Determination of rice herbicides, their transformation products and clofibric acid using on-line solid-phase extraction followed by liquid chromatography with diode array and atmospheric pressure chemical ionization mass spectrometric detection

A simultaneous method for the trace determination of acidic, neutral herbicides and their transformation products in estuarine waters has been developed through an on-line solid-phase extraction method followed by liquid chromatography with diode array and mass spectrometric detection. An atmospheric pressure chemical ionization (APCI) interface was used in the negative ionization mode after optimization of the main APCI parameters. Limits of detection ranged from 0.1 to 0.02 ng/ml for 50 mi of acidified estuarine waters preconcentrated into polymeric precolumns and using time-scheduled selected ion monitoring mode. Two degradation products of the acidic herbicides (4-chloro-2-methylphenol and 2,4-dichlorophenol) did not show good signal response using APCI-MS at the concentration studied due to the higher fragmentor voltage needed for their determination For molinate and the major degradation product of propanil, 3,4-dichloroaniline, positive ion mode was needed for APCI-MS detection. The proposed method was applied to the determination of herbicides in drainage waters from rice fields of the Delta del Ebro (Spain). During the S-month monitoring of the herbicides, 8-hydroxybentazone and 4-chloro-2-methylphenoxyacetic acid were successively found in those samples. (C) 2000 Elsevier B.V. B.V. All rights reserved.

Flow injection AAS determination of Cd, Cu, and Pb at trace levels in wine using solid phase extraction

A comparative study is reported between C-18 bonded silica gel and powdered polyethylene (PE) as sorbent for Cd, Cu, and Pb determination using ammonium diethyldithiophosphate (ADTP) as the complexing agent in a flow injection system. The complexes were formed in 0.14 mol L-1 HNO3 and processed in a simple flow system comprising a peristaltic pump, a manual injector-commutator, and a sorbent-packed minicolumn. Ethanol was selected as the eluent and analytes in the eluate were determined by flame atomic absorption spectrometry. The optimum concentration of the complexing agent was 0.1% (m/v) ADTP for Cu and Pb determination using either C-18 or PE, and 0.25% (m/v) ADTP for Cd determination using PE. The sample loading flow rates were 5.0, 3.6, and 3.0 mL min(-1) for Cu, Pb, and Cd, respectively. The best elution flow rate was 6.5 mL min(-1). For a 60-sec preconcentration time, the sampling rate was 40 h(-1) and the enrichment factors of 33, 36, and 11 times (C-18) or 18, 22, and 23 times (PE) were obtained for Cu, Pb, and Cd, respectively. The limits of detection (LOD) were 1.6 mug L-1 Cu, 11 mug L-1 Pb, and 2.0 mug L-1 Cd using C-18 or 2.9 mug L-1 Cu, 19 mug L-1 Pb, and 1.0 mug L-1 Cd using PE, respectively. The relative standard deviations (n = 12) were typically <2%, <2%, and <6% for Cd, Cu, and Pb, respectively. The recoveries of Cd, Cu, and Pb added to wine samples varied from 96-99%, 97-102%, and 90-99%, respectively, using C-18 or PE. Accuracy was checked for Cd, Cu, and Pb determination in six wine samples digested by block digestor and open-vessel microwave-assisted digestion systems. The results revealed that C-18 was more efficient for Cu and Pb determination, while PE was the best sorbent for Cd.

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.

Polysiloxane-poly(propylene oxide) hybrid discs as solid phase in anti-HCV detection using a recombinant core protein

In this work, siloxane-poly(propylene oxide) discs (PPO disc) prepared using the sol-gel process were used as solid phase in enzyme-linked immunosorbent assays (ELISA) for the detection of anti-hepatitis C virus (HCV) antibodies. The HCV RNA from serum (genotype 1b) was submitted to the RT-PCR technique and subsequent amplification of the HCV core 408 pb. This fragment was cloned into expression vector pET42a and expressed in Escherichia coli as recombinant protein with glutathione S-transferase (GST). Cell cultures were grown and induced having a final concentration of 0.4 x 10(-3) mol L-1 of IPTG. After induction, the cells were harvested and the soluble fraction was analyzed using polyacrilamide gel 15% showing a band with an approximate molecular weight of 44 kDa, the expected size for this GST-fused recombinant protein. The recombinant protein was purified and continued by immunological detection using HCV-positive serum and showed no cross-reactivity with positive samples for other infectious diseases. An ELISA was established using 1.25 ng of recombinant protein per PPO disc, a dilution of 1: 10,000 and 1:40 for a peroxidase conjugate and serum, respectively, and solutions of hydrogen peroxide and 3,3',5,5'-tetra-methylbenzidine in a ratio of 1: 1. The proposed methodology was compared with the ELISA conventional polystyrene-plate procedure and the performance of the PPO discs as a matrix for immunodetection gave an easy synthesis, good performance and reproducibility for commercial application. (c) 2007 Elsevier B.V. All rights reserved.

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.

Solid-phase extraction of metal ions from fuel ethanol with a nanostructured adsorbent

This work describes the synthesis and characterization of a new octakis[3-(2,2'-dipyridylamine)propyl]octasilsesquioxane (T8-Pr-DPA), and a study of the metal ion preconcentration in fuel ethanol. Batch and column experiments were conducted to investigate for the removal of heavy metal ions from fuel ethanol. The results showed that the Langmuir allowed to describe the sorption equilibrium data of the metal ions on T8-Pr-DPA in a satisfactory way. The following maximum adsorption capacities (in mmolg-1) were determined: 3.62 for Fe (III), 3.32 for Cr (III), 2.15 for Cu (II), 1.80 for Co (II), 1.62 for Pb (II), 1.32 for Ni (II) and 0.88 for Zn (II). The thermodynamic parameters for the adsorption process such as free energy of adsorption (δG), enthalpy of adsorption (δH) and entropy of adsorption (δS) were calculated. Thermodynamic parameters showed that the system has favorable enthalpic, Gibbs free energy, and entropic values. The sorption-desorption of the metal ions has made possible the development of a preconcentration and determination method of metal ions at trace level in fuel ethanol. The method of quantitative analysis for Fe, Cu, Ni and Zn in fuel ethanol by Flame AAS was validated. Several parameters have been taken into account and evaluated for the validation of method, namely: linearity, limit of detection, limit of quantification, and the relative standard deviation and accuracy. The accuracy of the method was assessed by testing analyte recovery in the fuel ethanol samples. © 2013 Elsevier B.V.

Matrix Effects on Water Analysis for Alkylphenols Using Solid Phase Extraction Gas Chromatography-Mass Spectrometry

Gas chromatography with mass spectrometry is frequently used for the quantification of many classes of substances, including alkylphenols. Alkylphenol polyethoxylates are nonionic surfactants used in a wide variety of industrial and consumer applications. Alkylphenol polyethoxylates can degrade to alkylphenols, which are endocrine disruptors. In analytical validation procedures, the most common parameters studied are the detection and quantification limits, linearity, and recovery; however, the matrix effects are sometimes neglected. Although some investigators have evaluated matrix effects, there is no consensus on how to evaluate them during method validation. In this study, the matrix effects of alkylphenol polyethoxylates (nonylphenol monoethoxylate, nonylphenol diethoxylate, octylphenol monoethoxylate, octylphenol diethoxylate) and alkylphenols (nonylphenol and octylphenol) were studied using solid phase extraction and gas chromatography-mass spectrometry analysis. For alkylphenol polyethoxylates, the matrix effects ranged from 16 to 4692%, whereas for alkylphenols (nonylphenol and octylphenol), the effects were insignificant. Therefore, constructing an analytical curve in the matrix for alkylphenol polyethoxylates is essential. © 2013 Copyright Taylor and Francis Group, LLC.

Determination of tetramethylthiuram disulfide (thiram) for residual analysis in food using spectrophotometry coupled with a solid-phase reactor (SPR) in a flow system

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

The Use of Headspace Solid-Phase Microextraction (HS-SPME) to Assess the Quality and Stability of Fruit Products: An Example Using Red Mombin Pulp (Spondias purpurea L.)

The present study aimed to evaluate the volatiles profile of red mombin (Spondias purpurea) pulp and its powder produced by spray-drying (SD) as an example to show utility of headspace solid-phase microextraction (HS-SPME) in the analysis of parameters such as the quality and stability of fruit products. Volatiles profiles of the pulp were identified by gas chromatography-mass spectrometry (GC-MS), quantified by gas chromatography-flame ionization detector (GC-FID) and compared to the profile of the powder stored at 0, 60 and 120 days in plastic (PP) or laminated packages (LP). The results showed that the technique was able to identify 36 compounds in the red mombin pulp, 17 out of which have been described for the first time in this fruit, showing that red mombin fresh pulp appears to be unique in terms of volatiles composition. However, only 24 compounds were detected in the powder. This decrease is highly correlated (r(2) = 0.99), at least for the majority of compounds, to the degree of volatility of compounds. Furthermore, the powder stored in PP or LP showed no statistical differences in the amounts of its components for a period of 120 days of storage. Finally, this work shows how HS-SPME analysis can be a valuable tool to assess the quality and stability of fruit products.

Analysis of Steroids using Solid Phase Microextraction-Gas Chromatography-Mass Spectrometry-Mass Spectrometry (SPME-GC-MS-MS)

Direct immersion SPME-GC-MS-MS was used for the analysis of steroids in water at part-per-trillion(ppt) and lower concentrations. The method was validated and extended to real sample analysis. The method were linear from 0.01 to 5 ng/ml with precision less than 10% relative standard deviation for a steroid mixture at 1 ng/ml. Limit of quantitation and limit of detection was found to be 200- 1200 pg/L and 30-200 pg/L respectively and recoveries ranged from 88-103 %. To understand the extraction efficiency of the fiber, a depletion study was performed. The fiber/ sample partition coefficients for the steroids were determined to be 1.0 x 104 to 1.5 x 104 . The extraction was performed without derivatization or the use of an internal standard. SPMEGC-MS-MS effectively demonstrated ultra-trace level detection of steroids in water.

High precision and selectivity for quantitation of enrofloxacin and ciprofloxacin in five chicken tissues using solid phase extraction and ESI LC-MS/MS for application in monitoring residues

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

Determination of organochlorine pesticides and polychlorinated biphenyls residues in municipal solid waste compost by gas chromatography with electron-capture detection

A simple and efficient method for the simultaneous gas chromatographic determination of ten organochlorine pesticides (alpha-HCH, beta-HCH, gamma-HCH, p,p'-DDT, o,p'-DDT, p,p'-DDD, p,p'-DDE, aldrin, endrin, and dieldrin) and six congeners of PCBs (PCB 28, 52, 118, 138, 153, and 180) in municipal solid waste compost is described. The procedure involves a solid-phase dispersion matrix using celite as dispersant sorbent, alumina as clean up sorbent and hexane-dichloromethane (7:3, v/v) mixture as eluting solvent. An additional purification step with copper was necessary to eliminate sulphur. Analysis of the sample was performed by GC-ECD. The method was validated with fortified samples at two concentration levels (0.025 and 0.05 mg kg(-1)). Average recovery ranged from 77 to 121% with relative standard deviation between 1 and 18%. The detection limits, which ranged from 0.003 to 0.01 mg kg-1, were lower than those established by the Baden-Wurttemberg directive (0.033 mg kg(-1)).

Lattice effects in the quasi-two-dimensional valence-bond-solid Mott insulator EtMe3P[Pd(dmit)(2)](2)

The organic charge-transfer salt EtMe3P[Pd(dmit)(2)](2) is a quasi-two-dimensional Mott insulator with localized spins S = 1/2 residing on a distorted triangular lattice. Here we report measurements of the uniaxial thermal expansion coefficients alpha(i) along the in-plane i = a and c axis as well as along the out-of-plane b axis for temperatures 1.4 K <= T <= 200 K. Particular attention is paid to the lattice effects around the phase transition at T-VBS = 25 K into a low-temperature valence-bond-solid phase and the paramagnetic regime above where effects of short-range antiferromagnetic correlations can be expected. The salient results of our study include (i) the observation of strongly anisotropic lattice distortions accompanying the formation of the valence-bond-solid phase, and (ii) a distinct anomaly in the thermal expansion coefficients in the paramagnetic regime around 40 K. Our results demonstrate that upon cooling through T-VBS the in-plane c axis, along which the valence bonds form, contracts while the second in-plane a axis elongates by the same relative amount. Surprisingly, the dominant effect is observed for the out-of-plane b axis which shrinks significantly upon cooling through T-VBS. The pronounced anomaly in alpha(i) around 40 K is attributed to short-range magnetic correlations. It is argued that the position of this maximum, relative to that in the magnetic susceptibility around 70 K, speaks in favor of a more anisotropic triangular-lattice scenario for this compound than previously thought.

Hygroscopic properties of solid agro-industrial by-products used in solid-state fermentation

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Pré-concentração de cádmio com Saccharomyces cerevisiae e determinação em águas fluviais usando espectrometria de emissão óptica com plasma indutivamente acoplado

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