Development and validation of a novel method for the analysis of chlorinated pesticides in soils using microwave-assisted extraction–headspace solid phase microextraction and gas chromatography–tandem mass spectrometry

A new procedure for determining eleven organochlorine pesticides in soils using microwave-assisted extraction (MAE) and headspace solid phase microextraction (HS-SPME) is described. The studied pesticides consisted of mirex, α- and γ-chlordane, p,p’-DDT, heptachlor, heptachlor epoxide isomer A, γ-hexachlorocyclohexane, dieldrin, endrin, aldrine and hexachlorobenzene. The HS-SPME was optimized for the most important parameters such as extraction time, sample volume and temperature. The present analytical procedure requires a reduced volume of organic solvents and avoids the need for extract clean-up steps. For optimized conditions the limits of detection for the method ranged from 0.02 to 3.6 ng/g, intermediate precision ranged from 14 to 36% (as CV%), and the recovery from 8 up to 51%. The proposed methodology can be used in the rapid screening of soil for the presence of the selected pesticides, and was applied to landfill soil samples.

Analysis of PCBs in soils and sediments by microwave-assisted extraction, headspace-SPME and high resolution gas chromatography with ion-trap tandem mass spectrometry

A procedure for the determination of seven indicator PCBs in soils and sediments using microwave-assisted extraction (MAE) and headspace solid-phase microextraction (HS-SPME) prior to GC-MS/MS is described. Optimization of the HS-SPME was carried out for the most important parameters such as extraction time, sample volume and temperature. The adopted methodology has reduced consumption of organic solvents and analysis runtime. Under the optimized conditions, the method detection limit ranged from 0.6 to 1 ng/g when 5 g of sample was extracted, the precision on real samples ranged from 4 to 21% and the recovery from 69 to 104%. The proposed method, which included the analysis of a certified reference material in its validation procedure, can be extended to several other PCBs and used in the monitoring of soil or sediments for the presence of PCBs.

Determination of pesticides in fruit and fruit juices by chromatographic methods. An overview

In order to combat a variety of pests, pesticides are widely used in fruits. Several extraction procedures (liquid extraction, single drop microextraction, microwave-assisted extraction, pressurized liquid extraction, supercritical fluid extraction, solid-phase extraction, solid-phase microextraction, matrix solid-phase dispersion, and stir bar sorptive extraction) have been reported to determine pesticide residues in fruits and fruit juices. The significant change in recent years is the introduction of the Quick, Easy, Cheap, Effective, Rugged, and Safe (QuEChERS) methods in these matrices analysis. A combination of techniques reported the use of new extraction methods and chromatography to provide better quantitative recoveries at low levels. The use of mass spectrometric detectors in combination with liquid and gas chromatography has played a vital role to solve many problems related to food safety. The main attention in this review is on the achievements that have been possible because of the progress in extraction methods and the latest advances and novelties in mass spectrometry, and how these progresses have influenced the best control of food, allowing for an increase in the food safety and quality standards.

Multiresidue pesticides analysis in soils using modified QuEChERS with disposable pipette extraction and dispersive solid-phase extraction

QuEChERS original method was modified into a new version for pesticides determination in soils. The QuEChERS method is based on liquid–liquid portioning with ACN and was followed by cleanup step using dispersive SPE and disposable pipette tips. Gas chromatographic separation with MS detection was carried out for pesticides quantification. The method was validated using recovery experiments for 36 multiclass pesticides. Mean recoveries of pesticides at each of the four spiking levels between 10–300 µg/kg of soil ranged from 70–120% for 26 pesticides with RSD values less than 15%. The method achieved low limit of detection less than 7.6 µ g/kg. Matrix effects were observed for 13 pesticides. Matrix effects were compensated by using matrix-matched calibration. The method was applied successfully using d-SPE or DPX in the analysis of the pesticides in soils from organic farming and integrated pest management.

Comparison of Disposable Pipette Extraction and Dispersive Solid-Phase Extraction in the QuEChERS Method for Analysis of Pesticides in Strawberries

In this study, we sought to assess the applicability of GC–MS/MS for the identification and quantification of 36 pesticides in strawberry from integrated pest management (IPM) and organic farming (OF). Citrate versions of QuEChERS (quick, easy, cheap, effective, rugged and safe) using dispersive solid-phase extraction (d-SPE) and disposable pipette extraction (DPX) for cleanup were compared for pesticide extraction. For cleanup, a combination of MgSO4, primary secondary amine and C18 was used for both the versions. Significant differences were observed in recovery results between the two sample preparation versions (DPX and d-SPE). Overall, 86% of the pesticides achieved recoveries (three spiking levels 10, 50 and 200 µg/kg) in the range of 70–120%, with <13% RSD. The matrix effects were also evaluated in both the versions and in strawberries from different crop types. Although not evidencing significant differences between the two methodologies were observed, however, the DPX cleanup proved to be a faster technique and easy to execute. The results indicate that QuEChERS with d-SPE and DPX and GC–MS/MS analysis achieved reliable quantification and identification of 36 pesticide residues in strawberries from OF and IPM.

Analysis of six fungicides and one acaricide in still and fortified wines using solid-phase microextraction-gas chromatography/tandem mass spectrometry

A multiresidue gas chromatographic method for the determination of six fungicides (captan, chlorthalonil, folpet, iprodione, procymidone and vinclozolin) and one acaricide (dicofol) in still and fortified wines was developed. Solid-phase microextraction (SPME) was chosen for the extraction of the compounds from the studied matrices and tandem mass spectrometry (MS/MS) detection was used. The extraction consists in a solvent free and automated procedure and the detection is highly sensitive and selective. Good linearity was obtained with correlation coefficients of regression (R2) > 0.99 for all the compounds. Satisfactory results of repeatability and intermediate precision were obtained for most of the analytes (RSD < 20%). Recoveries from spiked wine ranged from 80.1% to 112.0%. Limits of quantification (LOQs) were considerably below the proposedmaximumresidue limits (MRLs) for these compounds in grapes and below the suggested limits for wine (MRLs/10), with the exception of captan.

Multi-criteria design optimization study of solvent extraction in mixer–settler units

Solvent extraction is considered as a multi-criteria optimization problem, since several chemical species with similar extraction kinetic properties are frequently present in the aqueous phase and the selective extraction is not practicable. This optimization, applied to mixer–settler units, considers the best parameters and operating conditions, as well as the best structure or process flow-sheet. Global process optimization is performed for a specific flow-sheet and a comparison of Pareto curves for different flow-sheets is made. The positive weight sum approach linked to the sequential quadratic programming method is used to obtain the Pareto set. In all investigated structures, recovery increases with hold-up, residence time and agitation speed, while the purity has an opposite behaviour. For the same treatment capacity, counter-current arrangements are shown to promote recovery without significant impairment in purity. Recycling the aqueous phase is shown to be irrelevant, but organic recycling with as many stages as economically feasible clearly improves the design criteria and reduces the most efficient organic flow-rate.

Polycyclic aromatic hydrocarbons in gas and particulate phases of indoor environments influenced by tobacco smoke: levels, phase distributions, and health risks

As polycyclic aromatic hydrocarbons (PAHs) have a negative impact on human health due to their mutagenic and/or carcinogenic properties, the objective of this work was to study the influence of tobacco smoke on levels and phase distribution of PAHs and to evaluate the associated health risks. The air samples were collected at two homes; 18 PAHs (the 16 PAHs considered by U.S. EPA as priority pollutants, dibenzo[a,l]pyrene and benzo[j]fluoranthene) were determined in gas phase and associated with thoracic (PM10) and respirable (PM2.5) particles. At home influenced by tobacco smoke the total concentrations of 18 PAHs in air ranged from 28.3 to 106 ngm 3 (mean of 66.7 25.4 ngm 3),∑PAHs being 95% higher than at the non-smoking one where the values ranged from 17.9 to 62.0 ngm 3 (mean of 34.5 16.5 ngm 3). On average 74% and 78% of ∑PAHs were present in gas phase at the smoking and non-smoking homes, respectively, demonstrating that adequate assessment of PAHs in air requires evaluation of PAHs in both gas and particulate phases. When influenced by tobacco smoke the health risks values were 3.5e3.6 times higher due to the exposure of PM10. The values of lifetime lung cancer risks were 4.1 10 3 and 1.7 10 3 for the smoking and nonsmoking homes, considerably exceeding the health-based guideline level at both homes also due to the contribution of outdoor traffic emissions. The results showed that evaluation of benzo[a]pyrene alone would probably underestimate the carcinogenic potential of the studied PAH mixtures; in total ten carcinogenic PAHs represented 36% and 32% of the gaseous ∑PAHs and in particulate phase they accounted for 75% and 71% of ∑PAHs at the smoking and non-smoking homes, respectively.

Multiresidue method for the determination of organophosphorus pesticides in still wine and fortified wine using solid-phase microextraction and gas chromatography – Tandem mass spectrometry

A SPME-GC-MS/MS method for the determination of eight organophosphorus pesticides (azinphos-methyl, chlorpyriphos, chlorpyriphos-methyl, diazinon, fenitrothion, fenthion, malathion, and methidathion) in still and fortified wine was developed. The extraction procedure is simple, solvent free, and without any sample pretreatment. Limits of detection (LOD) and quantitation (LOQ) values in the range 0.1–14.3 lg/L and 0.2–43.3 lg/L, respectively, were obtained. The LOQ values are below the maximum residue levels (MRLs) established by European Regulation for grapes, with the exception of methidathion. Coefficients of correlation (R2) higher than 0.99 were obtained for the majority of the pesticides, in all different wines analyzed.

Use of solvent extraction to remediate soils contaminated with hydrocarbons

The main objective of this research is to exploit the possibility of using an ex situ solvent extraction technique for the remediation of soils contaminated with semi-volatile petroleum hydrocarbons. The composition of the organic phase was chosen in order to form a single phase mixture with an aqueous phase and simultaneously not being disturbed (forming stable emulsions) by the soil particles hauling the contaminants. It should also permit a regeneration of the organic solvent phase. As first, we studied the miscibility domain of the chosen ternary systems constituted by ethyl acetate–acetone–water. This system proved to satisfy the previous requirements allowing for the formation of a single liquid phase mixture within a large spectrum of compositions, and also allowing for an intimate contact with the soil. Contaminants in the diesel range within different functional groups were selected: xylene, naphthalene and hexadecane. The analytical control was done by gas chromatography with FID detector. The kinetics of the extractions proved to be fast, leading to equilibrium after 10 min. The effect of the solid–liquid ratio on the extraction efficiency was studied. Lower S/L ratios (1:8, w/v) proved to be more efficient, reaching recoveries in the order of 95%. The option of extraction in multiple contacts did not improve the recovery in relation to a single contact. The solvent can be regenerated by distillation with a loss around 10%. The contaminants are not evaporated and they remain in the non-volatile phase. The global results show that the ex situ solvent extraction is technically a feasible option for the remediation of semi-volatile aromatic, polyaromatic and linear hydrocarbons.

Remediation of soils combining soil vapor extraction and bioremediation: benzene

This work reports the study of the combination of soil vapor extraction (SVE) with bioremediation (BR) to remediate soils contaminated with benzene. Soils contaminated with benzene with different water and natural organic matter contents were studied. The main goals were: (i) evaluate the performance of SVE regarding the remediation time and the process efficiency; (ii) study the combination of both technologies in order to identify the best option capable to achieve the legal clean up goals; and (iii) evaluate the influence of soil water content (SWC) and natural organic matter (NOM) on SVE and BR. The remediation experiments performed in soils contaminated with benzene allowed concluding that: (i) SVE presented (a) efficiencies above 92% for sandy soils and above 78% for humic soils; (b) and remediation times from 2 to 45 h, depending on the soil; (ii) BR showed to be an efficient technology to complement SVE; (iii) (a) SWC showed minimum impact on SVE when high airflow rates were used and led to higher remediation times for lower flow rates; (b) NOM as source of microorganisms and nutrients enhanced BR but hindered the SVE due the limitation on the mass transfer of benzene from the soil to the gas phase.

Validation of a single-extraction procedure for sequential analysis of vitamin E, cholesterol, fatty acids, and total fat in seafood

Food lipid major components are usually analyzed by individual methodologies using diverse extractive procedures for each class. A simple and fast extractive procedure was devised for the sequential analysis of vitamin E, cholesterol, fatty acids, and total fat estimation in seafood, reducing analyses time and organic solvent consumption. Several liquid/liquid-based extractive methodologies using chlorinated and non-chlorinated organic solvents were tested. The extract obtained is used for vitamin E quantification (normal-phase HPLC with fluorescence detection), total cholesterol (normal-phase HPLC with UV detection), fatty acid profile, and total fat estimation (GC-FID), all accomplished in <40 min. The final methodology presents an adequate linearity range and sensitivity for tocopherol and cholesterol, with intra- and inter-day precisions (RSD) from 3 to 11 % for all the components. The developed methodology was applied to diverse seafood samples with positive outcomes, making it a very attractive technique for routine analyses in standard equipped laboratories in the food quality control field.

Comparative analysis of the ground reaction forces, during the support phase, in a group of pregnant women on their 3rd trimester of pregnancy and in a group of not pregnant women

PURPOSE: To analyze and compare the Ground Reaction Forces (GRF), during the stance phase of walking in pregnant women in the 3rd trimester of pregnancy, and non pregnant women. METHODS: 20 women, 10 pregnant and 10 non pregnant, voluntarily took part in this study. GRF were measured (1000 Hz) using a force platform (BERTEC 4060-15), an amplifier (BERTEC AM 6300) and an analogical-digital converter of 16 Bits (Biopac). RESULTS: The study showed that there were significant differences among the two groups concerning absolute values of time of the stance phase. In what concerns to the normalized values the most significant differences were verified in the maximums values of vertical force (Fz3, Fz1) and in the impulse of the antero-posterior force (Fy2), taxes of growth of the vertical force, and in the period of time for the antero-posterior force (Fy) be null. CONCLUSIONS: It is easier for the pregnant to continue forward movement (push-off phase). O smaller growth rates in what concerns to the maximum of the vertical force (Fz1) for the pregnant, can be associated with a slower speed of gait, as an adaptation strategy to maintain the balance, to compensate the alterations in the position of her center of gravity due to the load increase. The data related to the antero-posterior component of the force (Fy), shows that there is a significant difference between the pregnant woman’s left foot and right foot, which accuses a different functional behavior in each one of the feet, during the propulsion phase (TS).

Knowledge extraction from medium voltage load diagrams to support the definition of electrical tariffs

With the electricity market liberalization, distribution and retail companies are looking for better market strategies based on adequate information upon the consumption patterns of its electricity customers. In this environment all consumers are free to choose their electricity supplier. A fair insight on the customer´s behaviour will permit the definition of specific contract aspects based on the different consumption patterns. In this paper Data Mining (DM) techniques are applied to electricity consumption data from a utility client’s database. To form the different customer´s classes, and find a set of representative consumption patterns, we have used the Two-Step algorithm which is a hierarchical clustering algorithm. Each consumer class will be represented by its load profile resulting from the clustering operation. Next, to characterize each consumer class a classification model will be constructed with the C5.0 classification algorithm.

Shannon, rényie and tsallis entropy analysis of DNA using phase plane

This paper analyzes DNA information using entropy and phase plane concepts. First, the DNA code is converted into a numerical format by means of histograms that capture DNA sequence length ranging from one up to ten bases. This strategy measures dynamical evolutions from 4 up to 410 signal states. The resulting histograms are analyzed using three distinct entropy formulations namely the Shannon, Rényie and Tsallis definitions. Charts of entropy versus sequence length are applied to a set of twenty four species, characterizing 486 chromosomes. The information is synthesized and visualized by adapting phase plane concepts leading to a categorical representation of chromosomes and species.