Optimization of River Water Quality Surveys by Multivariate Analysis of Physicochemical, Bacteriological and Ecotoxicological Data

This study aims to optimize the water quality monitoring of a polluted watercourse (Leça River, Portugal) through the principal component analysis (PCA) and cluster analysis (CA). These statistical methodologies were applied to physicochemical, bacteriological and ecotoxicological data (with the marine bacterium Vibrio fischeri and the green alga Chlorella vulgaris) obtained with the analysis of water samples monthly collected at seven monitoring sites and during five campaigns (February, May, June, August, and September 2006). The results of some variables were assigned to water quality classes according to national guidelines. Chemical and bacteriological quality data led to classify Leça River water quality as “bad” or “very bad”. PCA and CA identified monitoring sites with similar pollution pattern, giving to site 1 (located in the upstream stretch of the river) a distinct feature from all other sampling sites downstream. Ecotoxicity results corroborated this classification thus revealing differences in space and time. The present study includes not only physical, chemical and bacteriological but also ecotoxicological parameters, which broadens new perspectives in river water characterization. Moreover, the application of PCA and CA is very useful to optimize water quality monitoring networks, defining the minimum number of sites and their location. Thus, these tools can support appropriate management decisions.

Novel LTCC-potentiometric microfluidic device for biparametric analysis of organic compounds carrying plastic antibodies as ionophores: Application to sulfamethoxazole and trimethoprim

Monitoring organic environmental contaminants is of crucial importance to ensure public health. This requires simple, portable and robust devices to carry out on-site analysis. For this purpose, a low-temperature co-fired ceramics (LTCC) microfluidic potentiometric device (LTCC/μPOT) was developed for the first time for an organic compound: sulfamethoxazole (SMX). Sensory materials relied on newly designed plastic antibodies. Sol–gel, self-assembling monolayer and molecular-imprinting techniques were merged for this purpose. Silica beads were amine-modified and linked to SMX via glutaraldehyde modification. Condensation polymerization was conducted around SMX to fill the vacant spaces. SMX was removed after, leaving behind imprinted sites of complementary shape. The obtained particles were used as ionophores in plasticized PVC membranes. The most suitable membrane composition was selected in steady-state assays. Its suitability to flow analysis was verified in flow-injection studies with regular tubular electrodes. The LTCC/μPOT device integrated a bidimensional mixer, an embedded reference electrode based on Ag/AgCl and an Ag-based contact screen-printed under a micromachined cavity of 600 μm depth. The sensing membranes were deposited over this contact and acted as indicating electrodes. Under optimum conditions, the SMX sensor displayed slopes of about −58.7 mV/decade in a range from 12.7 to 250 μg/mL, providing a detection limit of 3.85 μg/mL and a sampling throughput of 36 samples/h with a reagent consumption of 3.3 mL per sample. The system was adjusted later to multiple analyte detection by including a second potentiometric cell on the LTCC/μPOT device. No additional reference electrode was required. This concept was applied to Trimethoprim (TMP), always administered concomitantly with sulphonamide drugs, and tested in fish-farming waters. The biparametric microanalyzer displayed Nernstian behaviour, with average slopes −54.7 (SMX) and +57.8 (TMP) mV/decade. To demonstrate the microanalyzer capabilities for real applications, it was successfully applied to single and simultaneous determination of SMX and TMP in aquaculture waters.

Analysis of ground reaction force and electromyographic activity of the gastrocnemius muscle during double support

O documento em anexo encontra-se na versão post-print (versão corrigida pelo editor).

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).

Entropy analysis of DNA code dynamics in human chromosomes

Deoxyribonucleic acid, or DNA, is the most fundamental aspect of life but present day scientific knowledge has merely scratched the surface of the problem posed by its decoding. While experimental methods provide insightful clues, the adoption of analysis tools supported by the formalism of mathematics will lead to a systematic and solid build-up of knowledge. This paper studies human DNA from the perspective of system dynamics. By associating entropy and the Fourier transform, several global properties of the code are revealed. The fractional order characteristics emerge as a natural consequence of the information content. These properties constitute a small piece of scientific knowledge that will support further efforts towards the final aim of establishing a comprehensive theory of the phenomena involved in life.

Dynamical analysis of compositions

This paper analyzes musical opus from the point of view of two mathematical tools, namely the entropy and the multidimensional scaling (MDS). The Fourier analysis reveals a fractional dynamics, but the time rhythm variations are diluted along the spectrum. The combination of time-window entropy and MDS copes with the time characteristics and is well suited to treat a large volume of data. The experiments focus on a large number of compositions classified along three sets of musical styles, namely “Classical”, “Jazz”, and “Pop & Rock” compositions. Without lack of generality, the present study describes the application of the tools and the sets of musical compositions in a methodology leading to clear conclusions, but extensions to other possibilities are straightforward. The results reveal significant differences in the musical styles, demonstrating the feasibility of the proposed strategy and motivating further developments toward a dynamical analysis of musical compositions.

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.

Wavelet analysis of human DNA

This paper studies the human DNA in the perspective of signal processing. Six wavelets are tested for analyzing the information content of the human DNA. By adopting real Shannon wavelet several fundamental properties of the code are revealed. A quantitative comparison of the chromosomes and visualization through multidimensional and dendograms is developed.

A multidimensional scaling analysis of musical sounds based on pseudo phase plane

This paper studies musical opus from the point of view of three mathematical tools: entropy, pseudo phase plane (PPP), and multidimensional scaling (MDS). The experiments analyze ten sets of different musical styles. First, for each musical composition, the PPP is produced using the time series lags captured by the average mutual information. Second, to unravel hidden relationships between the musical styles the MDS technique is used. The MDS is calculated based on two alternative metrics obtained from the PPP, namely, the average mutual information and the fractal dimension. The results reveal significant differences in the musical styles, demonstrating the feasibility of the proposed strategy and motivating further developments towards a dynamical analysis of musical sounds.

Performance analysis of Java APIS for XML processing

Over time, XML markup language has acquired a considerable importance in applications development, standards definition and in the representation of large volumes of data, such as databases. Today, processing XML documents in a short period of time is a critical activity in a large range of applications, which imposes choosing the most appropriate mechanism to parse XML documents quickly and efficiently. When using a programming language for XML processing, such as Java, it becomes necessary to use effective mechanisms, e.g. APIs, which allow reading and processing of large documents in appropriated manners. This paper presents a performance study of the main existing Java APIs that deal with XML documents, in order to identify the most suitable one for processing large XML files.

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.

Analysis of polycyclic aromatic hydrocarbons in fish: optimisation and validation of microwave-assisted extraction

An accurate and sensitive method for determination of 18 polycyclic aromatic hydrocarbons (PAHs) (16 PAHs considered by USEPA as priority pollutants, dibenzo[a,l]pyrene and benzo[j]fluoranthene) in fish samples was validated. Analysis was performed by microwave-assisted extraction and liquid chromatography with photodiode array and fluorescence detection. Response surface methodology was used to find the optimal extraction parameters. Validation of the overall methodology was performed by spiking assays at four levels and using SRM 2977. Quantification limits ranging from 0.15–27.16 ng/g wet weight were obtained. The established method was applied in edible tissues of three commonly consumed and commercially valuable fish species (sardine, chub mackerel and horse mackerel) originated from Atlantic Ocean. Variable levels of naphthalene (1.03–2.95 ng/g wet weight), fluorene (0.34–1.09 ng/g wet weight) and phenanthrene (0.34–3.54 ng/g wet weight) were detected in the analysed samples. None of the samples contained detectable amounts of benzo[a]pyrene, the marker used for evaluating the occurrence and carcinogenic effects of PAHs in food.

Optimization of QuEChERS method for the analysis of organochlorine pesticides in soils with diverse organic matter

A QuEChERS method has been developed for the determination of 14 organochlorine pesticides in 14 soils from different Portuguese regions with wide range composition. The extracts were analysed by GC-ECD (where GC-ECD is gas chromatography-electron-capture detector) and confirmed by GC-MS/MS (where MS/MS is tandem mass spectrometry). The organic matter content is a key factor in the process efficiency. An optimization was carried out according to soils organic carbon level, divided in two groups: HS (organic carbon>2.3%) and LS (organic carbon<2.3%). Themethod was validated through linearity, recovery, precision and accuracy studies. The quantification was carried out using a matrixmatched calibration to minimize the existence of the matrix effect. Acceptable recoveries were obtained (70–120%) with a relative standard deviation of ≤16% for the three levels of contamination. The ranges of the limits of detection and of the limits of quantification in soils HS were from 3.42 to 23.77 μg kg−1 and from 11.41 to 79.23 μg kg−1, respectively. For LS soils, the limits of detection ranged from 6.11 to 14.78 μg kg−1 and the limits of quantification from 20.37 to 49.27 μg kg−1. In the 14 collected soil samples only one showed a residue of dieldrin (45.36 μg kg−1) above the limit of quantification. This methodology combines the advantages of QuEChERS, GC-ECD detection and GC-MS/MS confirmation producing a very rapid, sensitive and reliable procedure which can be applied in routine analytical laboratories.

Interlaboratory validation of an environmental monitoring method for trace analysis of endocrine disrupting compounds

Environmental pollution continues to be an emerging study field, as there are thousands of anthropogenic compounds mixed in the environment whose possible mechanisms of toxicity and physiological outcomes are of great concern. Developing methods to access and prioritize the screening of these compounds at trace levels in order to support regulatory efforts is, therefore, very important. A methodology based on solid phase extraction followed by derivatization and gas chromatography-mass spectrometry analysis was developed for the assessment of four endocrine disrupting compounds (EDCs) in water matrices: bisphenol A, estrone, 17b-estradiol and 17a-ethinylestradiol. The study was performed, simultaneously, by two different laboratories in order to evaluate the robustness of the method and to increase the quality control over its application in routine analysis. Validation was done according to the International Conference on Harmonisation recommendations and other international guidelines with specifications for the GC-MS methodology. Matrix-induced chromatographic response enhancement was avoided by using matrix-standard calibration solutions and heteroscedasticity has been overtaken by a weighted least squares linear regression model application. Consistent evaluation of key analytical parameters such as extraction efficiency, sensitivity, specificity, linearity, limits of detection and quantification, precision, accuracy and robustness was done in accordance with standards established for acceptance. Finally, the application of the optimized method in the assessment of the selected analytes in environmental samples suggested that it is an expedite methodology for routine analysis of EDC residues in water matrices.