Evaluation of pesticide adsorption in gas chromatographic injector and column

Components in complex matrices can cause variations in chromatographic response during analysis of pesticides by gas chromatography. These variations are related to the competition between analytes and matrix components for adsorption sites in the chromatographic system. The capacity of the pesticides chlorpyrifos and deltamethrin to be adsorbed in the injector and chromatographic column was evaluated by constructing three isotherms and changing the column heating rate to 10 and 30 ºC min-1. By using ANCOVA to compare the slope of calibration graphs, results showed that the higher the injector temperature (310 ºC) the lower the pesticide adsorption. Also, deltamethrin influenced the adsorption of chlorpyrifos on the column chromatographic.

Optimization of chromatographic conditions and comparison of extraction efficiencies of four different methods for determination and quantification of pesticide content in bovine milk by UFLC-MS/MS

This paper describes the optimization of a multiresidue chromatographic analysis for the identification and quantification of 20 pesticides in bovine milk, including three carbamates, a carbamate oxime, six organophosphates, two strobilurins, a pyrethroid, an oxazolidinedione, an aryloxyphenoxypropionate acid/ester, a neonicotinoid, a dicarboximide, and three triazoles. The influences of different chromatographic columns and gradients were evaluated. Furthermore, four different extraction methods were evaluated; each utilized both different solvents, including ethyl acetate, methanol, and acetonitrile, and different workup steps. The best results were obtained by a modified QuEChERS method that lacked a workup step, and that included freezing the sample for 2 hours at -20 ºC. The results were satisfactory, yielding coefficients of variation of less than 20%, with the exception of the 50 µg L-1 sample of famoxadone, and recoveries between 70 and 120%, with the exception of acephate and bifenthrin; however, both analytes exhibited coefficients of variation of less than 20%.

MONITORING OF ORGANOPHOSPHOROUS PESTICIDE RESDUES IN SAMPLES OF BANANA, PAPAYA, AND BELL PEPPER

The objective of this study was to monitor 11 organophosphorus pesticides in samples of papaya, bell pepper, and banana, commercialized in the metropolitan area of Vitória (ES, Brazil). The pesticides were determined by an optimized and validated method using high performance liquid chromatography with tandem mass spectrometry (HPLC-MS/MS). All three samples exhibited a matrix effect for most of the pesticides, mainly with signal suppression, and therefore the calibration curves were produced in matrices. Linearity revealed coefficients of determination (r2) greater than 0.9895 for all pesticides and recovery results ranged from between 76% and 118% with standard deviation no greater than 16%. Precision showed relative standard deviation values lower than 19% and HorRat values lower than 0.7, considering all pesticides. Limits of quantification were less than 0.01 mg/kg for all pesticides. Regarding analysis of the samples (50 of each), none of the pesticides exceeded the maximum residue limit determined by Brazilian legislation.

EVALUATION OF A BUFFERED SOLID PHASE DISPERSION PROCEDURE ADAPTED FOR PESTICIDE ANALYSES IN THE SOIL MATRIX

An evaluation of the pesticides extracted from the soil matrix was conducted using a citrate-buffered solid phase dispersion sample preparation method (QuEChERS). The identification and quantitation of pesticide compounds was performed using gas chromatography-mass spectrometry. Because of the occurrence of the matrix effect in 87% of the analyzed pesticides, the quantification was performed using matrix-matched calibration. The method's quantification limits were between 0.01 and 0.5 mg kg-1. Repeatability and intermediate precision, expressed as a relative standard deviation percentage, were less than 20%. The recoveries in general ranged between 62% and 99%, with a relative standard deviation < 20%. All the responses were linear, with a correlation coefficient (r) ≥0.99.

Outplanting performace of eucalyptus clonal cuttings produced in different containers and substrates

The objective of this work was to evaluate the outplanting growth of Eucalyptus grandis e E. saligna clones, produced by cuttings in tubes (50cm³) and in pressed blocks (40x60x07cm) - 175 cm³/ seedlings, with different substrates (BT - sugarcane bagasse+sugarcane filter cake; AR - carbonized rice hull + eucalyptus bark; TF - peat). The experiment was arranged in a randomized block design, in a 2x7 factorial (2 clones and 7 treatments), with four replicates with 25 plants. Survival was evaluated two months later. Plant growth was monitored through height and ground level diameter at 20, 40, 60, 120 and 180 days after outplanting. To evaluate the effect of the containers on stem and root biomass in both clones, 180 days after outplanting, the cuttings grown in BT substrate with fertilizer were selected. One plant per plot of each clone, grown in tubes and in pressed blocks was selected. The E. grandis and E. saligna cuttings grown in pressed blocks with sugarcane bagasse+sugarcane filter cake presented greater height and diameter after out planting. Both clones presented larger root, bark, log and branch biomass production in plants produced in the block system. Cuttings of E. saligna grown in pressed blocks showed 80% most wood biomass 180 days after outplanting, compared to that grown in tubes. In E. grandis, the differences in diameter and height, in function of the cutting production system, decreased along time, while in E. saligna these differences increased along the evaluation period.

PRODUCTION OF AUSTRALIAN CEDAR SEEDLINGS INOCULATED WITH ARBUSCULAR MYCORRHIZAL FUNGI IN DIFFERENT TYPES OF CONTAINERS

ABSTRACT The present study aimed to evaluate the growth and the levels of N, P, K, Ca and Mg in Australian cedar seedlings which had been inoculated with arbuscular mycorrhizal fungi (AMF) in different types of containers. The experiment was carried out in a greenhouse and the experimental design was that of randomized complete blocks (RCB), with a 4 x 4 factorial design consisting of four inoculation treatments with AMF (Rhizophagus clarum, Gigaspora margarita, a mixed inoculation (R. clarum + G. margarita) and the control (with no AMF inoculation); four types of containers (plastic bags measuring 250 cm3, tubes of 55 and 130 cm3 and pressed blocks 440 cm3. plant-1), with four repetitions. The height, the diameter of the stem base, the aerial part dry weight (APDW), the dry weight of the root (DWR) and the total plant dry weight (DW) were measured, along with the Dickson quality index, the percentage of mycorrhizal colonization and the levels of N, P, K, Ca and Mg in the aerial part dry weight. One hundred and thirty eight days (138) days after sowing, the greatest growth and/or the highest levels of P, K and Ca could be observed in the aerial part dry weight of the Australian cedar seedlings which had been planted in the pressed block container and inoculated with a mixture of the two AMF species (G. margarita + R. clarum) or with just R. clarum. Thus it can be seen that AMF can make a significant contribution to the production of Australian cedar seedlings.

Evaluation of alternative containers to determining the working width of fertilizer spreaders

Farmers have difficult of determining the evenness of transverse distribution and the working width, due the tests with this aim require equipments and complex methodologies. So, this study evaluates some alternative containers with the aim to allow a more accessible adjustment of the full width of the solid fertilizer spreaders. Four different containers were tested: i) standard container constructed in accordance with ISO 5690/1; ii) container of polyethylene (plastic trays) with screen shading to prevent the ricochet of material; iii) containers composed by boxes of long-life milk, and iv) containers composed by flowerpots (number 3.5). Also, three different spreaders were used for the tests. Alternative containers showed greater retention of particles than the standardized containers. The full width of work obtained for the coefficients of variation of 12.5; 15; 17.5 and 20%, ranged due the containers in the different pathways. The flowerpots of polyethylene showed similar results to the standardized containers. The heights of the containers were more important for its efficiency than its area of collection.

Sensibility analysis of the pearl model for pesticide leaching in the State of Mato Grosso do Sul, Brazil

For an accurate use of pesticide leaching models it is necessary to assess the sensitivity of input parameters. The aim of this work was to carry out sensitivity analysis of the pesticide leaching model PEARL for contrasting soil types of Dourados river watershed in the state of Mato Grosso do Sul, Brazil. Sensitivity analysis was done by carrying out many simulations with different input parameters and calculating their influence on the output values. The approach used was called one-at-a-time sensitivity analysis, which consists in varying independently input parameters one at a time and keeping all others constant with the standard scenario. Sensitivity analysis was automated using SESAN tool that was linked to the PEARL model. Results have shown that only soil characteristics influenced the simulated water flux resulting in none variation of this variable for scenarios with different pesticides and same soil. All input parameters that showed the greatest sensitivity with regard to leached pesticide are related to soil and pesticide properties. Sensitivity of all input parameters was scenario dependent, confirming the need of using more than one standard scenario for sensitivity analysis of pesticide leaching models.

Formation of beetroot seedlings in different protected environments, substrates and containers in Aquidauana region, State of Mato Grosso do Sul, Brazil

This study with beetroot seedlings, cultivar Top Tall Early Wonder, was carried out at the State University of Mato Grosso do Sul (UEMS/Aquidauana), from October to November 2008. Three environments of cultivation were used: greenhouse; nursery with monofilament screen of 50 % of shading; and nursery with aluminized thermal reflective screen of 50% of shading. In these environments, three polystyrene trays of 72, 128 and 200 cells, filled with four substrates, were tested: soil; Plantmax®; coconut fiber and vermiculite. There were no replication environments and then each one was considered an experiment alone. For each environment, it was adopted a completely randomized design in factorial scheme 3x4 (three trays x four substrates), with four replications, performing individual analysis of variance and joint analysis of experiments for environment comparisons. The monofilament screen is the best environment for seedlings produced in tray of 72 cells, and the greenhouse was the best environment for seedlings produced in trays of 128 cells. The best seedlings were formed in the tray of 72 cells. Vermiculite was the best substrate.

Physicochemical composition, minerals, and pesticide residues in organic grape juices

Demand for organic products is intensified in many countries each year. Following this trend, Brazil produces increasing volumes of organic grape juice. In this way, a survey of organic grape juices made from grapes produced according to this system was carried out where physicochemical composition, minerals, trace elements, and pesticide residues were determined. Variables related to grape juice composition were performed by physicochemical procedures; minerals and trace elements, by inductively plasma optical emission spectrometry; pesticide residues, by liquid chromatography-mass spectrometry. Main results show that the physicochemical composition of organic grape juices was in general in accordance to the Brazilian legislation. The mean concentrations of trace elements were very low, varying from 0.002 (Cd) to 0.970 (Ba) mg L–1. Pesticide residues were not detected in any sample analyzed (MRL= 10 µg L–1). These results show that the Serra Gaúcha viticultural region present conditions to produce organic grape juices, despite the adverse climate factors that occurs in some years. Nevertheless, these products should be made with grape varieties, such as the labrusca ones, less susceptibles to the main grapevine pathogens.

Evaluation of pesticide residues in oranges from São Paulo, Brazil

Pesticides in “PERA” orange samples (N = 57) from São Paulo City, Brazil were assessed and the pesticide intake contribution was estimated for chronic risk assessment. Seventy-six pesticides were evaluated by the gas chromatography multi-residue method, including isomers and metabolites (4.332 determinations). The mean recoveries at the limit of quantification level were in the range of 72-115% and the relative standard deviation for five replicate samples was 1-11%. The limits of detection and quantification ranged from 0.005 to 0.4 mg.kg−1 and from 0.01 to 0.8 mg.kg−1, respectively. Pesticides were found in 42.1% of the samples at levels ranging from 0.06 to 2.9 mg.kg−1. Of the contaminated samples, 3.5% contained residues (bifenthrin and clofentezine) above the maximum residue level and 12.3% contained unauthorized pesticides (azinphos-ethyl, parathion, myclobutanil, profenofos, and fenitrothion). The estimated risk characterization for orange intake by adults and children, respectively, ranged from 0.04 to 6.6% and from 0.1 to 26.5% of the acceptable daily intake. The detection of irregular residues emphasizes the need for better implementation of Good Agriculture Practices and greater control of formulated products. Other pesticides surveyed did not pose a health risk due to consumption.

Of empty thoughts and blind intuitions Kant's answer to McDowell

This paper examines the relation between intuition and concept in Kant in light of John McDowell's neo-Kantian position that intuitions are concept-laden.2 The focus is on Kant's twofold pronouncement that thoughts without content are empty and that intuitions without concepts are blind. I show that intuitions as singular representations are not instances of passive data intake but the result of synthetic unification of the given manifold of the senses by the power of the imagination under the guidance of the understanding. Against McDowell I argue that the amenability of intuitions to conceptual determination is not due some pre-existing, absolute conceptuality of the real but to the "work of the subject."3 On a more programmatic level, this paper seeks to demonstrate the limitations of a selective appropriation of Kant and the philosophical potential of a more comprehensive and thorough consideration of his work. Section 1 addresses the unique balance in Kant's philosophy between the work on particular problems and the orientation toward a systematic whole. Section 2 outlines McDowell's take on the Kantian distinction between intuition and concept in the context of the Kant readings by Sellars and Strawson. Section 3 exposes McDowell's relapse into the Myth of the Given. Section 4 proposes a reading of Kant's theoretical philosophy as an epistemology of metaphysical cognition. Section 5 details Kant's original account of sensible intuition in the Inaugural-Dissertation of 1770. Section 6 presents the transition from the manifold of the senses to the synthesis in the imagination and the unification through the categories in the Critique of pure reason (1781 and 1787). Section 7 addresses Kant's formalism in epistemology and metaphysics.

Empty Pool

The Brock pool as it begins to be filled with water.

The fast atom bombardment mass spectrometric analysis of the carbamate pesticide carbaryl

The carbamate pesticide, carbaryl, was quantitatively studied using fast atom bombardment mass spectrometry (FAB-MS). Mass spectra were obtained in the positive ion-mode using both 2-nitrophenyloctyl ether (NPOE) and 3-nitrobenzyl alcohol (NBA) as matrix liquids. The sample was applied by three different techniques; simple mixing, solvent mixing and surface precipitation. Smaller volumes of matrix liquid were found to produce more favourable ion currents. Detection limits were largely independent of the matrix or application technique used. The relationship between ion current and the mass of analyte was found to be intricately related to the choice of matrix liquid.