Development of a rapid method for the determination of antibiotic residues in honey using UPLC-ESI-MS/MS

Abstract An accurate, reliable and fast multianalyte/multiclass ultra-performance liquid chromatography–tandem mass spectrometry (UPLC–MS/MS) method was developed and validated for the simultaneous analysis of 23 pharmaceuticals, belonging to different classes amphenicols, sulfonamides, tetracyclines, in honey samples. The method developed consists of ultrasonic extraction followed by UPLC–ESI–MS/MS with electrospray ionization in both positive mode and negative mode. The influence of the extraction solvents and mobile phase composition on the sensitivity of the method, and the optimum conditions for sample weight and extraction temperature in terms of analyte recovery were extensively studied. The identification of antibiotics is fulfilled by simultaneous use of chromatographic separation using an Acquity BEH C18 (100 mm x 2.1 mm, 1.7 µm) analytical column with a gradient elution of mobile phases and tandem mass spectrometry with an electrospray ionization. Finally, the method developed was applied to the determination of target analytes in honey samples obtained from the local markets and several beekeepers in Muğla, Turkey. Ultrasonic-extraction of pharmaceuticals from honey samples is a well-established technique by UPLC–ESI–MS/MS, the uniqueness of this study lies in the simultaneous determination of a remarkable number of compounds belonging to 23 drug at the sub-nanogram per kilogram level.

Flutuação populacional de Anastrepha fraterculus (Wiedemann, 1830) (Diptera, Tephritidae) na Região Oeste de Santa Catarina, Brasil

Fruit flies are the major pests in fruit orchards and require a frequent insecticide aplication control, which increases production cost and chemical residues in fruits. Adults of Anastrepha fraterculus were sampled from twelve peach, plum, orange, tangerine and acid lime orchards in four counties in the Western Region of Santa Catarina. Modified McPhail plastic traps, baited with glucose 10%, were used to collect the flies from October 1998 to September 2000. Trap monitoring, bait replacement and fruit flies sorting by species and sex were done weekly. A total of 4,164 specimens of A. fraterculus was collected and highest population was registered in the county of Chapecó (64,8% of all sampled flies). Adults were collected all year long, with the highest population peaks occurring from December and January, although the fluctuation was different for each fruit species due to their particular phenology and in different years. Positive correlation among temperature, atmospheric humidity and population levels of adults of A. fraterculus was observed. According to the degree days obtained for each year, 4851.9, 4632.9 and 4983.7, respectively in 1998, 1999 and 2000, it was established that A. fraterculus could present an average of 11.2 generations a year.

Determinação do ponto de névoa em surfactantes não iônicos por espectroscopia de impedância elétrica

In this paper, we analyze the use of electrical impedance spectroscopy applied to determination of cloud point. The slope of admittance measured at 100 kHz is reduced to temperature above the critical value which characterizes the phase transition, in a strong indication that this process is activated during the clouding. Additionally to this study we explored the influence of parameters such as additives and temperature on the performance of phase separation of residues (silver nanoparticles) by cloud point extraction. The interaction with salt maximizes the separation of chemical residues in a progressively reduced temperature.

Chemical and physical properties of organic residues

Due to human activity, large amounts of organic residue are generated daily. Therefore, an adequate use in agricultural activities requires the characterization of the main properties. The chemical and physical characterization is important when planning the use and management of organic residue. In this study, chemical and physical properties of charcoal, coffee husk, pine-bark, cattle manure, chicken manure, coconut fiber, sewage sludge, peat, and vermiculite were determined. The following properties were analyzed: N-NH4+, N-N0(3)-, and total concentrations of N, P, S, K, Ca, Mg, Mn, Zn, Cu, and B, as well as pH, Electrical Conductivity (EC) and bulk density. Coffee husk, sewage sludge, chicken manure and cattle manure were generally richer in nutrients. The EC values of these residues were also the highest (0.08 - 40.6 dS m-1). Peat and sewage sludge had the highest bulky density. Sodium contents varied from 0 to 4.75 g kg-1, with the highest levels in chicken manure, cattle manure and sewage sludge. Great care must be taken when establishing proportions of organic residues in the production of substrates with coffee husk, cattle or chicken manure or sewage sludge in the calculation of the applied fertilizer quantity in crop fertilization programs.

Biomass decomposition and nutrient release from black oat and hairy vetch residues deposited in a vineyard

A significant quantity of nutrients in vineyards may return to the soil each year through decomposition of residues from cover plants. This study aimed to evaluate biomass decomposition and nutrient release from residues of black oats and hairy vetch deposited in the vines rows, with and without plastic shelter, and in the between-row areas throughout the vegetative and productive cycle of the plants. The study was conducted in a commercial vineyard in Bento Gonçalves, RS, Brazil, from October 2008 to February 2009. Black oat (Avena strigosa) and hairy vetch (Vicia villosa) residues were collected, subjected to chemical (C, N, P, K, Ca, and Mg) and biochemical (cellulose - Cel, hemicellulose - Hem, and lignin - Lig content) analyses, and placed in litter bags, which were deposited in vines rows without plastic shelter (VPRWS), in vines rows with plastic shelter (VPRS), and in the between-row areas (BR). We collected the residues at 0, 33, 58, 76, and 110 days after deposition of the litter bags, prepared the material, and subjected it to analysis of total N, P, K, Ca, and Mg content. The VPRS contained the largest quantities and percentages of dry matter and residual nutrients (except for Ca) in black oat residues from October to February, which coincides with the period from flowering up to grape harvest. This practice led to greater protection of the soil surface, avoiding surface runoff of the solution derived from between the rows, but it retarded nutrient cycling. The rate of biomass decomposition and nutrient release from hairy vetch residues from October to February was not affected by the position of deposition of the residues in the vineyard, which may especially be attributed to the lower values of the C/N and Lig/N ratios. Regardless of the type of residue, black oat or hairy vetch, the greatest decomposition and nutrient release mainly occurred up to 33 days after deposition of the residues on the soil surface, which coincided with the flowering of the grapevines, which is one of the phenological stages of greatest demand for nutrients.

Availability of heavy metals in contaminated soil evidenced by chemical extractants

Heavy metals have been accumulating in Brazilian soils, due to natural processes, such as atmospheric deposition, or human industrial activities. For certain heavy metals, when in high concentrations in the soil, there is no specific extractant to determine the availability of these elements in the soil. The objective of the present study was to evaluate the availability of Cd, Cu, Fe, Mn, Pb and Zn for rice and soybeans, using different chemical extractants. In this study we used seven soil samples with different levels of contamination, in completely randomized experimental design with four replications. We determined the available concentrations of Cd, Cu, Fe, Mn, Pb and Zn extracted by Mehlich-1, HCl 0.1 mol L-1, DTPA, and organic acid extractants and the contents in rice and soybeans, which extracts were analyzed by ICP-OES. It was observed that Mehlich-1, HCl 0.1 mol L-1 and DTPA extractants were effective to assess the availability of Cd, Cu, Pb and Zn for rice and soybeans. However, the same was not observed for the organic acid extractant.

Doses and methods of distribution of potassium chloride on soybean crop (Glycine max (L.) Merrill) in a red latosol, affecting soil salinity, grain production and chemical composition of leaves

The present work deal t wi th an experiment under field conditions and a laboratory test of soil incubation the objectives were as follows: a. to study effects on soybean grain product ion and leaf composition of increasing doses of potassium chloride applied into the soil through two methods of distribution; b. to observe chemical modifications in the soils incubated with increasing doses of potassium chloride; and, c. to correlate field effects with chemical alterations observed in the incubation test, The field experiment was carried out in a Red Latosol (Haplustox) with soybean cultivar UFV - 1. Potassium chloride was distributed through two methods: banded (5 cm below and 5 cm aside of the seed line) and broadcasted and plowed-down. Doses used were: 0; 50; 100 and 200 kg/ha of K2O. Foliar samples were taken at flowering stage. Incubation test were made in plastic bags with 2 kg of air dried fine soil, taken from the arable layer of the field experiment, with the following doses of KC1 p,a. : 0; 50; 100; 200; 400; 800; 1,600; 3.200; 6,400 and 12,800 kg/ha of K(2)0. In the conditions observed during the present work, results allowed the following conclusions: A response by soybean grain production for doses of potassium chloride, applied in both ways, banded or broadcasted, was not observed. Leaf analysis did not show treatment influence over the leaf contents for N, P, K, Ca, Mg, and CI, Potassium chloride salinity effects in both methods of distribution for all the tested closes were not observed.

Crop sequences in no-tillage system: effects on soil fertility and soybean, maize and rice yield

Decomposing crop residues in no-tillage system can alter soil chemical properties, which may consequently influence the productivity of succession crops. The objective of this study was to evaluate soil chemical properties and soybean, maize and rice yield, grown in the summer, after winter crops in a no-tillage system. The experiment was carried out in Jaboticabal, SP, Brazil (21 ° 15 ' 22 '' S; 48 ° 18 ' 58 '' W) on a Red Latosol (Oxisol), in a completely randomized block design, in strip plots with three replications. The treatments consisted of four summer crop sequences (maize monocrop, soybean monocrop, soybean/maize rotation and rice/bean/cotton rotation) combined with seven winter crops (maize, sunflower, oilseed radish, pearl millet, pigeon pea, grain sorghum and sunn hemp). The experiment began in September 2002. After the winter crops in the 2005/2006 growing season and before the sowing of summer crops in the 2006/2007 season, soil samples were collected in the layers 0-2.5; 2.5-5.0; 5-10; 10-20; and 20-30 cm. Organic matter, pH, P, K+, Ca2+, Mg2+, and H + Al were determined in each soil sample. In the summer soybean/maize rotation and in maize the organic matter contents and P levels were lower, in the layers 0-10 cm and 0-20 cm, respectively. Summer rice/bean/cotton rotation increased soil K levels at 0-10 cm depth when sunn hemp and oilseed radish had previously been grown in the winter, and in the 0-2.5 cm layer for millet. Sunn hemp, millet, oilseed radish and sorghum grown in the winter increased organic matter contents in the soil down to 30 cm. Higher P levels were found at the depths 0-2.5 cm and 0-5 cm, respectively, when sunn hemp and oilseed radish were grown in the winter. Highest grain yields for soybean in monoculture were obtained in succession to winter oilseed radish and sunn hemp and in rotation with maize, after oilseed radish, sunn hemp and millet. Maize yields were highest in succession to winter oilseed radish, millet and pigeon pea. Rice yields were lowest when grown after sorghum.

Organic matter quality and dynamics in tropical soils amended with sugar industry residue

Soil organic matter depletion caused by agricultural management systems have been identified as a critical problem in most tropical soils. The application of organic residues from agro-industrial activities can ameliorate this problem by increasing soil organic matter quality and quantity. Humic substances play an important role in soil conservation but the dynamics of their transformations is still poorly understood. This study evaluated the effect of compost application to two contrasting tropical soils (Inceptisol and Oxisol) for two years. Soil samples were incubated with compost consisting of sugarcane filter cake, a residue from the sugar industry, at 0, 40, 80, and 120 Mg ha-1. Filter cake compost changed the humic matter dynamics in both content and quality, affecting the soil mineralogical composition. It was observed that carbon mineralization was faster in the illite-containing Inceptisol, whereas humic acids were preserved for a longer period in the Oxisol. In both soils, compost application increased fulvic acid contents, favoring the formation of small hydrophilic molecules. A decrease in fluorescence intensity according to the incubation time was observed in the humic acids extracted from amended soils, revealing important chemical changes in this otherwise stable C pool.

Chemical and mineralogical changes in a Brazilian Rhodic Paleudult under different land use and managements

Changes in land use and management can affect the dynamic equilibrium of soil systems and induce chemical and mineralogical alterations. This study was based on two long-term experiments (10 and 27 years) to evaluate soil used for no-tillage maize cultivation, with and without poultry litter application (NTPL and NTM), and with grazed native pasture fertilized with cattle droppings (GrP), on the chemical and mineralogical characteristics of a Rhodic Paleudult in Southern Brazil, in comparison with the same soil under native grassland (NGr). In the four treatments, soil was sampled from the 0.0-2.5 and 2.5-5.0 cm layers. In the air-dried fine soil (ADFS) fraction (∅ < 2 mm), chemical characteristics of solid and liquid phases and the specific surface area (SSA) were evaluated. The clay fraction (∅ < 0.002 mm) in the 0.0-2.5 cm layer was analyzed by X-ray diffraction (XRD) after treatments for identification and characterization of 2:1 clay minerals. Animal waste application increased the total organic C concentration (COT) and specific surface area (SSA) in the 0.0-2.5 cm layer. In comparison to NGr, poultry litter application (NTPL) increased the concentrations of Ca and CECpH7, while cattle droppings (GrP) increased the P and K concentrations. In the soil solution, the concentration of dissolved organic C was positively related with COT levels. With regard to NGr, the soil use with crops (NTM and NTPL) had practically no effect on the chemical elements in solution. On the other hand, the concentrations of most chemical elements in solution were higher in GrP, especially of Fe, Al and Si. The Fe and Al concentrations in the soil iron oxides were lower, indicating reductive/complexive dissolution of crystalline forms. The X-ray diffraction (XRD) patterns of clay in the GrP environment showed a decrease in intensity and reflection area of the 2:1 clay minerals. This fact, along with the intensified Al and Si activity in soil solution indicate dissolution of clay minerals in soil under cattle-grazed pasture fertilized with animal droppings.

Residues of carbosulfan and its carbofuran metabolites and 3-hydroxy-carbofuran in oranges

The objectives of this study were to evaluate the residues of the insecticide carbosulfan and its carbofuran metabolites and 3-hydroxy-carbofuran in orange compartments (whole fruit, bagasse and juice) and comparison between the residual levels found in fruits with the maximum residue level and the safety interval established by the Brazilian legislation. Two field experiments were carried out, both with the following treatments: a-check; b-one application of 10 g of carbosulfan . 100 L-1 of water; c-one application with twice the rate applied in treatment b; d-four applications with the same rate applied in treatment b. Samples were taken at (-1), zero, 1, 3, 7, 14, 21 and 28 days after the last or unique application. The quantitative determinations were done by gas chromatography technique, using a nitrogen-phosphorus detector. The carbosulfan metabolism to its carbofuran metabolite was rapid (3 days), being both analytes concentrated in the bagasse (peel + flavedo + albedo). However, the metabolism of carbofuran to 3-hydroxy-carbofuran was of low intensity or this metabolite was quickly dissipated. Carbosulfan residues and its metabolites did not penetrate into the fruit, thus not contaminating the juice. The use of the pesticide was adequate, with respect to fruit consumption, in relation to the Brazilian legislation.

TREATMENT OF WASTE FROM ATOMIC EMISSION SPECTROMETRIC TECHNIQUES AND REUSE IN UNDERGRADUATE LAB CLASSES FOR QUALITATIVE ANALYSIS

Flame atomic absorption spectrometry (FAAS) and inductively coupled plasma optical emission spectrometry (ICP OES) are widely used in academic institutions and laboratories for quality control to analyze inorganic elements in samples. However, these techniques have been observed to underperform in sample nebulization processes. Most of the samples processed through nebulization system are discarded, producing large volumes of waste. This study reports the treatment and reuse of the waste produced from ICP OES technique in a laboratory of analytical research at the Universidade Federal do Ceará, Brazil. The treatment of the waste was performed by the precipitation of elements using (NH4)2CO3. Subsequently, the supernatant solution can be discarded in accordance with CONAMA 430/2011. The precipitate produced from the treatment of residues can be reused as a potential sample in undergraduate qualitative analytical chemistry lab classes, providing students the opportunity to test a real sample.

Atrazine bound residues formation and dissipation in subtropical soil under swine wastewater application

The effects of swine wastewater on atrazine dissipation and formation of bound residues in subtropical clay soil were investigated in this study. The experiment was carried out in laboratory, under room conditions, where samples of Rhodic Hapludox soil received 168.61 mg kg-1 of atrazine and were incubated for 60 days in the following treatments: T1 (sterilized soil + swine wastewater), T2 (sterilized soil + distilled water), T3 (Non sterilized soil + swine wastewater) and T4 (Non sterilized soil + distilled water). The extractable residues and bound residues of atrazine were extracted and analyzed by high performance liquid chromatography. The results showed no effect of swine wastewater on atrazine dissipation. However, the addition of swine wastewater favored the increase of bound residues, which can increase the persistence of atrazine in the environment and reduce its bioavailability.

Important amino acid residues of potato plant uncoupling protein (StUCP)

Chemical modifications were used to identify some of the functionally important amino acid residues of the potato plant uncoupling protein (StUCP). The proton-dependent swelling of potato mitochondria in K+-acetate in the presence of linoleic acid and valinomycin was inhibited by mersalyl (Ki = 5 µM) and other hydrophilic SH reagents such as Thiolyte MB, iodoacetate and 5,5'-dithio-bis-(2-nitrobenzoate), but not by hydrophobic N-ethylmaleimide. This pattern of inhibition by SH reagents was similar to that of brown adipose tissue uncoupling protein (UCP1). As with UCP1, the arginine reagent 2,3-butadione, but not N-ethylmaleimide or other hydrophobic SH reagents, prevented the inhibition of StUCP-mediated transport by ATP in isolated potato mitochondria or with reconstituted StUCP. The results indicate that the most reactive amino acid residues in UCP1 and StUCP are similar, with the exception of N-ethylmaleimide-reactive cysteines in the purine nucleotide-binding site.

Hemolymphatic components in vectors of Trypanosoma cruzi: study in several species of the subfamily Triatominae (Hemiptera: Reduviidae)

The members of the subfamily Triatominae (Hemiptera : Reduviidae) comprise a great number of species of medical importance in the transmission of the T. cruzi (American trypanosomiasis). The aim of this study was to contribute to the knowledge about the chemical composition in proteins, lipids, lipoproteins, and carbohydrates of vectors of Chagas' disease corresponding to twelve members of the subfamily Triatominae. This study was carried out in ninphs of the fifth instar and adult males of the species: T. delpontei, T. dimidiata, T. guasayana, T. infestans, T. mazzotti, T. pallidipennis, T. patagonica, T. platensis, T. rubrovaria, T. sordida of the Triatoma genus, and D. maximus and P. megistus of the Dipatalogaster and Panstrongylus genera respectively. The results show on one hand, qualitative differences in the protein composition, and on the other hand, similarity in the lipoprotein profiles. Lipids, proteins, and carbohydrates did not show significant differences between species or/and stages.