Geophysical investigation using resistivity and GPR methods: a case study of a lubricant oil waste disposal area in the city of Ribeiro Preto, So Paulo, Brazil

Geophysics has been shown to be effective in identifying areas contaminated by waste disposal, contributing to the greater efficiency of soundings programs and the installation of monitoring wells. In the study area, four trenches were constructed with a total volume of about 25,000 m(3). They were almost totally filled with re-refined lubricating oil waste for approximately 25 years. No protection liners were used in the bottoms and laterals of the disposal trenches. The purpose of this work is to evaluate the potential of the resistivity and ground penetrating radar (GPR) methods in characterizing the contamination of this lubricant oil waste disposal area in Ribeiro Preto, SP, situated on the geological domain of the basalt spills of the Serra Geral Formation and the sandstones of the Botucatu Formation. Geophysical results were shown in 2D profiles. The geophysical methods used enabled the identification of geophysical anomalies, which characterized the contamination produced by the trenches filled with lubricant oil waste. Conductive anomalies (smaller than 185 Omega m) immediately below the trenches suggest the action of bacteria in the hydrocarbons, as has been observed in several sites contaminated by hydrocarbons in previously reported cases in the literature. It was also possible to define the geometry of the trenches, as evidenced by the GPR method. Direct sampling (chemical analysis of the soil and the water in the monitoring well) confirmed the contamination. In the soil analysis, low concentrations of several polycyclic aromatic hydrocarbons (PAHs) were found, mainly naphthalene and phenanthrene. In the water samples, an analysis verified contamination of the groundwater by lead (Pb). The geophysical methods used in the investigation provided an excellent tool for environmental characterization in this study of a lubricant oil waste disposal area, and could be applied in the study of similar areas.

Aerosol inorganic composition at a tropical site: Discrepancies between filter-based sampling and a semi-continuous method

The concentrations of the water-soluble inorganic aerosol species, ammonium (NH4+), nitrate (NO3-), chloride (Cl-), and sulfate (SO42-), were measured from September to November 2002 at a pasture site in the Amazon Basin (Rondnia, Brazil) (LBA-SMOCC). Measurements were conducted using a semi-continuous technique (Wet-annular denuder/Steam-Jet Aerosol Collector: WAD/SJAC) and three integrating filter-based methods, namely (1) a denuder-filter pack (DFP: Teflon and impregnated Whatman filters), (2) a stacked-filter unit (SFU: polycarbonate filters), and (3) a High Volume dichotomous sampler (HiVol: quartz fiber filters). Measurements covered the late dry season (biomass burning), a transition period, and the onset of the wet season (clean conditions). Analyses of the particles collected on filters were performed using ion chromatography (IC) and Particle-Induced X-ray Emission spectrometry (PIXE). Season-dependent discrepancies were observed between the WAD/SJAC system and the filter-based samplers. During the dry season, when PM2.5 (D-p <= 2.5 mu m) concentrations were similar to 100 mu g m(-3), aerosol NH4+ and SO42- measured by the filter-based samplers were on average two times higher than those determined by the WAD/SJAC. Concentrations of aerosol NO3- and Cl- measured with the HiVol during daytime, and with the DFP during day- and nighttime also exceeded those of the WAD/SJAC by a factor of two. In contrast, aerosol NO3- and Cl- measured with the SFU during the dry season were nearly two times lower than those measured by the WAD/SJAC. These differences declined markedly during the transition period and towards the cleaner conditions during the onset of the wet season (PM2.5 similar to 5 mu g m(-3)); when filter-based samplers measured on average 40-90% less than the WAD/SJAC. The differences were not due to consistent systematic biases of the analytical techniques, but were apparently a result of prevailing environmental conditions and different sampling procedures. For the transition period and wet season, the significance of our results is reduced by a low number of data points. We argue that the observed differences are mainly attributable to (a) positive and negative filter sampling artifacts, (b) presence of organic compounds and organosulfates on filter substrates, and (c) a SJAC sampling efficiency of less than 100%.

Versatile microanalytical system with porous polypropylene capillary membrane for calibration gas generation and trace gaseous pollutants sampling applied to the analysis of formaldehyde, formic acid, acetic acid and ammonia in outdoor air

The analytical determination of atmospheric pollutants still presents challenges due to the low-level concentrations (frequently in the mu g m(-3) range) and their variations with sampling site and time In this work a capillary membrane diffusion scrubber (CMDS) was scaled down to match with capillary electrophoresis (CE) a quick separation technique that requires nothing more than some nanoliters of sample and when combined with capacitively coupled contactless conductometric detection (C(4)D) is particularly favorable for ionic species that do not absorb in the UV-vis region like the target analytes formaldehyde formic acid acetic acid and ammonium The CMDS was coaxially assembled inside a PTFE tube and fed with acceptor phase (deionized water for species with a high Henry s constant such as formaldehyde and carboxylic acids or acidic solution for ammonia sampling with equilibrium displacement to the non-volatile ammonium ion) at a low flow rate (8 3 nLs(-1)) while the sample was aspirated through the annular gap of the concentric tubes at 25 mLs(-1) A second unit in all similar to the CMDS was operated as a capillary membrane diffusion emitter (CMDE) generating a gas flow with know concentrations of ammonia for the evaluation of the CMDS The fluids of the system were driven with inexpensive aquarium air pumps and the collected samples were stored in vials cooled by a Peltier element Complete protocols were developed for the analysis in air of NH(3) CH(3)COOH HCOOH and with a derivatization setup CH(2)O by associating the CMDS collection with the determination by CE-C(4)D The ammonia concentrations obtained by electrophoresis were checked against the reference spectrophotometric method based on Berthelot s reaction Sensitivity enhancements of this reference method were achieved by using a modified Berthelot reaction solenoid micro-pumps for liquid propulsion and a long optical path cell based on a liquid core waveguide (LCW) All techniques and methods of this work are in line with the green analytical chemistry trends (C) 2010 Elsevier B V All rights reserved

Environmental formaldehyde analysis by active diffusive sampling with a bundle of polypropylene porous capillaries followed by capillary zone electrophoretic separation and contactless conductivity detection

Compared to other volatile carbonylic compounds present in outdoor air, formaldehyde (CH2O) is the most toxic, deserving more attention in terms of indoor and outdoor air quality legislation and control. The analytical determination of CH2O in air still presents challenges due to the low-level concentration (in the sub-ppb range) and its variation with sampling site and time. Of the many available analytical methods for carbonylic compounds, the most widespread one is the time consuming collection in cartridges impregnated with 2,4-dinitrophenylhydrazine followed by the analysis of the formed hydrazones by HPLC. The present work proposes the use of polypropylene hollow porous capillary fibers to achieve efficient CH2O collection. The Oxyphan (R) fiber (designed for blood oxygenation) was chosen for this purpose because it presents good mechanical resistance, high density of very fine pores and high ratio of collection area to volume of the acceptor fluid in the tube, all favorable for the development of air sampling apparatus. The collector device consists of a Teflon pipe inside of which a bundle of polypropylene microporous capillary membranes was introduced. While the acceptor passes at a low flow rate through the capillaries, the sampled air circulates around the fibers, impelled by a low flow membrane pump (of the type used for aquariums ventilation). The coupling of this sampling technique with the selective and quantitative determination of CH2O, in the form of hydroxymethanesulfonate (HMS) after derivatization with HSO3-, by capillary electrophoresis with capacitively coupled contactless conductivity detection (CE-(CD)-D-4) enabled the development of a complete analytical protocol for the CH2O evaluation in air. (C) 2008 Published by Elsevier B.V.

Application of solid sampling device for direct determination of chromium and nickel in lubricating oils by graphite furnace atomic absorption spectrometry

One method using a solid sampling device for the direct determination of Cr and Ni in fresh and used lubricating oils by graphite furnace atomic absorption spectrometry are proposed. The high organic content in the samples was minimized using a digestion step at 400 degrees C in combination with an oxidant mixture 1.0% (v v(-1)) HNO3+15% (v v(-1)) H2O2+0.1% (m v(-1)) Triton X-100 for the in situ digestion. The 3-field mode Zeeman-effect allowed the spectrometer calibration up to 5 ng of Cr and Ni. The quantification limits were 0.86 mu g g(-1) for Cr and 0.82 mg g(-1) for Ni, respectively. The analysis of reference materials showed no statistically significant difference between the recommended values and those obtained by the proposed methods.

Convex combinations of long memory estimates from different sampling rates

Convex combinations of long memory estimates using the same data observed at different sampling rates can decrease the standard deviation of the estimates, at the cost of inducing a slight bias. The convex combination of such estimates requires a preliminary correction for the bias observed at lower sampling rates, reported by Souza and Smith (2002). Through Monte Carlo simulations, we investigate the bias and the standard deviation of the combined estimates, as well as the root mean squared error (RMSE), which takes both into account. While comparing the results of standard methods and their combined versions, the latter achieve lower RMSE, for the two semi-parametric estimators under study (by about 30% on average for ARFIMA(0,d,0) series).

Non invasive methods for genetic analysis applied to ecological and behavioral studies in Latino-America

Documenting the presence and abundance of the neotropical mammals is the first step for understanding their population ecology, behavior and genetic dynamics in designing conservation plans. The combination of field research with molecular genetics techniques are new tools that provide valuable biological information avoiding the disturbance in the ecosystems, trying to minimize the human impact in the process to gather biological information. The objective of this paper is to review the available non invasive sampling techniques that have been used in Neotropical mammal studies to apply to determine the presence and abundance, population structure, sex ratio, taxonomic diagnostic using mitochondrial markers, and assessing genetic variability using nuclear markers. There are a wide range of non invasive sampling techniques used to determine the species identification that inhabit an area such as searching for tracks, feces, and carcasses. Other useful equipment is the camera traps that can generate an image bank that can be valuable to assess species presence and abundance by morphology. With recent advances in molecular biology, it is now possible to use the trace amounts of DNA in feces and amplify it to analyze the species diversity in an area, and the genetic variability at intraspecific level. This is particularly helpful in cases of sympatric and cryptic species in which morphology failed to diagnose the taxonomic status of several species of brocket deer of the genus Mazama.

Variable parameter and double sampling (X)over-bar charts in the presence of correlation: The Markov chain approach

The general assumption under which the (X) over bar chart is designed is that the process mean has a constant in-control value. However, there are situations in which the process mean wanders. When it wanders according to a first-order autoregressive (AR (1)) model, a complex approach involving Markov chains and integral equation methods is used to evaluate the properties of the (X) over bar chart. In this paper, we propose the use of a pure Markov chain approach to study the performance of the (X) over bar chart. The performance of the chat (X) over bar with variable parameters and the (X) over bar with double sampling are compared. (C) 2011 Elsevier B.V. All rights reserved.

GFAAS Determination of Zinc in Fish Feed and Feces Using Slurry Sampling

This paper presents a simple, fast, and sensitive method to determine zinc in samples of feces and fish feed by electrothermal atomic absorption spectrometry through the direct introduction of slurries of the samples into the spectrometer's graphite tube. The procedure is based on the injection of 10 mu L of an acidified aqueous solution containing 0.50% w/v of feces or feed and 0.50% v/v HNO(3) into graphite tube. The limits of detection and quantification calculated for 20 readings of the blank of the standard slurries (0.50% w/v of feces or feed devoid of zinc) were 0.04 and 0.13 mu g L(-1) for the standard feces slurries and 0.05 and 0.17 mu g L(-1) for the standard feed slurries. The proposed method was applied in studies of digestibility of zinc in different fish feeds, and their results proved compatible with that obtained from samples mineralized by acid digestion using microwave oven.

VSSI (X)over-bar charts with sampling at fixed times

A standard (X) over bar chart for controlling the process mean takes samples of size no at specified, equally-spaced, fixed-time points. This article proposes a modification of the standard (X) over bar chart that allows one to take additional samples, bigger than no, between these fixed times. The additional samples are taken from the process when there is evidence that the process mean moved from target. Following the notation proposed by Reynolds (1996a) and Costs (1997) we shortly call the proposed (X) over bar chart as VSSIFT (X) over bar chart: where VSSIFT means variable sample size and sampling intervals with fixed times. The (X) over bar chart with the VSSIFT feature is easier to be administered than a standard VSSI (X) over bar chart that is not constrained to sample at the specified fixed times. The performances of the charts in detecting process mean shifts are comparable.

The carpal pad as an alternative sampling site for blood glucose testing in dogs

To investigate the feasibility and validity of sampling blood from the carpal pad in hospitalised healthy and diabetic dogs. METHODS The carpal pad was compared to the ear as a sampling site in 60 dogs (30 healthy and 30 diabetic dogs). RESULTS Lancing the pads was very well tolerated. The average glucose concentrations in blood samples obtained from the ears and carpal pads exhibited a strong positive correlation (r = 0.938) and there were no significant differences between them (P = 0.914). In addition, 98.3% of the values obtained were clinically acceptable when assessed by the error grid analysis. CLINICAL SIGNIFICANCE The carpal pad is a good alternative sampling site for home monitoring, especially in animals with a soft and/or light-coloured pad.

X̄ chart with variable sample size and sampling intervals

Recent theoretical studies have shown that the X̄ chart with variable sampling intervals (VSI) and the X̄ chart with variable sample size (VSS) are quicker than the traditional X̄ chart in detecting shifts in the process. This article considers the X̄ chart with variable sample size and sampling intervals (VSSI). It is assumed that the amount of time the process remains in control has exponential distribution. The properties of the VSSI X̄ chart are obtained using Markov chains. The VSSI X̄ chart is even quicker than the VSI or VSS X̄ charts in detecting moderate shifts in the process.

VSSI X̄ charts with sampling at fixed times

A standard X̄ chart for controlling the process mean takes samples of size n0 at specified, equally-spaced, fixed-time points. This article proposes a modification of the standard X chart that allows one to take additional samples, bigger than n0, between these fixed times. The additional samples are taken from the process when there is evidence that the process mean moved from target. Following the notation proposed by Reynolds (1996a) and Costa (1997) we shortly call the proposed X chart as VSSIFT X chart where VSSIFT means variable sample size and sampling intervals with fixed times. The X chart with the VSSIFT feature is easier to be administered than a standard VSSI X chart that is not constrained to sample at the specified fixed times. The performances of the charts in detecting process mean shifts are comparable. Copyright © 1998 by Marcel Dekker, Inc.

Exfoliative cytology of the oral mucosa: Comparison of two collection methods

This study compared the sampling efficacy cia cytobrush and metal spatula for exfoliative cytology of the oral mucosa. Thirty students with no detectable oral alterations upon clinical examination were submitted to exfoliative cytology of the lateral border of the tongue, using a metal spatula on the left side and a cytobrush on the right side. The smears were stained using the Papanicoiaou technique and evaluated for cellularity, cell type, cell distribution, homogeneity, and cellular distortion, as well as the presence ol mucus, inflammatory infiltrate, and hemorrhage. A statistical test (Z-test) with a 95% confdence interval (Cl) showed a significant difference between the metal spatula and cytobrush in terms of cellularity (p = 0.02) and homogeneity (p = 0.01). No difference between the two methods was observed regarding cell type (p = 0.4, Z-test) or cell distribution for the 95% confidence interval (p = 0.2, Fisher's test). Cell distortion and the presence of mucus were observed in five cases that used the metal spatula and in two cases that used the cytobrush. No hemorrhage or inflammatory infItrate was detected in any of the slides. Based on the results of this study, the cytobrush produced qualitatively better smears in terms of cellularity and homogeneity compared to the metal spatula.

Digital soil mapping: evaluation of sampling systems for soil surveys and refinement of soil maps at lower cost using legacy data

In soil surveys, several sampling systems can be used to define the most representative sites for sample collection and description of soil profiles. In recent years, the conditioned Latin hypercube sampling system has gained prominence for soil surveys. In Brazil, most of the soil maps are at small scales and in paper format, which hinders their refinement. The objectives of this work include: (i) to compare two sampling systems by conditioned Latin hypercube to map soil classes and soil properties; (II) to retrieve information from a detailed scale soil map of a pilot watershed for its refinement, comparing two data mining tools, and validation of the new soil map; and (III) to create and validate a soil map of a much larger and similar area from the extrapolation of information extracted from the existing soil map. Two sampling systems were created by conditioned Latin hypercube and by the cost-constrained conditioned Latin hypercube. At each prospection place, soil classification and measurement of the A horizon thickness were performed. Maps were generated and validated for each sampling system, comparing the efficiency of these methods. The conditioned Latin hypercube captured greater variability of soils and properties than the cost-constrained conditioned Latin hypercube, despite the former provided greater difficulty in field work. The conditioned Latin hypercube can capture greater soil variability and the cost-constrained conditioned Latin hypercube presents great potential for use in soil surveys, especially in areas of difficult access. From an existing detailed scale soil map of a pilot watershed, topographical information for each soil class was extracted from a Digital Elevation Model and its derivatives, by two data mining tools. Maps were generated using each tool. The more accurate of these tools was used for extrapolation of soil information for a much larger and similar area and the generated map was validated. It was possible to retrieve the existing soil map information and apply it on a larger area containing similar soil forming factors, at much low financial cost. The KnowledgeMiner tool for data mining, and ArcSIE, used to create the soil map, presented better results and enabled the use of existing soil map to extract soil information and its application in similar larger areas at reduced costs, which is especially important in development countries with limited financial resources for such activities, such as Brazil.