Phytochemical Investigation of Cuscuta campestris Yunck. Stem Extract and Evaluation of Its Bioherbicidal Effect on Amaranthus retroflexus L. and Portulaca oleracea L.

This study focused on characterizing chemically and evaluating in vitro allelopathic and bioherbicidal potential of secondary metabolites extracted from the stem of Cuscuta campestris in seed germination, early seedling growth and early plant growth of Amaranthus retroflexus and Portulaca oleracea. The combined effects of stem extract and a reduced dose of herbicide metribuzin were also examined. Plant extract contained 17 phenolic compounds and the most abundant phenols were flavonoids: quercetin, (+)-catechin, daidzin, luteolin, and rutin. The seeds of P. oleracea were less sensitive than the seeds of A. retroflexus. The seed bioassay confirmed the inhibitory effect of stem extract on germination and early growth of both weed seedlings at concentrations of 0.75 % and 1 %, and a minor inhibitory effect in the plant bioassay. On the other hand, a synergy of C. campestris stem extract and metribuzin was revealed, as their combination achieved better results in the control of both weed species. Based on obtained data C. campestris stem extract could be a potential source of natural-based weed control molecules.

In Silico Investigation of Selected Pesticides and Their Determination in Agricultural Products Using QuEChERS Methodology and HPLC-DAD.

In this study, we considered some pesticides as active substances within formulations for the protection of plant-based food in the Republic of Serbia in silico, because these pesticides have not often been investigated in this way previously, and in an analytical way, because there are not very many available fast, cheap, and easy methods for their determination in real agricultural samples. Seven pesticides were detected in selected agricultural products (tomatoes, cucumbers, peppers, and grapes) using the QuEChERS methodology and HPLC-DAD. Standard curves for the investigated pesticides (chlorantraniliprole, methomyl, metalaxyl, thiacloprid, acetamiprid, emamectin benzoate, and cymoxanil) show good linearity, with R2 values from 0.9785 to 0.9996. The HPLC-DAD method is fast, and these pesticides can be determined in real spiked samples in less than 15 min. We further characterized the pesticides we found in food based on physicochemical properties and molecular descriptors to predict the absorption, distribution, metabolism, elimination, and toxicity (ADMET) of the compounds. We summarized the data supporting their effects on humans using various computational tools to determine their potential adverse effects. The results of our prediction study show that all of the selected pesticides considered in this study have good oral bioavailability, and those with high toxicity, therefore, could be harmful to human health. Chlorantraniliprole was shown in a molecular docking study as a good starting point for a new Alzheimer's disease drug candidate.

Characterization of the clomazone sorption process in four agricultural soils using different kinetic models.

Kinetic studies are important for understanding the parameters and processes involved in the sorption of pesticides to soil. Considering the agricultural and environmental relevance of clomazone, its sorption kinetics was studied in four agricultural soils (Regosol, Planosol, Chernozem and Vertisol) at two concentrations (0.5 and 15 mg L-1). Different kinetic models were applied to the experimental data. The pseudo-second-order model described the data much better than the hyperbolic and pseudo-first-order models, and the kinetic rate constants indicated concentration-dependent clomazone sorption kinetics. The application of the two-site nonequilibrium model (TSNE) revealed a more time-dependent sorption of the lower clomazone concentration than that of the higher clomazone concentration, and the greatest concentration impact occurred in Regosol. Elovich and intraparticle diffusion models predicted more intensive sorption during the slower second phase and that sorption kinetics is governed more by mass transfer across the boundary layer than by a intraparticle diffusion process at higher clomazone concentration. Intraparticle diffusion is the rate-controlling process in Regosol at lower concentration, while this process and the boundary layer control the sorption kinetics in other soils. Significant correlations between some kinetic parameters and soil properties indicate an impact of the soil texture on the clomazone sorption mechanism, which must be considered in assessing the clomazone leaching behavior.

Phytotoxicity and allelopathic potential of Juglans regia L. leaf extract.

Implementation of plant extracts that are rich in phytochemicals and have the allelopathic potential for weed management could help reduce the use of chemical herbicides. The present study investigated the herbicidal potential of walnut (Juglans regia L.) leaf extract (WLE) against two weeds, Amaranthus retroflexus L. and Chenopodium album L., by testing in vitro their seed germination and seedling growth, and then evaluated in vivo the oxidative stress of potted plants. The effects of the walnut leaf extract were also tested on maize (Zea mays L.) to eliminate possible negative impacts on a cultivated plant. Total phenolic acids and total flavonoid content in the extract were determined in prior bioassays, followed by separation and analysis of flavonoids and phenolic acids by high-performance liquid chromatography (HPLC). Phytochemical analysis revealed that the obtained extract was notably rich in phenolic compounds, while HPLC analysis confirmed the presence of (+)-catechin, luteolin, myricetin, rutin, (-)-epicatechin, genistin, protocatechuic acid, and caffeic acid as major extract components. The results obtained in bioassays revealed a significant negative impact of the walnut leaf extract on germination and seedling growth of the tested weeds, as well as significant oxidative stress in weeds grown in pots. Although it affected the maize seedling growth in vitro similar to the tested weeds, maize germination was less sensitive to treatment, and the extract did not have a significant negative impact in terms of oxidative stress in maize plants grown in pots. The findings show that walnut leaf extract may have a promising role in replacing chemical herbicides in maize.

Atropine and Scopolamine in Maize Products from the Retail Stores in the Republic of Serbia.

The cereal grains, which represent the cultivated grasses fruits, supply almost half of the total caloric requirements for humans and provide more nourishment compared with any other class of the food. Out of many cereals used for food, maize, rice, and wheat are the most important food resources for humans, representing 94% of the total cereals consumption. According to the data of the Republic Institute of Statistics for the year 2018, the harvested areas of corn amount to 906,753 hectares. The production of about 7 million tons was achieved with an average yield of 7.7 t/ha according to the Ministry of Agriculture of the Republic of Serbia. Serbia is still among the ten largest exporters of wheat and corn in the world for the period of 2014/15-2017/18. More precisely, it ranks seventh in the export of corn. Utilization of maize products for food animal nutrition (1000 t) is 491,48, and for industrial processing (1000 t) 278,862 expressed as the total consumption (1000 t) is 769,910. Therefore, a total of 103 samples of maize products were analyzed for the presence of toxins, i.e., tropane alkaloids (TAs). The samples were collected from the retail stores in the Republic of Serbia in 2021 and analyzed for the presence of atropine and scopolamine (33 corn grits, 39 polenta, and 31 semolina samples). Therefore, the Recommendation 2015/976/EU on the monitoring of TAs in food was adopted by the EU Commission to obtain more occurrence data on TAs in food. The monitoring extent, however, is restricted because reliable analytical methods and appropriate sensitivity are limited. There was a limit of 1 g/kg for each atropine and scopolamine in cereals containing millet, sorghum, buckwheat, or their derivatives. All the samples were analyzed by the LC-MS/MS. The LOQ was set at 1.0 µg/kg. Out of the total 103 tested samples, 32 samples (31.1%) were contaminated with atropine and scopolamine in concentrations above the LOQ. The highest concentrations of the studied TAs were observed in a semolina sample-atropine: 58.80 µg/kg, scopolamine: 10.20 µg/kg. The obtained results indicate that the TAs concentrations are above the LOQ which can be considered potential human and animal health hazards.

Infestation of Field Dodder (Cuscuta campestris Yunck.) Promotes Changes in Host Dry Weight and Essential Oil Production in Two Aromatic Plants, Peppermint and Chamomile.

Peppermint (Mentha piperita L.) and chamomile (Chamomilla recutita (L.) Rausch.) are aromatic plants with considerable economic value. These plants and their essential oils are used in medicine, cosmetics, and the food industry. One of the main limiting factors in peppermint and chamomile commercial cultivation is weed competition since weeds are able to decrease both oil amount and biomass yield. The purpose of the present study was to determine the effect of parasitism by field dodder (Cuscuta campestris Yunck.) on peppermint and chamomile dry weight and their essential oil yield and composition. Essential oils from both noninfested and infested peppermint and chamomile plants were obtained by hydrodistillation and characterized chemically by gas chromatography (GC) coupled with mass spectrometry (MS). The amount of dry matter accumulated by peppermint and chamomile plants infested by field dodder was lower (25% and 63%, respectively) compared to noninfested plants. Essential oil yield increased for peppermint (3.87% (v/w) and 3.63% (v/w)), but decreased for chamomile (0.2% (v/w) and 0.5% (v/w)) both from infested and noninfested plants, respectively. The oil composition profile significantly differed in terms of content. In peppermint plants, field dodder infestation increased menthone content by 23%, and decreased the content of both menthol by 11% and pulegone by 67%. Furthermore, δ-cadinene was detected only in oil extracted from infested peppermint plants. Compared to peppermint, chamomile plants were significantly more affected by field dodder in terms of essential oil yield, as well as oil composition and plant dry weight. In chamomile plants, (E)-dendrolasin was detected in the oil of noninfested plants, and 1,4-dimethyl-7-(1-methylethyl)-azulen-2-ol was detected only in the oil of infested plants.

Chemical Composition of Ambrosia trifida Essential Oil and Phytotoxic Effect on Other Plants.

This study aimed to identify the main components of an essential oil produced from leaves of Ambrosia trifida and to evaluate its potential allelopathic effect on seed germination and seedling growth of lettuce, watermelon, cucumber and tomato. The essential oil was obtained by hydrodistillation and characterized chemically by gas chromatography (GC) coupled with both mass spectrometry (MS) and flame ionization detector (FID). Total 69 compounds were identified, with limonene (20.7 %), bornyl acetate (15.0 %), borneol (14.7 %) and germacrene D (11.6 %) as the major components. The working solutions of the essential oil emulsified with Tween 20 and dissolved in distilled water were prepared at four concentration levels (0.01, 0.1, 0.5 % and 1 %, v/v). The results obtained showed that increase in essential oil concentration leads to decrease in seed germination, as well as shoot and radical length of lettuce, watermelon, cucumber and tomato. The obtained data revealed a highly significant effect (p<0.05) between control and 1 % and 0.5 % oil concentrations in all treatments. The essential oil of A. trifida exhibited more powerful phytotoxic effects on lettuce, watermelon and tomato than on cucumber regarding germination and early seedling growth.

Bio-herbicidal effects of five essential oils on germination and early seedling growth of velvetleaf (Abutilon theophrasti Medik.).

The evaluation of the inhibition effect exerted by the essential oils of basil (Ocimum basilicum), sage (Salvia officinalis), thyme (Thymus vulgaris), lemon balm (Melissa officinalis) and goldenrod (Solidago virgaurea) on seeds germination and early seedling growth of velvetleaf (Abutilon theophrasti Medik.) weed was examined in a laboratory bioassay. The essential oils were obtained by hydrodistillation and characterized chemically by gas chromatography coupled with both mass spectrometry and flame ionization detector. The working solutions of essential oil emulsified with Tween 20 and dissolved in distilled water were prepared at three concentration levels (0.01%, 0.1% and 1%, vol/vol). The results obtained showed that increase of essential oil concentration leads to decrease of seed germination, shoot and radical length of velvetleaf. The obtained data revealed a highly significant effect (P < 0.05) between control and 1% and 0.1% oil concentrations in all treatments. The essential oils of basil, thyme and lemon balm exhibited more powerful bio-herbicidal effect compared to sage and goldenrod essential oils on the germination and early seedling growth of velvetleaf weed.

Comparison of QuEChERS with Traditional Sample Preparation Methods in the Determination of Multiclass Pesticides in Soil.

Background: The increased use of pesticides leads to permanent pollution of soil, and there is a need for continuous monitoring of these agrochemicals in soil. Objective: Three methods for the simultaneous determination of 12 pesticides belonging to eight chemical groups in soil samples were tested and compared based on analytical parameters. Methods: The quick, easy, cheap, effective, rugged, and safe (QuEChERS); traditional solid-liquid extraction (SLE); and Soxhlet extraction were used for soil sample preparation, while detection and quantification of pesticides were performed using gas chromatography-mass spectrometry (GC-MS). Results: The tested methods featured good sensitivity, and with the exception for carbofuran (Soxhlet method, LOD = 29 µg/kg), for the rest of the pesticides, the studied LODs were less than 12 µg/kg. Except for simazine and carbofuran, LODs obtained by Soxhlet extraction were lower than values obtained by other two methods, whereas QuEChERS gave lower LODs than the traditional SLE method for all compounds except atrazine and acetochlor. The recoveries obtained applying QuEChERS, traditional SLE, and Soxhlet methods for multiple analyses of soil samples fortified at 10, 75, and 200 µg/kg of each pesticide were in the ranges 54-103, 40-91, and 12-92%, respectively. Except for chlorothalonil, the highest recoveries were obtained by the QuEChERS method. Soxhlet was better than traditional SLE method for chlorothalonil, heptachlor, and aldrin; organophosphorus pesticides (fenitrothion and diazinon) and trifluralin, gave similar recoveries for both methods. All three methods were proven to be repeatable, with RSDs lower than 19%. Conclusions: Although all tested methods showed as satisfactory regarding most analytical parameters, QuEChERS method showed much better results in terms of confidence, indicating that traditional SLE and Soxhlet extraction still need improvements for determination of multiclass pesticides in soil samples.

Examination of the influence of phenyltrimethylammonium chloride (PTMA) concentration on acetochlor adsorption by modified montmorillonite.

The results presented in this paper show an impact of the concentration of the aromatic organic cation on the adsorption of acetochlor on the surface of the organic-modified montmorillonite. Natural montmorillonite from Bogovina (Boljevac municipality, Serbia) was used for organic modification in this experiment. Cation exchange capacity of this montmorillonite (86 mmol 100 g-1 of clay) was determined using the methylene blue method. In pretreatment, montmorillonite was modified with NaCl. For the purpose of organic modification, three different concentrations of phenyltrimethylammonium chloride (PTMA) have been selected, based on calculated CEC value: 43 mmol 100 g-1 of clay (0.5 CEC), 86 mmol 100 g-1 of clay (1 CEC) and 129 mmol 100 g-1 of clay (1.5 CEC). The changes in the properties of the inorganic and organic modified montmorillonite were examined using X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR) and batch equilibrium method. Freundlich coefficients show higher uptake of the herbicide by montmorillonite modified with PTMA, compared to inorganic-modified montmorillonite. The results also indicate the influence of the organic cation concentration on the adsorption of the selected herbicide.

A method for reducing environmental pollution by using essential oils in rodent pest management program.

Strong-smelling plant extracts, such as essential oils, have a variety of feeding effects on mammals. Considering current concerns over long-term health issues and environmental effects of chemicals, plant-based products with repellent or antifungal activities may represent good solutions for improvement of rodent pest control programs. The present study was therefore focused on examining the effects of bergamot, lavender, and thyme essential oils as additional bait components on daily intakes of cereal-based baits by wild house mice. Lavender essential oil, containing linalool and linalyl acetate as main components, and thyme essential oil with a prevailing thymol component had no effects on house mice diet. Bergamot essential oil, whose main components were linalool, limonene, and linalyl acetate, showed a repellent effect on house mouse diet.

The photocatalytic degradation of carbofuran and Furadan 35-ST: the influence of inert ingredients.

A comparative study on photocatalytic degradation of the pesticide carbofuran and its commercial product Furadan 35-ST in an aqueous suspension of ZnO, irradiated by long-wave light (315-400 nm), is presented in this study. In order to assess the effects of inert ingredients present in the commercial product Furadan 35-ST, non-competitive and competitive adsorption and kinetic studies of carbofuran degradation processes were conducted. A higher photochemical degradation rate was found for pure carbofuran in comparison to a two-component system, carbofuran and single addition of ingredients at appropriate concentrations, and the commercial product Furadan 35-ST. The overall effect of inert ingredients was evaluated from a competitive study using the model system of Furadan 35-ST. The results of a mineralization study, obtained by ion chromatography (IC) and total organic carbon (TOC) analyses, revealed the formation of acetate, oxalate, and formate ions. Photodegradation products of carbofuran, three of them detected for the first time, were identified based on high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) and gas chromatography-mass spectrometry (GC-MS) results, and their photodegradation pathways were proposed.

Influence of the organic complex concentration on adsorption of herbicide in organic modified montmorillonite.

This study was undertaken to determine the impact of the organic complex concentration on the adsorption of herbicide (acetochlor) at the surface of the organic modified montmorillonite. In this work, natural montmorillonite from Bogovina (Boljevac municipality, Serbia) was used for organic modification. Cation-exchange capacity of this montmorillonite was determined using a methylene blue method (86 mmol/100 g of clay). Montmorillonite has been modified first with NaCl and then with hexadecyltrimethylammonium bromide (HDTMA-bromide) organic complex. Saturation of cation exchange capacity (CEC) was 50%, 100%, and 150%. Changes in the properties of the inorganic and organic montmorillonite have been examined using the X-ray diffraction, Fourier transform infrared spectroscopy, and batch equilibrium method. Montmorillonite modified with HDTMA-bromide demonstrated higher uptake of the herbicide, compared to the inorganic montmorillonite. Comparing the values Freundlich coefficients in batch equilibrium method, it can be seen that the adsorption of acetochlor decreased in the series: 0.5 CEC HM > 1 CEC HM > 1.5 CEC HM > NaM.

Evaluation of Lactobacillus plantarum and Saccharomyces cerevisiae in the Presence of Bifenthrin.

This work describes the effect of insecticide bifenthrin on Lactobacillus plantarum and Saccharomyces cerevisiae. Growths of used microorganisms in growth media supplemented with pesticide were studied. Determination of bacterial and yeast fermentation efficiency in wheat supplemented with bifenthrin was conducted. Additionally, investigation of bifenthrin dissipation during microbiological activity was performed. Experiments applying bifenthrin in different concentrations highlighted a negligible impact of the pesticide on the growth of L. plantarum and S. cerevisiae. This insecticide overall negatively affected the yeast fermentation of wheat, while its presence in wheat had a slight negative impact on lactic acid fermentation. The results of bifenthrin dissipation during lactic acid and yeast fermentations of wheat showed that activities of L. plantarum and S. cerevisiae caused lower pesticide reductions. Average bifenthrin residue reduction within samples fermented with L. plantarum was 5.4 % (maximum ~16 %), while within samples fermented with S. cerevisiae, it was 11.6 % (maximum ~17 %).

The potency of Saccharomyces cerevisiae and Lactobacillus plantarum to dissipate organophosphorus pesticides in wheat during fermentation.

The degradation behaviour of pirimiphos methyl with Saccharomyces cerevisiae and chlorpyrifos methyl with Lactobacillus plantarum in wheat during fermentation was studied. Yeast fermentation was especially effective for reduction of pirimiphos methyl applied at 5 mg kg-1 (maximum residue limit-MRL) causing dissipation for max 48.8%. Pesticide reduction rate decreased with an increase of fortification rate. Thus in samples fortified with 25 and 75 mg kg-1 a reduction up to 27.1%, and 23.7% respectively, was observed. Activity of L. plantarum was especially effective for reduction of chlorpyrifos methyl applied at 3 mg kg-1 (MRL) causing dissipation for max 56.7%. This reduction rate decreased with an increase of fortification rate. In samples contaminated with 15 and 45 mg kg-1 dissipation reached up to 38.6% and 34.7% respectively. For both experiments, initial inoculums sizes had no statistically significant effect on pesticides dissipation level, while concerning fermentation temperatures at all fortification levels the highest degradations occurred at 30 °C. Overall, regardless fermentation parameters, the degradation rate constants of pirimiphos methyl fermented with yeast were increased comparing with control samples by 255-573, 56-116 and 119-594% in samples contaminated at MRL, 5MRL and 15MRL of pesticide, while the degradation rate constants of chlorpyrifos methyl fermented with lactobacilli were increased by 74-769, 59-237 and 46-469% respectively. These results evidenced that yeast and lactobacilli played an important role in promoting pirimiphos methyl i.e. chlorpyrifos methyl dissipation in wheat.