Determination of herbicides residues in soil by small scale extraction

Herbicidas tais como trifluralina, simazina, atrazina, metribuzina e metolaclor são usados na agricultura brasileira. A eficiência de um método em pequena escala para a determinação destes herbicidas e dois produtos de degradação em amostras de solo foi avaliada. Os compostos foram extraídos das amostras de solo (5 g) com 20 ml de acetato de etila em agitador mecânico por 50 min. Após a extração, o sobrenadante foi filtrado em sulfato de sódio anidro, concentrado e analisado por cromatografia a gás de alta resolução com detector termiônico específico. Valores médios de recuperação obtidos de amostras de solo fortificadas em três níveis diferentes variaram de 81 a 115 % com valores de desvio padrão relativo entre 1,2 e 12,7 %. Os limites de detecção do método variaram de 0,01 a 0,06 mg kg-1. A metodologia foi aplicada a amostras de solo de fazendas localizadas próximas à cidade de Araraquara, estado de São Paulo, Brasil.

CTAB methods for DNA extraction of sweetpotato for microsatellite analysis

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Extraction and clean-up procedure for analysis of organochlorine pesticide residues in ethoxylated lanolin

In the present study an evaluation was made of a method for the determination of organochlorine pesticide residues in ethoxylated lanolin. Samples were homogenized with Celite, transferred to chromatographic columns, prepacked with silica gel deactivated to 10%. The pesticide elution was processed with n-hexane-dichloromethane and the concentrated eluate was analyzed using gas-liquid chromatography (GC) with electron capture detection (ECD). The composition of the elution solvent was a significant factor for the recovery of the pesticides. Mean recoveries obtained for fortified samples ranged from 87 to 94% for p,p'-DDE, dieldrin, endrin, p,p'-DDD and p,p'-DDT. Optimization of the experimental conditions resulted in a small-scale method that combines extraction and cleanup in a single step. (C) 2000 Elsevier B.V. S.A. All rights reserved.

Determination of carbofuran and 3-hydroxycarbofuran residues in coconut water by solid-phase extraction and liquid chromatography with UV detection

A simple method was developed to determine carbofuran and 3-hydroxycarbofuran in coconut water. The procedure involved solid-phase extraction using C-18 cartridges with acetonitrile for elution. The analysis of these compounds was carried out by liquid chromatography with UV detection at 275 nm using a gradient solvent system. The method was validated with fortified samples at different concentration levels (0.01-2.5 mu g/mL). Average recoveries ranged from 81 to 95% with relative standard deviation between 1.6 and 12.5%. Each recovery analysis was repeated at least five times. Detection limits ranged from 0.008 to 0.01 mu g/mL. The analytical procedure was applied to coconut water samples from palms submitted to treatment with commercial formulation under field conditions.

On-line extraction and determination of carbofuran in raw milk by direct HPLC injection on an ISRP column

A method has been developed for extraction and determination of carbofuran in milk. The method involved direct injection of raw milk on to a human serum albumin dimethyloctyl-silica gel (HSA-Cs) column and the use of 80:20 (v/v) 0.01 M phosphate buffer pH 5.5 - acetonitrile as mobile phase. UV spectrophotometric detection was performed at 220 nm. Identification was based on retention time. Quantification was performed by automatic peak-area determination and was calibrated by use of an external standard.

Screening and confirmation of PAHs in vegetable oil samples by use of supercritical fluid extraction in conjunction with liquid chromatography and fluorimetric detection

A fast, simple, non-destructive method for the direct screening of polycyclic aromatic hydrocarbons (PAHs) in vegetable oil samples is proposed. The method uses a supercritical fluid extraction (SFE) system coupled on-line with a fluorimetric detector to determine PAHs. This special assembly avoids the main problems encountered in the determination of PAHs in complex matrices such as vegetable oils. PAHs are selectively extracted by using silica gel in the thimble and cleaned up by passage through a C18 column. Interferences are preferentially retained by the silica gel during the SFE process while PAHs are adsorbed in the C18 column and the remainder of the matrix is sent to waste. Finally, the C18 column is purged to remove residual CO2 gas and adsorbed PAHs are recovered by desorption with a solvent. The extracts from positive samples are subsequently analyzed by liquid chromatography (LC) with fluorescence detection. The proposed method allows the confirmation of vegetable oil safety and hence provides a new tool for consumer protection. (C) 2004 Elsevier B.V. All rights reserved.

A method for evaluating Ra-228 in environmental matrices and its use at Pocos de Caldas plateau, Brazil

This work describes a methodology developed for performing the extraction, detection and quantification of Ra-228 in waters, suspended solids and sediments. The technique proved to be useful for analyzing samples from the hydrological environment of Morro do Ferro, Pocos de Caldas plateau, Brazil. The 228Ra activity in underground waters of 5 boreholes drilled in the area varied from 0.02 up to 14.5 Bq/l, whereas for the surficial waters the variation was from 0.04 to 0.51 Bq/l; for the suspended solids, the values ranged from 1.5 up to 419 Bq/g, whereas it was possible to find a value of 2.04 Bq/g for the sediments. These results show the applicability of the method for characterizing different matrices of environmental interest. (C) 2002 Elsevier B.V. Ltd. All rights reserved.

Differential pulse polarographic determination of ceftazidime in urine samples with and without prior extraction

Ceftazidime shows two main polarographic reduction peaks at pH 4.0, that at -0.45 V owing to reduction of the C=N bond in the methylethoxyimino group and that at -1.00 V owing to the reductive elimination of pyridine: the first peak is particularly suitable for the determination of ceftazidime. Ceftazidime can also be determined indirectly using the tensammetric peak at -0.60 V (in Britton-Robinson buffer pH 9.5) of pyridine liberated on hydrolysis. Ceftazidime can be determined in urine using the direct method only after Cls solid phase extraction, but it can be determined directly in the urine by hydrolysing it and using the pyridine peak. (C) 1997 Elsevier B.V. B.V.

A simplified method for the determination of fenpropathrin residues in fruits

A simple and efficient method is described for the determination of fenpropathrin in oranges, pears, apples and strawberries. The procedure: is based on the extraction of each homogenized fruit sample with hexane:acetone (1:1, v/v) mixture, followed, by a cleanup technique on a column packed with florisil, using a hexane:ethyl ether (7:3, v/v) mixture, and gas chromatographic, analysis with electron capture detection (ECD). The fortification levels (0.5; 1.0; 2.0 mg kg(-1)) were selected according to the maximum residue limits (MRLs) established for fenpropathrin by Brazilian legislation. Mean recoveries from five replicates of fortified fruit samples ranged from 83 % to 98 %, with:coefficients of variation from 1.4 to 13.5 and detection limits varying from 0.1 to 0.2 mg kg(-1).

Validation of an immunoassay method for the determination of traces of carbaryl in vegetable and fruit extracts by liquid chromatography with photodiode array and mass spectrometric detection

A competitive enzyme-linked immunosorbent assay (ELISA) method for carbaryl quantitation in crop extracts was validated by liquid chromatography (LC) with diode array detection (DAD). For this purpose, six crops (banana, carrot, green bean, orange, peach and potato) were chosen for recovery and reproducibility studies. The general sample preparation included extraction with methanol followed by liquid-liquid partitioning and clean-up on Celite-charcoal adsorbent column of the vegetable extracts. ELISA samples consisted of a diluted LC extract in assay phosphate buffer (pH 7.5). The potential effect of methanol in these samples was evaluated. It was observed that a maximum content of 10% methanol present in the assay buffer could be tolerated without expressive losses in the ELISA performance. Under these conditions, a IC50 similar to 1.48 mu g l(-1) was obtained. A minimum matrix effect with a 1:50 dilution of the methanolic extracts in assay buffer was noticed, except for green bean samples that inhibited completely the assay. For the vegetable extracts, the ELISA sensitivities varied from 3.9 to 5.7 mu g l(-1), and good recoveries (82-96%) with R.S.D.s ranging from 5.7 to 12.1% were found. An excellent correlation between the LC-DAD and ELISA techniques was obtained. The confirmation of the carbaryl in less concentrated samples was achieved by LC-mass spectrometry interfaced with atmospheric pressure chemical ionisation. The [M + H](+)= 202 and [M + H-57](+)=145 ions, equivalent to the protonated molecular and l-naphthol ions, respectively, were used to carbaryl identification in these samples. (C) 1998 Elsevier B.V. B.V. All rights reserved.

Spectrophotometric detection of arsenic using flow-injection hydride generation following sorbent extraction preconcentration

An automated system with a C-18 bonded silica gel packed minicolumn is proposed for spectrophotometric detection of arsenic using flow-injection hydride generation following sorbent extraction preconcentration. Complexes formed between arsenic(III) and ammonium diethyl dithiophosphate (ADDP) are retained on a C-18 sorbent. The eluted As-DDP complexes are merged with a 1.5% (w/v) NaBH4 and the resulting solution is thereafter injected into the hydride generator/gas-liquid separator. The arsine generated is carried out by a stream of N-2 and trapped in an alkaline iodine solution in which the analyte is determined by the arsenomolybdenum blue method. With preconcentration time of 120 s, calibration in the 5.00-50.0 mu g As l(-1) range and sampling rate of about 20 samples h(-1) are achieved, corresponding to 36 mg ADDP plus 36 mg ammonium heptamolybdate plus 7 mg hydrazine sulfate plus 0.7 mg stannous chloride and about 7 mi sample consumed per determination. The detection limit is 0.06 mu g l(-1) and the relative standard deviation (n = 12) for a typical 17.0 mu g As l(-1) sample is ca. 6%. The accuracy was checked for arsenic determination in plant materials from the NIST (1572 citrus leaves; 1573 tomato leaves) and the results were in agreement with the certified values at 95% confidence level. Good recoveries (94-104%) of spiked tap waters, sugars and synthetic mixtures of trivalent and pentavalent arsenic were also found. (C) 1999 Elsevier B.V. B.V. All rights reserved.

An HPLC-PAD method to analyse flavonoid glycosides and styrylpyrones from Cryptocarya species (Lauraceae)

An HPLC-PAD method has been developed in order to evaluate simultaneously the main secondary metabolites, flavonoid glycosides and styrylpyrones, of leaves of Cryptocarya moschata. The sample preparation, consisting of extraction, liquid-liquid extraction and centrifugation, requires minimum sample manipulation but produces high yields with reproducibility, selectivity and simplicity. HPLC on a C, column presents each class of metabolites grouped and with good resolution of the main compounds. The experimental conditions can be used to study inter- and intra-specific variability of secondary metabolites in Cryptocarya spp. Copyright (c) 2005 John Wiley A Sons, Ltd.

Multiresidue analysis of pesticides in water from rice cultures by on-line solid phase extraction followed by LC-DAD

An automated on-line solid phase extraction procedure followed by liquid chromatography with diode array detection was investigated for the determination of different classes of pesticides in water samples containing varied amount of humic substances. The different pesticides used were: carbendazin, carbofuran, atrazine, diuron, propanil, molinate, alachlor, parathion-ethyl, diazinon, trifluralin and the degradation products deisopropylatrazine and deethylatrazine. Humic substances extracted from a Brazilian sediment were used from 5 to 80 mg/l and their influence on recoveries was evaluated in neutral and acidic media. Recoveries higher than 70% were obtained for all the pesticides, from the preconcentration of 75 mi of aqueous sample fortified at 2 ng/ml using precolumns packed with PLRP-S. Good recoveries were obtained at neutral pH for most of the analytes up to 40 mg/l of humic acid. Only at 80 mg/l the recoveries were significantly affected, both at acidic and neutral pH. The method was applied to the determination of pesticides in river water spiked at 0.1 to 1 ng/ml. Detection limits obtained for water containing 10 mg/l of humic acid were between 0.05 and 0.3 ng/ml.

Small-scale method for the determination of selected organochlorine pesticides in soil

A small-scale method was developed for the simultaneous determination of γ-HCH, heptachlor, aldrin, dicofol, mirex, endosulfan I, endosulfan II and endosulfan sulphate in soil. The extraction and clean-up steps were combined into one step by transferring soil samples to chromatographic columns prepacked with neutral alumina. The pesticides elution was processed with n-hexane : dichloromethane (7:3) and the concentrated eluate was analysed using gas-liquid chromatography with electron capture detection. Analyses of the in vitro fortified samples with the selected pesticides were performed at three different levels. Mean recoveries for aldrin, γ-HCH and heptachlor, at levels of 2, 10 and 20 ng/g, ranged from 71 to 87%; for dicofol, at levels of 8, 40 and 80 ng/g, ranged from 97 to 103%; for endosulfan I and II, at levels of 5, 25 and 50 ng/g, ranged from 88 to 96%; for mirex, at levels of 6, 30 and 60 ng/g, ranged from 86 to 110%; and for endosulfan sulphate, at levels of 15, 75 and 150 ng/g, ranged from 93 to 104%. The method can be used for rapid determination of these pesticides in soil. © Springer-Verlag 1996.

Rapid, quantitative determination of polar compounds in fats and oils by solid-phase extraction and size-exclusion chromatography using monostearin as internal standard

A rapid and simple method was developed for quantitation of polar compounds in fats and oils using monostearin as internal standard. Starting from 50 mg of oil sample, polar compounds were obtained by solid-phase extraction (silica cartridges) and subsequently separated by high-performance size-exclusion chromatography into triglyceride polymers, triglyceride dimers, oxidized triglyceride monomers, diglycerides, internal standard and fatty acids. Quantitation of total polar compounds was achieved through the internal standard method and then amounts of each group of compounds could be calculated. A pool of polar compounds was used to check linearity, precision and accuracy of the method, as well as the solid-phase extraction recovery. The procedure was applied to samples with different content of polar compounds and good quantitative results were obtained, especially for samples of low alteration level.