Analysis of polycyclic aromatic hydrocarbons in atmospheric particulate samples by microwaveassisted extraction and liquid chromatography

A methodology based on microwave-assisted extraction (MAE) and LC with fluorescence detection (FLD) was investigated for the efficient determination of 15 polycyclic aromatic hydrocarbons (PAHs) regarded as priority pollutants by the US Environmental Protection Agency and dibenzo(a,l)pyrene in atmospheric particulate samples. PAHs were successfully extracted from real outdoor particulate matter (PM) samples with recoveries ranging from 81.4±8.8 to 112.0±1.1%, for all the compounds except for naphthalene (62.3±18.0%) and anthracene (67.3±5.7%), under the optimum MAE conditions (30.0 mL of ACN for 20 min at 110ºC). No clean-up steps were necessary prior to LC analysis. LOQs ranging from 0.0054 ng/m3 for benzo( a)anthracene to 0.089 ng/m3 for naphthalene were reached. The validated MAE methodology was applied to the determination of PAHs from a set of real world PM samples collected in Oporto (north of Portugal). The sum of particulate-bound PAHs in outdoor PM ranged from 2.5 and 28 ng/m3.

Shane Meadows’ country: analysis of the film this is England (2006)

This Is England is social realist film portraying racism and poverty in 1980s Britain through the eyes of Shaun, a 12 year old boy, who has lost his father in the Falklands war and as to come to terms with his own identity, the difficult transition from childhood to adolescence and the need to fit in a determined group/tribe/gang. The following article aims at analysing relevant aspects depicted from the film emphasizing the so much debated reality of life during 80s. In This is England Shane Meadows manages to rediscover his own self geography, by revisiting his adolescent years. It is a biographical film about the importance of peer pressure and the results of an excess of nationalism, at the same time it typifies some issues related to the 80s youth culture.

A multiresidue method for the analysis of carbamate and urea pesticides from soils by microwave-assisted extraction and liquid chromatography with photodiode array detection

A multiresidue approach using microwave-assisted extraction and liquid chromatography with photodiode array detection was investigated for the determination of butylate, carbaryl, carbofuran, chlorpropham, ethiofencarb, linuron,metobromuron, and monolinuron in soils. The critical parameters of the developed methodology were studied. Method validation was performed by analyzing freshly and aged spiked soil samples. The recoveries and relative standard deviations reached using the optimized conditions were between 77.0 ± 0.46% and 120 ± 2.9% except for ethiofencarb (46.4 ± 4.4% to 105 ± 1.6%) and butylate (22.1 ± 7.6% to 49.2 ± 11%). Soil samples from five locations of Portugal were analysed.

Electrochemical analysis of opiates—an overview

The analysis of opiates is of vital interest in drug abuse monitoring and research. This review presents a general overview of the electrochemical methods used for detection and quantification of opiates in a variety of matrices. Emphasis has been placed on the voltammetric methods used for study and determination of morphine, codeine, and heroin. Specific issues that need to be solved and better explained as well as future trends in the use of electrochemical methods in the examination of opiates are also discussed.

Electrochemical study of butylate: application to the analysis of water

The electroactivity of butylate (BTL) is studied by cyclic voltammetry (CV) and square wave voltammetry (SWV) at a glassy carbon electrode (GCE) and a hanging mercury drop electrode (HMDE). Britton–Robinson buffer solutions of pH 1.9–11.5 are used as supporting electrolyte. CV voltammograms using GCE show a single anodic peak regarding the oxidation of BTL at +1.7V versus AgCl/ Ag, an irreversible process controlled by diffusion. Using a HMDE, a single cathodic peak is observed, at 1.0V versus AgCl/Ag. The reduction of BTL is irreversible and controlled by adsorption. Mechanism proposals are presented for these redox transformations. Optimisation is carried out univaryingly. Linearity ranges were 0.10–0.50 mmol L-1 and 2.0–9.0 µmolL-1 for anodic and cathodic peaks, respectively. The proposed method is applied to the determination of BTL in waters. Analytical results compare well with those obtained by an HPLC method.

Citrate selective electrodes for the flow injection analysis of soft drinks, beers and pharmaceutical products

Aiming the establishment of simple and accurate readings of citric acid (CA) in complex samples, citrate (CIT) selective electrodes with tubular configuration and polymeric membranes plus a quaternary ammonium ion exchanger were constructed. Several selective membranes were prepared for this purpose, having distinct mediator solvents (with quite different polarities) and, in some cases, p-tert-octylphenol (TOP) as additive. The latter was used regarding a possible increase in selectivity. The general working characteristics of all prepared electrodes were evaluated in a low dispersion flow injection analysis (FIA) manifold by injecting 500µl of citrate standard solutions into an ionic strength (IS) adjuster carrier (10−2 mol l−1) flowing at 3ml min−1. Good potentiometric response, with an average slope and a repeatability of 61.9mV per decade and ±0.8%, respectively, resulted from selective membranes comprising additive and bis(2-ethylhexyl)sebacate (bEHS) as mediator solvent. The same membranes conducted as well to the best selectivity characteristics, assessed by the separated solutions method and for several chemical species, such as chloride, nitrate, ascorbate, glucose, fructose and sucrose. Pharmaceutical preparations, soft drinks and beers were analyzed under conditions that enabled simultaneous pH and ionic strength adjustment (pH = 3.2; ionic strength = 10−2 mol l−1), and the attained results agreed well with the used reference method (relative error < 4%). The above experimental conditions promoted a significant increase in sensitivity of the potentiometric response, with a supra-Nernstian slope of 80.2mV per decade, and allowed the analysis of about 90 samples per hour, with a relative standard deviation <1.0%.

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.

Life cycle analysis of biodiesel production

Biodieselhas attracted considerable attention as a renewable, biodegradable, and nontoxic fuel and can contribute to solving the energy problems, significantly reducing the emission of gases which cause global warming. The first stage of this work was to simulate different alternative processes for producing biodiesel. The method used for the production of biodiesel is the transesterification of vegetable oilswith an alcohol in the presence of a catalyst. The raw materials used were palm oils and waste cooking oil. The second stage was a life cycle analysis for all alternatives under study, followed by an economic analysis for the alternatives that present minor impacts and which are more promising from an economic point of view. Finally,we proceeded to compare the different alternatives fromboth the point of view of life cycle and economic analysis. The feasibility of all processes was proven and the biodiesel obtained had good specifications. From the standpoint of life cycle analysis, the best alternative was the process of alkaline catalysiswith acid pretreatment for waste cooking oil. The economic analysis was done to the previous mentioned process and to the process that uses raw virgin oils, methanol, and sodium hydroxide. This process has lower investment costs but the process of alkaline catalysis with acid pre-treatment, whose main raw material is waste oil, is much more profitable and has less environmental impacts.

Construction and evaluation of cysteine selective electrodes for FIA analysis of pharmaceuticals

A flow injection analysis (FIA) system comprising a cysteine selective electrode as detection system was developed for determination of this amino acid in pharmaceuticals. Several electrodes were constructed for this purpose, having PVC membranes with different ionic exchangers and mediator solvents. Better working characteristics were attained with membranes comprising o-nitrophenyl octyl ether as mediator solvent and a tetraphenylborate based ionic-sensor. Injection of 500 µL standard solutions into an ionic strength adjuster carrier (3x10-3 M) of barium chloride flowing at 2.4mL min-1, showed linearity ranges from 5.0x10-5 to 5.0x10-3 M, with slopes of 76.4±0.6mV decade-1 and R2>0.9935. Slope decreased significantly under the requirement of a pH adjustment, selected at 4.5. Interference of several compounds (sodium, potassium, magnesium, barium, glucose, fructose, and sucrose) was estimated by potentiometric selectivity coefficients and considered negligible. Analysis of real samples were performed and considered accurate, with a relative error to an independent method of +2.7%.

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.

Power law and entropy analysis of catastrophic phenomena

Catastrophic events, such as wars and terrorist attacks, tornadoes and hurricanes, earthquakes, tsunamis, floods and landslides, are always accompanied by a large number of casualties. The size distribution of these casualties has separately been shown to follow approximate power law (PL) distributions. In this paper, we analyze the statistical distributions of the number of victims of catastrophic phenomena, in particular, terrorism, and find double PL behavior. This means that the data sets are better approximated by two PLs instead of a single one. We plot the PL parameters, corresponding to several events, and observe an interesting pattern in the charts, where the lines that connect each pair of points defining the double PLs are almost parallel to each other. A complementary data analysis is performed by means of the computation of the entropy. The results reveal relationships hidden in the data that may trigger a future comprehensive explanation of this type of phenomena.

Analysis of the combined exposure to noise and ototoxic substances—pilot study

Abstract: Ototoxic substances have been associated to damage of the auditory system, and its effects are potentiated by noise exposure. The present study aims at analyzing auditory changes from combined exposure to noise and organic solvents, through a pilot study in the furniture industry sector. Audiological tests were performed on 44 workers, their levels of exposure to toluene, xylene and ethylbenzene were determined and the levels of noise exposure were evaluated. The results showed that workers are generally exposed to high noise levels and cabin priming filler and varnish sector workers have high levels of exposure to toluene. However, no hearing loss was registered among the workers. Workers exposed simultaneously to noise and ototoxic substances do not have a higher degree of hearing loss than those workers exposed only to noise. Thus, the results of this study did not show that the combined exposure to noise and the organic solvent is associated with hearing disorders.

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.

Multidimensional scaling analysis of the dynamics of a country economy

This paper analyzes the Portuguese short-run business cycles over the last 150 years and presents the multidimensional scaling (MDS) for visualizing the results. The analytical and numerical assessment of this long-run perspective reveals periods with close connections between the macroeconomic variables related to government accounts equilibrium, balance of payments equilibrium, and economic growth. The MDS method is adopted for a quantitative statistical analysis. In this way, similarity clusters of several historical periods emerge in the MDS maps, namely, in identifying similarities and dissimilarities that identify periods of prosperity and crises, growth, and stagnation. Such features are major aspects of collective national achievement, to which can be associated the impact of international problems such as the World Wars, the Great Depression, or the current global financial crisis, as well as national events in the context of broad political blueprints for the Portuguese society in the rising globalization process.

A few what-ifs on using statistical analysis of stochastic simulation runs to extract timeliness properties

Modern real-time systems, with a more flexible and adaptive nature, demand approaches for timeliness evaluation based on probabilistic measures of meeting deadlines. In this context, simulation can emerge as an adequate solution to understand and analyze the timing behaviour of actual systems. However, care must be taken with the obtained outputs under the penalty of obtaining results with lack of credibility. Particularly important is to consider that we are more interested in values from the tail of a probability distribution (near worst-case probabilities), instead of deriving confidence on mean values. We approach this subject by considering the random nature of simulation output data. We will start by discussing well known approaches for estimating distributions out of simulation output, and the confidence which can be applied to its mean values. This is the basis for a discussion on the applicability of such approaches to derive confidence on the tail of distributions, where the worst-case is expected to be.