. The HM analysis was performed in the laboratory of the Kazakh-Japanese Innovation Center. The residual amounts of HMs were determined using an absorption spectrometer with a voltammetric analyzer. The content of cadmium (Cd), lead (Pb), mercury (Hg), and arsenic (As) in all the studied samples of soil, feed, mare's milk, and manure did not exceed the threshold limit values (TLVs), suggesting that the intake of these toxic elements into the human body with food was low. RESULTS: The average Cd concentration was in the range of 0.29-0.31 mg/kg in soil samples and in the range of 0.20-0.27 mg/kg in feed samples. In milk, the Cd concentration varied from 0.01 to 0.02 mg/L and was lower in summer and higher in fall. The total average Cd content in horse manure was 0.1844 mg/kg. The concentration of Pb in soil samples ranged from 1.09 to 1.30 mg/kg with the lowest value in spring and the highest in fall. In the feed, the concentration of Pb varied from 0.14 to 0.76 mg/kg and in milk from 0.03 to 0.15 mg/L. The average concentrations of Hg and As in soil samples averaged 0.022 and 0.019 mg/kg, respectively, and were within the TLVs. CONCLUSION: In the study areas, the calculated transition rates in the soil-feed-milk-manure system revealed that the greatest transition of HMs was observed for Pb and Cd, and a smaller migration was observed for Hg and As. The tendency of accumulation of trace elements continued in the feed.

Development of precise micro analytical tool to identify potential insecticide hazards to bees in guttation fluid using LC-ESI-MS/MS.

This paper illustrates the development of a miniaturized and precise analytical tool for biomonitoring of honey bee exposure to insecticides. This is the first work describing an analytical method for determination of very low concentrations of a wide range of insecticides in maize guttation fluid. Seed treatment with systemic insecticides or their foliar application causes the accumulation of compounds in the guttation liquid, which consists of excess water and compounds removed by plants and is a source of water for bees. A micro-QuEChERS protocol using 1 g of sample was used for analysis of over 140 insecticides belonging to 30 different chemical classes by LC-ESI-MS/MS. The determination of insecticides in guttation fluid is a difficult analytical task due to 1) the complexity of the sample matrix, 2) small amounts of test samples and 3) trace levels of analytes (often equal sublethal dose of insecticide for bees). An efficient sample treatment is proposed, involving 1 g of sample, extraction with 1% formic acid in acetonitrile, frozen, ultrasound-assisted, centrifugation and dispersive solid phase extraction with nano graphene oxide. Other tested sorbents: Fe3O4MNPs and two mixtures PSA/C18/GCB and Z-Sep did not give satisfactory parameters during sample purification. The graphene oxide proved to be the best, ensuring negligible matrix effects and analyte recoveries between 70% and 120% with relative standard deviations <20% for most of the compounds studied. The proposed method enables assessment of risk to honey bees resulting from exposure to guttation fluids containing toxic insecticides at very low concentrations.