Biological monitoring — as a method of hygienic assessment of the effects of pesticides on workers

Introduction. When conducting registration tests of the active substances of pesticides, it is essential to assess the risk for workers using these pesticide preparations in field experiments, where there is a direct human interaction with a potentially hazardous substance. The use of personal protective equipment and strict adherence to the regulations for the use of pesticide preparations cannot guarantee complete protection against contact with aggressive components. Biomonitoring occupies a special place in studies on the assessment of exposure of workers with pesticides, which makes it possible to assess the actual, rather than potential, absorption of a biologically active substance. Purpose of the work. Study of biomaterial (urine) of employees participating in field experiments when working with drugs based on active substances of the neonicotinoid group to determine their trace amounts by high performance liquid chromatography with a mass detector and risk assessment for those working with these pesticides. Materials and methods. Preparation of urine samples and their subsequent analysis for the content of residual amounts of acetamiprid, imidacloprid, thiamethoxam and its metabolite clothianidin were performed in accordance with the certified method “Measurement of the concentration of active substances of pesticides of the neonicotinoid class in urine”. The measurements were carried out using a method based on a tandem high performance liquid chromatography with a triple quadrupole mass detector, which makes it possible to estimate the minimum levels of active substances by two transitions of the parent ions (for quantitative calculation and confirmation by the ionic ratio). Electrostatic sputtering was used as a source of ionization; measurements were carried out in the multiple reaction monitoring mode. Results. The detected levels of imidacloprid in the urine of the researchers correspond to the data on the exposure assessment obtained from the results of measuring the concentration of this active substance in the air of the working area, as well as in washes from the skin of workers in agriculture. The maximum content of imidacloprid was revealed during the sowing of the etched seed material. Conclusion. Based on the data obtained, it was concluded that biomonitoring is the preferred method in a production environment due to its simplicity and sufficient information content.

A Narrative Review of the Current Knowledge on Fruit Active Aroma Using Gas Chromatography-Olfactometry (GC-O) Analysis

Fruit aroma, a mixture of chemical compounds with odor, is a strong attractant derived from a complex mixture of different amounts and intensities (threshold) of chemical compounds found in fruits. The odor-producing compounds of fruit aroma are derived from carbohydrates, lipids, phenolic compounds, and mono- and sesquiterpenes, among others. The identification of compounds responsible for fruit aroma is usually conducted using gas chromatography coupled with olfactometry (GC-O). This technique separates the chemical compounds from the aroma of foods using a chromatographic column and divides the resultant outflow between the physical detector and a testing outlet (sniffing port). Trained judges describe the perceived odor in terms of the intensity of the odor zones perceived according to their training method. Moreover, the use of GC-O coupled with a mass detector (GC-MS-O) allows for the retrieval of chemical information such as identification and quantification of compounds, which can be correlated to sensory information. This review aimed to demonstrate the application of GC-MS-O in the identification of precursor compounds in fruit aroma, considering important factors for the application, main results, and most recent advances in this field.

Assessment of Mycotoxin Exposure in a Rural County of Chile by Urinary Biomarker Determination

Aflatoxin B1 (AFB1), ochratoxin A (OTA), zearalenone (ZEN), and deoxynivalenol (DON) are frequent mycotoxins that may cause carcinogenic, mutagenic, estrogenic, or gastrointestinal effects. The aim of this study was to assess the exposure to and risk from AFB1, OTA, ZEN, and DON in 172 participants of the Maule Cohort (MAUCO) by a biomarker analysis in urine and to associate their exposure with food consumption and occupation. Mycotoxins in the first morning urine were analyzed by solid-phase extraction and quantified by Ultra-High-Performance Liquid Chromatography with a mass–mass detector. Participants’ information regarding food consumption, occupation, and other characteristics was obtained from a baseline and 2-year follow-up survey of the cohort. The prevalence and mean levels of mycotoxins in the urine were as follows: DON 63%, 60.7 (±78.7) ng/mL; AFB1 8%, 0.3 (±0.3) ng/mL; α-zearalenol (α-ZEL) 4.1%, 41.8 (±115) ng/mL; β-ZEL 3.5%, 17.4 (±16.1) ng/mL; AFM1 2%, 1.8 (±1.0) ng/mL; OTA 0.6% (1/172), 1.3 ng/mL; and ZEN 0.6%, 1.1 ng/mL. These results were translated into exposures of DON, ZEN, and aflatoxins of public health concern. Participants who consumed coffee and pepper the day before had a significantly greater presence of DON (OR: 2.3, CI95 1.17–4.96) and total ZEL (OR: 14.7, CI95 3.1–81.0), respectively, in their urine. Additionally, we observed associations between the habitual consumption of beer and DON (OR: 2.89, CI95 1.39–6.42). Regarding the levels of mycotoxins and the amount of food consumed, we found correlations between DON and nuts (p = 0.003), total ZEL and cereals (p = 0.01), and aflatoxins with capsicum powder (p = 0.03) and walnuts (p = 0.03). Occupation did not show an association with the presence of mycotoxins in urine.

Analysis of volatile compounds and antioxidant activity of Colombian ginger (Zingiber officinale) essential oil obtained by hydrohydraulic distillation assisted by microwave radiation

The (Zingiber officinale) is a plant of the zingiberáceas family, its rhizome is widely used in gastronomy for its pungent aroma and flavor. Essential oils (EO) are natural compounds; they have 25 to 70 components with different concentrations. Α-Zingiberene and α-Felandrene are the main components with volumes between 20% and 70%. For the extraction of the AE samples from 10 Colombian geographical locations were used, obtained by microwave radiated hydrodistillation (MWHD) and stored at 4°C in amber vials. 50 µL of EA and 1.0 µL of (n-tetradecane) internal standard were dissolved in dichloromethane to a final volume of 1.0 mL. The EO components were performed on a triple quadruple mass detector gas chromatograph (BRUKER 450GC-320). For its antioxidant activity (AA) the methodology of Prior for DPPH* and ABTS+ was used. The extractions showed a yield between 0.053 and 0.109 percent; and 300 g of sample at 700 watts and 40 minutes of process were used. The chromatographic profile showed 43 components referring to ketones, alcohols, cyclic ethers, aldehydes and 23 hydrocarbons, with α-Zingiberene being the majority, considered as a molecular marker of this EO. The AA presents significant differences between the samples evaluated for the localities studied.

Current Challenges and Recent Developments in Mass Spectrometry–Based Metabolomics

High-resolution mass spectrometry (MS) has advanced the study of metabolism in living systems by allowing many metabolites to be measured in a single experiment. Although improvements in mass detector sensitivity have facilitated the detection of greater numbers of analytes, compound identification strategies, feature reduction software, and data sharing have not kept up with the influx of MS data. Here, we discuss the ongoing challenges with MS-based metabolomics, including de novo metabolite identification from mass spectra, differentiation of metabolites from environmental contamination, chromatographic separation of isomers, and incomplete MS databases. Because of their popularity and sensitive detection of small molecules, this review focuses on the challenges of liquid chromatography-mass spectrometry–based methods. We then highlight important instrumentational, experimental, and computational tools that have been created to address these challenges and how they have enabled the advancement of metabolomics research.

Aromatic and Sensory Characterization of Maturana Blanca Wines Made with Different Technologies

Vitis vinífera L. cv. Maturana Blanca is an autochthonous minor variety recently recovered in the Rioja Qualified Denomination of Origin (D.O.Ca Rioja, Spain) for the production of monovarietal white wines with singular and differentiated characteristics. In this paper, Maturana Blanca wines made with different technologies were analyzed by sensory analysis and aromatic profile by gas chromatography-mass detector. Maturana Blanca wines were characterized by low pH, high acidity, and yellowish tonalities. The compounds that most influenced the aroma of Maturana Blanca wines were those related to fruity (acetates and ethyl esters), floral aromas (2-phenylethanol), and spicy notes (γ-decalactone). These wines were mainly characterized by volatile compounds of fruity aromas of banana and apple. The use of pre-fermentative maceration increased the concentration of ethyl esters and acetates and produced wines with higher odor activity values, indicating a greater aromatic intensity. The aromatic profile of Maturana Blanca wines fermented in oak barrels showed a greater complexity as they were also characterized by the presence of important amounts of furfural, whiskey lactone, and eugenol. The sensory analysis confirmed the results obtained in the aromatic analysis, and described the wines as fresh and balanced in mouth, with notes of acidity and medium to high persistence. These results will contribute to a better knowledge of this white variety.

The chromatographic analysis of extracts from poplar (Populus sp.) - Laying program GC-MS

The chromatographic analysis of extracts from poplar (Populus sp.) - Laying program GC-MS. The aim of the study was to develop the method of analysis by gas chromatography of the liquid obtained after extraction with cyclohexane of wood of different poplar varieties (Populus sp.). After applying an appropriate method, the application of gas chromatography with mass detector facilitates the analysis of the chemical composition of extracts from different types of lignocellulosic biomass. It is also possible to verify included compounds as well as to compare the content of individual compounds contained in the analysed sample. Moreover, this sample will make it possible to determine the significance of the influence of given substances on biofuel production processes based on lignocellulosic materials. One of the key chemical substances influencing the process of enzymatic hydrolysis and fermentation are extraction substances contained in lignocellulose materials used in 2nd and 3rd generation biofuels. These compounds can inhibit the whole process of producing biofuels from lignocellulosic biomass.

Bioanalytical LC-MS/MS method for Determination and comparison of Selexipag Assay in various Biological materials and its Application to Pharmacokinetics Studies in Rat plasma

A rapid, sensitive and selective bioanalytical method was developed and validated by Liquid Chromatography - Mass spectrometry (LC-MS/MS) for determination and comparison of Selexipag% assay in various biological materials. Selexipag wasextractedand compared its % assay after protein precipitation technique from various biological materials such as rat plasma, rabbit plasma, human plasma and urine. Ambrisentan was selected as internal standard. Selected analytical column Waters, X-Bridge C18 3.5µ (50 x 4.6 mm), mobile phase consists of Hexane sulfonic acid and Acetonitrile (80:20 v/v) at a flow rate of 1.0 mL /minin isocratic modeand Selexipag was determined by the +ve mode of electrospray ionization by using Mass detector. The method was developed to assess the lowerlimit of detection (LLOD)(0.5 ng/mL), lower limit of quantification(LLOQ) (5 ng/mL) concentrations and Linearity range of 1 ng/mL to 20 ng/mLconcentration with regression correlation coefficient 0.999 were observed for Selexipag in Rat plasma. The test samples at lower, medium and higher concentrationsof Selexipag shows precision (% CV was 0.8 to 1.11) and accuracy results (97.3 % to 100.6%) for inter-day and intra-day analysis at0.5, 5, 10, 15 ng/mL concentrationsof Selexipag. Appreciable recoveries for Selexipag were observed when extracted in Rat plasma compared with other biological materials. Stability of Selexipag exists in all conditions like wet extract, bench top, freeze-thaw and in instrument auto sampler as per FDA guidelines. This method indicates good results of accuracy, precision, linearity, recovery, stability and pharmacokinetic studies in rat plasma for clinical trials.

Influence of Bacillus subtilis and Trichoderma harzianum on Penthiopyrad Degradation under Laboratory and Field Studies

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.