Determining pyroxasulfone herbicide in honey samples using liquid-liquid extraction with low temperature purification (LLE-LTP).

Pyroxasulfone is a selective, systemic, pre-emergence herbicide which acts to inhibit weeds in potato, coffee, sugar cane, eucalyptus, and soybean plantations, among others. This active ingredient was classified by Brazilian legislation as a very dangerous product for the environment, and to date there are no studies involving the development of extraction methods for monitoring this compound in environmental matrices. Therefore, the objective of this study was to optimize and validate liquid-liquid extraction with low temperature purification followed by a gas chromatography coupled to mass spectrometry analysis to determine this herbicide in honey samples. The results showed that the best extractor phase was acetonitrile and ethyl acetate (6.5 mL:1.5 mL), with recovery rates close to 100% and relative standard deviations below 11%. The validation proved that the extraction method was selective, precise, accurate and linear in the range of 3-225 µg kg-1, reaching a limit of quantification of 3 µg kg-1, with a -25.95% matrix effect. Monitoring on real samples did not reveal episodes of environmental contamination with pyroxasulfone residue.

Development of methods based on low-temperature partitioning (LTP) for monitoring cresols and chlorophenols in sewage sludge, soil, and water in column leaching.

Cresols and chlorophenols are chemical contaminants that are potentially toxic to humans and can be found in sewage sludge. These chemical contaminants can migrate into the sludge-soil-water system when sludge is used as a conditioner for agricultural soils. Thus, the objective of this study was to develop methodologies based on extraction with low-temperature partitioning (LTP) to determine cresols and chlorophenols in sewage sludge, soil, and water. The analysis was performed by gas chromatography coupled with mass spectrometry (GC-MS). The validated methods were applied to monitor cresols and chlorophenols in a column-leaching study of a sludge-soil-water system. Satisfactory results were achieved for selectivity, limit of quantification (LOQ), linearity, accuracy, and precision. In the column leaching study, only 2,4,6-trichlorophenol was quantified in sludge samples after 20 days of the experiment. None of the studied compounds were quantified in soil and leached water samples, due to the degradation promoted by the microorganisms present in the sewage sludge. Finally, validated methods were suitable for monitoring cresols and chlorophenols in the sludge-soil-water system.

Extraction method for determining dinotefuran insecticide in water samples.

Dinotefuran is a compound belonging to the third generation of nicotinoid insecticides, and has been effective in combating pests that are resistant to conventional insecticides, such as organophosphates, carbamates, and pyrethroids. This molecule presents high-water solubility (39,830 mg L-1 at 25 °C) compared to other pesticides, which facilitates its drag and leaching to lower soil layers. Therefore, the present study aimed to optimize and validate liquid-liquid extraction with low temperature purification (LLE-LTP) to determine dinotefuran residues in water by high performance liquid chromatography with diode array detection (HPLC-DAD). The results revealed that the analyte recovery ranged from 85.44 to 89.72% with a relative standard deviation <5.8. LLE-LTP was selective, precise, accurate, and linear in the range from 10.0 to 210 µg L-1, and presented limits of detection and quantification of 5.00 and 10.00 µg L-1, respectively. The matrix effect was <14%. The stability study of dinotefuran in water revealed significant stability of this molecule in water in the absence of light (>130 days), and a half-life of 7 days in water with sunlight. LLE-LTP coupled to HPLC-DAD was a simple, easy, and efficient method for extracting and analyzing dinotefuran in water samples.

Determination of p-cresol levels in smoked meat products using QuEChERS method and gas chromatography-mass spectrometry.

p-Cresol is known as an environmental chemical contaminant that has toxic effects on humans. However, the presence of p-cresol in smoked foods has been seen as a flavor constituent. The present study had as objective to optimize and validate the QuEChERS method for the determination of p-cresol in beef hamburger, which was chosen as a representative matrix for six smoked meat products. The analysis was performed by gas chromatography coupled with mass spectrometry (GC-MS). The method showed limit of quantification (LOQ) of 40 µg kg-1, linearity between 40 and 200 µg kg-1, recovery higher than 70% and relative standard deviation lower than 14%. The proposed method was applied to six different smoked foods and the p-cresol concentration ranged from 148 to 872 µg kg-1 and only the turkey breast pate showed a concentration lower than the LOQ. The descending order of p-cresol level in smoked samples was: sausage > shredded tuna > salami > turkey breast > hamburger > turkey breast pate. In three analyzed samples, the results showed that the p-cresol migrates from the surface to the food inner. Finally, the proposed method was simple and efficient to quantify high levels of this contaminant in smoked foods and it could be a useful tool for the monitoring food safety and quality.

Optimization and validation of LLE-LTP to determine florpyrauxifen-benzyl herbicide in water samples by HPLC-DAD.

Florpyrauxifen-benzyl is a systemic herbicide which acts on weeds of common occurrence in rice cultivation areas using flooded or rainfed systems. The Brazilian Health Regulatory Agency (ANVISA) authorized the commercialization of this pesticide, but did not establish guidelines with an extraction and quantification method of residues of this compound as a form of environmental monitoring. Therefore, the present study aimed to optimize and validate the liquid-liquid extraction with low temperature purification (LLE-LTP) to determine florpyrauxifen-benzyl content in water samples by high performance liquid chromatography with diode array detection (HPLC-DAD). The recovery ranged from 95.84 to 105.4% with a relative standard deviation less than 1.5. LLE-LTP was selective, precise, accurate, linear in the range from 4.00 to 150 µg L-1, and the limit of quantification was 4.00 µg L-1. The stability study of the compound in water revealed its degradation in 25 days and DT50 in approximately 5 days. LLE-LTP coupled to HPLC-DAD presented itself as a simple, easy and efficient method of extracting and analyzing it in water samples.

Optimization and validation of liquid-liquid extraction with low-temperature purification (LLE-LTP) for determining fluopyram fungicide in water samples using HPLC-DAD.

Fluopyram is a fungicide and nematicide that belongs to the chemical group of benzamides, which act as succinate dehydrogenase inhibitors (SDHIs) on the mitochondrial respiratory chain of fungi. Despite being well known in several countries, there are few studies involving the optimization and validation of extraction methods for determining fluopyram in water samples. Therefore, this study aimed to optimize and validate liquid-liquid extraction with low-temperature purification (LLE-LTP) to determine fluopyram fungicide in water samples using high-performance liquid chromatography with diode array detection (HPLC-DAD). A two-level full factorial design was employed to optimize LLE-LTP which enabled achieving a recovery rate close to 100% and relative standard deviations (RSD) < 10.0%. The validation showed that the extraction method may be considered selective, precise, accurate, and linear in the range of 6.0 to 200 µg L-1. The LOD and LOQ were 4.0 and 6.0 µg L-1, respectively, proving the efficiency of this method for trace level determination of this fungicide in water samples. LLE-LTP coupled to HLPC-DAD analysis showed a matrix effect of less than 8% and it was applied in monitoring 20 environmental water samples, but no fluopyram residue was detected in the samples.

Determination of DDT in honey samples by liquid-liquid extraction with low-temperature purification (LLE-LTP) combined to HPLC-DAD.

Honey is widely consumed worldwide, however, this food can be contaminated by chemical contaminants, such as the insecticide dichlorodiphenyltrichloroethane (DDT). Despite legal restrictions on DDT use, this organochlorine pesticide has been detected in honey collected in several developed and developing countries, representing risks to human health, animals, and the environment due to its high environmental persistence, potential carcinogenicity, and ecotoxicological effects. Thus, the development of an analytical method for DDT monitoring in this matrix is important to ensure food security. Therefore, this study aimed to optimize and validate a simple, low-cost, and efficient method using the liquid-liquid extraction with low-temperature purification (LLE-LTP) to determine DDT in honey samples by high-performance liquid chromatography with diode array detector (HPLC-DAD). The proposed method was validated according to SANTE guidelines, being considered selective, precise, accurate, and linear in the range of 8.0-160 µg kg-1. The limits of detection (LOD) and quantification (LOQ) achieved were 4.0 and 8.0 µg kg-1, respectively. This LOQ value is lower than the maximum residue limit established by the Brazilian and European Union legislation. Therefore, the LLE-LTP combined to HPLC-DAD allows the routine analysis of DDT in honey samples and can be widely applied in studies to monitor this pesticide, especially in developing countries, where DDT use is still allowed.

p-Cresol in cheese: Is it a flavouring compound or chemical contaminant?

p-Cresol has been identified as a flavouring compound in cheeses; however, scientific studies have already identified p-cresol as a potential chemical contaminant in environmental matrices. Thus, the objective of this study was to evaluate four traditional methods for extracting p-cresol from cheese samples in order to validate the best method, and finally to apply it to five cheese samples with different origins, processing and ripeness times. The analyses were performed by gas chromatography-mass spectrometry after derivatisation of p-cresol with anhydride acetic and pyridine. Better results were achieved by the QuEChERS method, which showed recovery higher than 80%, relative standard deviation lower than 16%, limit of quantification of 5 µg kg-1 and linearity between 5 and 400 µg kg-1 with R2 0.99. p-Cresol was quantified in almost all of the samples analysed at different concentration levels, which were in an increasing order at µg kg-1: Cheddar (< LOQ), Parmesan (8 ± 0.7), Gorgonzola (103 ± 14), smoked Provolone (365 ± 28) and barbecue cheese (1001 ± 187). Although no maximum residue limit has been established for p-cresol in food, the results suggest that cheeses exposed to charcoal combustion notably increase the p-cresol levels and may represent a hazard to human health, especially in risk groups such as patients with chronic kidney disease who have serious problems with p-cresol.

Simultaneous and direct determination of glyphosate and AMPA in water samples from the hydroponic cultivation of eucalyptus seedlings using HPLC-ICP-MS/MS.

Glyphosate is the main herbicide currently used in the world due to wide applicability and efficiency in controlling weeds in many crops. However, its overuse may lead to undesirable impacts on the environment and to human health in the long run. This present study aimed to optimize and validate solid phase extraction (SPE) using an anionic resin for the simultaneous and direct determination of glyphosate and aminomethylphosphonic acid (AMPA) in water samples using high-performance liquid chromatography combined with inductively coupled plasma with triple quadrupole mass spectrometer (HPLC-ICP-MS/MS). The results showed that recovery percentage and relative standard deviation were 103.9 ± 7.9 and 99.40 ± 9.9% for glyphosate and AMPA, respectively. The validation certified that the method was precise, accurate, linear, and selective, with a limit of quantification of 1.09 and 0.29 µg L-1 for glyphosate and AMPA, respectively. The optimized methodology reached the concentration factor of 250 times and was successfully applied to analyze water samples from hydroponic cultivation of the eucalyptus seedlings. The results showed that the exudation process occurs at glyphosate doses starting from 2 L ha-1.

Catharanthus roseus potential for phyto-stabilizing metals in sewage sludge.

This work evaluated the potential of Catharanthus roseus in phytoremediation of As, Ba, Cd, Cu, Cr, Ni, Pb, Se and Zn in sewage sludge-based substrates. C. roseus was cultivated for 108 days in a treatment containing sewage sludge:vermiculite (70:30%) and in the control with 100% commercial substrate. The plants cultivated in sludge showed approximately four times greater height, number of leaves and stem diameter, as well as 89% higher fresh mass than those of the control. The highest concentrations of the metals were obtained in the roots of plants grown in the sludge, and ranged from 2.04 (Cd) to 1121 mg kg-1 (Zn). Cu, Cd and Zn had a higher bioconcentration factor than 1 in both treatments. On the other hand, the translocation factor value in the control was greater than 1 for Ba, Cd, Cu, Ni, Se and Zn. The results showed that C. roseus was efficient in the phytoremediation of the evaluated metals, in which the translocation process was progressive in the treatment that presented higher metal content.

Determination of three cresol isomers in sewage sludge by solid-liquid extraction with low temperature purification and gas chromatography-mass spectrometry.

Cresols are chemical contaminants derivative from phenol which can be found in sewage sludge. However, little attention has been given to monitoring these compounds in environmental matrices in the literature. Thus, the objective of this study was to develop a simple method based on solid-liquid extraction with low temperature purification for determining three cresol isomers in sludge. The quantification of these compounds was performed by gas chromatography coupled to mass spectrometry with a previous derivatization step. After a detailed study, the cresol recovery was higher than 91%, with relative standard deviation lower than 12% and a limit of quantification of 20 µg kg-1. Linearity was achieved between 10 and 90 µg L-1 (R2 > 0.98) with the standard solutions prepared in matrix extracts due to the trouble caused by the matrix effect. The proposed method was applied with success for monitoring cresols in sewage sludge samples coming from six different wastewater treatment plants. All samples showed contamination by cresols, mainly p-cresol with values between 32.3 and 516.9 µg kg-1. The majority of the analyzed samples showed a total sum of the isomers higher than the maximum residue limit established by Brazilian legislation (160 µg kg-1).

Easy and fast extraction methods to determine organochlorine pesticides in sewage sludge, soil, and water samples based at low temperature.

Organochlorine pesticides present in sewage sludge can contaminate soil and water when they are used as either fertilizer or agricultural soil conditioner. In this study, the technique solid-liquid extraction with low temperature purification was optimized and validated for determination of ten organochlorine pesticides in sewage sludge and soil samples. Liquid-liquid extraction with low temperature purification was also validated for the same compounds in water. Analyses were performed by gas chromatography-mass spectrometry operating in the selective ion monitoring mode. After optimization, the methods showed recoveries between 70% and 115% with relative standard deviation lower than 13% for all target analytes in the three matrices. The linearity was demonstrated in the range of 20 to 70 µg L-1, 0.5 to 60 µg L-1, and 3 to 13 µg L-1, for sludge, soil, and acetonitrile, respectively. The limit of quantification ranged between 2 and 40 µg kg-1, 1 and 6 µg kg-1, and 0.5 µg L-1 for sludge, soil, and water, respectively. The methods were used in the study of pesticide lixiviation carried out in a poly vinyl chlorine column filled with soil, which had its surface layer mixed with sludge. The results showed that pesticides are not leached into soil, part of them is adsorbed by the sewage sludge (4-40%), and most pesticides are lost by volatilization.

New Pyrethroids for Use Against Tuta Absoluta (Lepidoptera: Gelechiidae): Their Toxicity and Control Speed.

Insect pests are responsible for major losses in crop productivity, and insecticides are the main tools used to control these organisms. There is increasing demand for new products for pest management. Therefore, the aim of this study was to assess the toxicity of pyrethroids with acid moiety modifications to measure the insecticidal activity of these compounds on Tuta absoluta (Meyrick) (Lepidoptera: Gelechiidae). First, we synthesized E/Z mixtures of five pyrethroids: [9], [10], [11], [12], and [13]. Then, we separated the cis and trans pyrethroid isomers of [9], [10], [11], and [12]. We assessed the toxicity of these compounds against T. absoluta. The E/Z mixtures of the five pyrethroids (30 µg of substance per mg-1 of insect) caused high (100%) and rapid (<12 h) tomato borer mortality. The cis isomer of pyrethroid [10] was the most toxic to T. absoluta, causing mortality similar to permethrin. The other isomers were less powerful than permethrin.

Fast extraction of polychlorinated dibenzo-p-dioxin and polychlorinated dibenzofuran in sewage sludge and soil samples.

The current environmental legislations recommend monitoring chemical contaminants such as polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans before the use of sewage sludge on the agricultural land. In this study, a solid-liquid extraction with low-temperature purification (SLE-LTP) was optimized and validated to determine 2,3,7,8-tetrachlorodibenzo-p-dioxin and 2,3,7,8-tetrachlorodibenzofuran in sewage sludge and soil samples. The analyses were performed by gas chromatography-mass spectrometry operating in the selective ion mode (GC-MS-SIM). Acetonitrile:ethyl acetate 6.5:1.5 (v/v) was the best extraction phase, and the recoveries percentages were close to 100%. The linearity was demonstrated in the range of 1.25-25 µg L-1 of 1.25-20 µg L-1 for sewage sludge and soil, respectively. Matrix effect was proved for the two compounds and in the two matrices studied. Extraction percentages were between 78 and 109% and relative standard deviations ≤ 19%. The proposed method is faster than methods described in the literature because showed a few steps. The quantification limits (LOQ) in sewage sludge were 6.4 and 32 ng TEQ kg-1 for 2,3,7,8-TCDF and 2,3,7,8-TCDD, respectively. In soil, LOQs were 0.8 and 8.0 ng TEQ kg-1 for 2,3,7,8-TCDF and 2,3,7,8-TCDD, respectively. These values are lower than the maximum residue limits established by European Legislation. The method was applied to 22 agricultural soil samples from different Brazilian cities and 2,3,7,8-TCDF was detected in one of these samples.

Toxicity of new pyrethroid in pest insects Asciamonuste and Diaphania hyalinata, predator Solenopsis saevissima and stingless bee Tetragonisca angustula.

There is increasing demand for new products for vegetable pest management. Thus, the aim of this study was to assess the toxicity of pyrethroids with acid moiety modifications to measure the insecticidal activity of these compounds on the lepidopteran vegetable pests Diaphania hyalinata (L.) (Lepidoptera: Pyralidae) and Asciamonuste (Latreille) (Lepidoptera: Pieridae) and evaluate their selectivity for the predatory ant Solenopsis saevissima (F. Smith) (Hymenoptera: Formicidae) and pollinator Tetragonisca angustula (Latreille) (Hymenoptera: Apidae: Meliponinae). Racemic mixtures of five new pyrethroids (30 µg molecule mg-1 insect body weight) resulted in high (100%) and rapid (stable LD50 after 12 h) mortality in D. hyalinata and A. monuste. In A. monuste, the trans-pyrethroid [12] isomer showed similar toxicity to permethrin. For D. hyalinata, the trans-pyrethroid [9] isomer and cis-pyrethroid [10] isomer were as toxic as permethrin. Due to their low selectivity, these new pyrethroids should be applied on the basis of ecological selectivity principles to minimize impacts on nontarget organisms S. saevissima and T. angustula.

Determination of Eucalyptus spp lignin S/G ratio: a comparison between methods.

The syringyl/guaiacyl ratio was determined for six different Eucalyptus spp. wood clones cultivated in four regions in Brazil. The determinants were made by pyrolysis-gas chromatography-mass spectrometry (Py-GC-MS) and the results were compared with those obtained by alkaline nitrobenzene oxidation method. The S/G ratios were obtained considering all the identified lignin derivatives in the pyrograms and also using two groups of markers. The first group of markers consisted of guaiacol, 4-methylguaiacol, 4-vinylguaiacol, trans-isoeugenol, syringol, 4-methylsyringol, 4-vinylsyringol and trans-4-propenylsyringol compounds as markers. The second group included guaiacol, 4-methylguaiacol, 4-vinylguaiacol, vanillin, 4-ethylsyringol, 4-vinylsyringol, syringaldehyde, syringylacetone and trans-4-propenylsyringol. It was observed from the statistical analysis that the values of S/G obtained by Py-GC-MS using the two groups of markers did not differ significantly from those obtained by nitrobenzene oxidation method.

Synthesis and insecticidal activity of new pyrethroids.

BACKGROUND: Pyrethroids are among the most potent pesticides known, with great potential for structural variation with retention or enhancement of potency. The simple methyl ester is easier to prepare (at least one step shorter) than the more complex pyrethroids modified on the alcohol moiety. The objective was to synthesise methyl esters of pyrethroid acids containing an aromatic ring on the acid moiety and evaluate their biological activity against Ascia monuste orseis Latr., Tuta absoluta Meyrick, Periplaneta americana (L.), Musca domestica L. and Sitophilus zeamais (Motsch.). RESULTS: The synthetic sequence required seven steps: protection of the hydroxyl groups of D-mannitol, diol oxidative cleavage with sodium metaperiodate, alkene formation by Wittig reaction with methoxycarbonylmethylidene(triphenyl)phosphorane, cyclopropanation, acetal hydrolysis with perchloric acid and oxidative cleavage with sodium metaperiodate gave methyl (1S, 3S)-3-formyl-2,2-dimethylcyclopropane-1-carboxylate. The final step comprised reaction of the aldehyde with five different aromatic phosphorus ylides to give the pyrethroids. CONCLUSION: An efficient and versatile synthesis of ten new pyrethroid methyl esters has been accomplished from the readily available D-mannitol in seven steps. All compounds showed insecticidal activity, and methyl (1S, 3S)-3-[(Z)-2-(4-chlorophenyl)vinyl]-2,2-dimethylcyclopropane-1-carboxylate was the most active, killing 90% of A. monuste orseis and 100% of T. absoluta and P. americana.

Effect of storage time on the composition and content of wood extractives in Eucalyptus cultivated in Brazil.

Lipophilic wood extractives commonly referred to as pitch, cause significant problems for the pulp and paper industries. The reduction of these extractives is an important aspect that concerns industries around the world. In the present work the change in the amount and chemical composition of lipophilic extractives from Eucalyptus spp. stored for 20, 40, 60, 100, 140 and 180 days after harvesting was investigated. The results showed a decrease in extractives content with storage time, with the most significant decrease occurring 60 days after harvesting. In addition, fatty acids and sterols were the main classes of compounds responsible for the significant decrease in extractive content. Data were analyzed by principal component analysis. PC1 explains approximately 99% of the total variance, and beta-sitosterol was the major compound responsible for the differentiation. These studies demonstrate that in terms of economical aspects, quality of the pulp and paper and minimization of pitch formation, the best period of wood storage is 60 days.