Determination of organochlorine pesticides (OCPs) in breast milk from Rio Grande do Sul,Brazil, using a modified QuEChERS method and gas chromatography-negative chemical ionisation-mass spectrometry

ABSTRACT

The food chain is the main source of exposure to humans by organochlorine pesticides (OCPs) due to the bioaccumulation. Breast milk can accumulate OCPs, so this matrix is often used as an environmental bioindicator. The currently available methods for the determination of several OCPs and metabolites in breast milk involve, in general, multi-step sample preparation and quantification techniques with low selectivity, high cost and much time and labour. Thus, a fast and efficient method based on sample preparation using the quick, easy, cheap, effective, rugged and safe (QuEChERS) method combined with gas chromatography coupled to mass spectrometry with negative chemical ionisation (GC-NCI-MS) was developed, validated and applied for determination of 16 OCPs and metabolites in breast milk samples. The extract was cleaned by dispersive solid-phase extraction (d-SPE) using MgSO₄ and C18, evaporated in a Turbovap® system, redissolved and analysed by GC-NCI-MS. The method was validated showing acceptable recoveries (72–118%) and precision (RSD <19%). Method limits of detection (LODs) and quantification (LOQs) ranged from 0.75 to 7.5 ng g^?1 and from 2.5 to 25 ng g^?1 lipid, respectively. The method was successfully applied to 20 samples of breast milk from different regions of the Rio Grande do Sul state, Brazil, of which 75% contained residues below the LOQs.     

Structural characterization and in vivo evaluation of retinyl palmitate in non-ionic lamellar liquid crystalline system

Carrier systems for lipophilic drugs, such as the liquid crystalline systems (LCS) have been extensively studied to improve effect and selectivity. Retinyl palmitate (RP) is widely used in pharmaceutical and cosmetics products to improve the skin elasticity. The aim of this study was the development, characterization and the in vivo effectiveness of RP in non-ionic LCS structures. LCS containing polyether functional siloxane as oil phase, silicon glycol copolymer as surfactant and water in the ratio 30:10:60, with and without RP were studied. The results of the polarized light microscopy, small-angle X-ray scattering and rheology analysis indicated the presence of typical LCS structures with lamellar arrangement. Regardless of the presence of RP, the rheological studies showed the pseudo plastic behavior of the systems. However, highest hysteresis area was verified when comparing the system in the presence and in the absence of RP. Stability study SAXS monitored, carried out up to 30 days in various storage temperature conditions (25±2 °C, 37±2 °C and 5±2 °C) demonstrated the great structural stability of the LCS systems. The in vivo effectiveness analysis suggests that the RP-loaded LCS provided a significant reduction of the orbicular wrinkles in human volunteers (P=0.048).     

Simultaneous determination of pesticides, biopesticides and mycotoxins in organic products applying a quick, easy, cheap, effective, rugged and safe extraction procedure and ultra-high performance liquid chromatography-tandem mass spectrometry

A method for the simultaneous determination of pesticides, biopesticides and mycotoxins from organic products was developed. Extraction of more than 90 compounds was evaluated and performed by using a modified QuEChERS-based (acronym of Quick, Easy, Cheap, Effective, Rugged, and Safe) sample preparation procedure. The method was based on a single extraction with acidified acetonitrile, followed by partitioning with salts, avoiding any clean-up step prior the determination by ultra-high performance liquid chromatography/tandem quadrupole mass spectrometry (UHPLC–MS/MS). Validation studies were carried out in wheat, cucumber and red wine as representative matrixes. Recoveries of the spiked samples were in the range between 70 and 120% (with intra-day precision, expressed as relative standard deviation, lower than 20%) for most of the analysed compounds, except picloram and quinmerac. Inter-day precision, expressed as relative standard deviation, was lower than 24%. Limits of quantification were lower than 10 μg kg⁻¹ and the developed method was successfully applied to the analysis of organic food products, detecting analytes belonging to the three types of compounds.     

Locally oriented potential field for controlling multi-robots

In this paper, we present an extension of the boundary value problem path planner (BVP PP) to control multiple robots in a robot soccer scenario. This extension is called Locally Oriented Potential Field (LOPF) and computes a potential field from the numerical solution of a BVP using local relaxations in different patches of the solution space. This permits that a single solution of the BVP endows distinct robots with different behaviors in a team. We present the steps to implement LOPF as well as several results obtained in simulation.     

Method validation for the analysis of 169 pesticides in soya grain, without clean up, by liquid chromatography-tandem mass spectrometry using positive and negative electrospray ionization

Part of a comprehensive study on the comparison of different extraction methods, GC-MS(/MS) and LC-MS/MS detection methods and modes, for the analysis of soya samples is described in this paper. The validation of an acetone-based extraction method for analysis of 169 pesticides in soya, using LC-MS/MS positive and negative electrospray ionisation (ESI) mode, is reported. Samples (5 g) were soaked with 10 g water and subsequently extracted with 100 mL of a mixture of acetone, dichloromethane and light petroleum (1:1:1), in the presence of 15 g anhydrous sodium sulphate. After centrifugation, aliquots of the extract were evaporated and reconstituted in 1.0 mL of methanol, before direct injection of the final extract (corresponding with 0.05 g soya mL(-1)) into the LC-MS/MS system. Linearity, r(2) of calibration curves, instrument limit of detection/quantitation (LOD/LOQ) and matrix effect were evaluated, based on seven concentrations measured in 6-fold. Good linearity (at least r(2)> or =0.99) of the calibration curves was obtained over the range from 0.1 or 0.25 to 10.0 ng mL(-1), corresponding with pesticide concentrations in soya bean extract of 2 or 5-200 microg kg(-1). Instrument LOD values generally were 0.1 or 0.25 ng mL(-1). Matrix effects were negligible for approximately 90% of the pesticides. The accuracy, precision and method LOQ were determined via recovery experiments, spiking soya at 10, 50, 100 microg kg(-1), six replicates per level. In both ESI modes, method LOQ values were mostly 10 or 50 microg kg(-1) and more than 70% of pesticides analysed by each mode met the acceptability criteria of recovery (70-120%) and RSD (< or =20%), at one or more of the three levels studied. A fast, easy and efficient method with acceptable performance was achieved for a difficult matrix as soya, without cleanup.     

Comparison of several extraction procedures for the determination of biopesticides in soil samples by ultrahigh pressure LC-MS/MS

A new procedure has been proposed for the determination of biopesticides (nicotine, sabadine, veratridine, rotenone, azadirachtin, cevadine, deguelin, spynosad D, and pyrethrins) and piperonyl butoxide in agricultural soils. Several extraction procedures such as solid-liquid extraction using mechanical shaking, sonication, pressurized liquid extraction, and modified QuEChERS (quick, easy, cheap, effective, rugged, and safe) have been tested, obtaining better results when QuEChERS procedure without further cleanup steps was applied. The determination of the compounds was carried out by ultra high pressure liquid chromatography coupled to tandem mass spectrometry, using methanol and aqueous solution of ammonium formate 5 mM as mobile phase. The method was validated for all compounds at concentrations ranging from 10 to 100 μg/kg and recoveries ranged from 68 to 116%, except for nicotine and sabadine, with recoveries lower than 50%. Precision was estimated through intra- and inter-day studies, obtaining intra-day precision lower than 20% for most of the compounds, and inter-day precision was lower than 25%. Limits of detection and quantification were also estimated, obtaining limits of quantification equal or lower than 10 μg/kg. Finally, the method was applied to the analysis of 20 real agricultural soil samples and no biopesticide residues were found over the limit of quantification.     

Discussion About the Magnetic Field Dimensionality,Invariant Axis Condition,and Coulomb Gauge to Solve the Grad-Shafranov Equation

We discuss the relationship between the Coulomb gauge, the existence of an invariant axis, and the dimensionality (2-D or 2\(\frac {1}{2}\)-D) of the magnetic field in a mathematical-physical formalism that leads us to the Grad-Shafranov (GS) equation. In the literature, we found that a 2-D magnetic structure is used as a prerequisite to derive the GS equation from the Vlasov equation. However, other consulted works are based on a 2\(\frac {1}{2}\)-D (two-and-a-half) magnetic structure as a prerequisite to derive the GS equation from the balance of forces between the pressure gradient and the magnetic force, respectively. We replaced the magnetic vector potential on Ampère’s equation and used the Coulomb gauge to obtain a system of three Poisson equations, one for each component. We also used the same procedure explained above, but without the Coulomb gauge. Comparing z-component in both equation systems, we concluded that there are two possible solutions. We suggest using a 2\(\frac {1}{2}\)-D magnetic field configuration instead of a 2-D, when working with kinetic theory or magnetostatic equilibrium to derive the GS equation. We clarified that there is no relationship between the Coulomb gauge and the magnetic field dimensionality. In this problem, the invariant axis condition is imposed, which means that \(\vec {\nabla }\cdot \vec {A}\) is independent of z, i.e., \(\vec {\nabla }\cdot \vec {A}\) could have any value in which an invariant axis is a sufficient condition to obtain the GS equation.     

Rheological Measurements and Thermal Characterization of Lamellar Gel Phase Emulsions Developed with Cetearyl Alcohol/Nonionic Ethoxylated Surfactants

The aim of this research was to characterize emulsion systems (ES) containing nonionic ethoxylated surfactants by using rheological, microscopic, and thermogravimetric assays. Three formulations were developed: ES-1: 8.0% (w/w) oleth-20; ES-2: 4.0% (w/w) oleth-20 / 4.0% (w/w) steareth-21; and ES-3: 8.0% (w/w) steareth-21. The systems showed typical non-Newtonian pseudo-plastic behavior. The presence of a lamellar gel phase was observed for all systems, with ES-2 being more pronounced. Through thermogravimetry, the profiles of the three systems were found to be similar, consisting of two main events, the first one being characterized by loss of water and, beyond 110°C, by loss of the oil phase.