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.

Direct determination of iron in sand using solid sampling graphite furnace atomic absorption spectrometry

A fast and reliable method for the direct determination of iron in sand by solid sampling graphite furnace atomic absorption spectrometry was developed. A Zeeman-effect 3-field background corrector was used to decrease the sensitivity of spectrometer measurements. This strategy allowed working with up to 200 mu g of samples, thus improving the representativity. Using samples with small particle sizes (1-50 mu m) and adding 5 mu g Pd as chemical modifier, it was possible to obtain suitable calibration curves with aqueous reference solutions. The pyrolysis and atomization temperatures for the optimized heating program were 1400 and 2500 degrees C, respectively. The characteristic mass, based on integrated absorbance, was 56 pg, and the detection limits, calculated considering the variability of 20 consecutive measurements of platform inserted without sample was 32 pg. The accuracy of the procedure was checked with the analysis of two reference materials (IPT 62 and 63). The determined concentrations were in agreement with the recommended values (95% confidence level). Five sand samples were analyzed, and a good agreement (95% confidence level) was observed using the proposed method and conventional flame atomic absorption spectrometry. The relative standard deviations were lower than 25% (n = 5). The tube and boat platform lifetimes were around 1000 and 250 heating cycles, respectively.

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.

Adaptive, Decentralized, And Real-Time Sampling Strategies For Resource Constrained Hydraulic And Hydrologic Sensor Networks

We discuss the development and performance of a low-power sensor node (hardware, software and algorithms) that autonomously controls the sampling interval of a suite of sensors based on local state estimates and future predictions of water flow. The problem is motivated by the need to accurately reconstruct abrupt state changes in urban watersheds and stormwater systems. Presently, the detection of these events is limited by the temporal resolution of sensor data. It is often infeasible, however, to increase measurement frequency due to energy and sampling constraints. This is particularly true for real-time water quality measurements, where sampling frequency is limited by reagent availability, sensor power consumption, and, in the case of automated samplers, the number of available sample containers. These constraints pose a significant barrier to the ubiquitous and cost effective instrumentation of large hydraulic and hydrologic systems. Each of our sensor nodes is equipped with a low-power microcontroller and a wireless module to take advantage of urban cellular coverage. The node persistently updates a local, embedded model of flow conditions while IP-connectivity permits each node to continually query public weather servers for hourly precipitation forecasts. The sampling frequency is then adjusted to increase the likelihood of capturing abrupt changes in a sensor signal, such as the rise in the hydrograph – an event that is often difficult to capture through traditional sampling techniques. Our architecture forms an embedded processing chain, leveraging local computational resources to assess uncertainty by analyzing data as it is collected. A network is presently being deployed in an urban watershed in Michigan and initial results indicate that the system accurately reconstructs signals of interest while significantly reducing energy consumption and the use of sampling resources. We also expand our analysis by discussing the role of this approach for the efficient real-time measurement of stormwater systems.

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).

Convergence analysis of sampling-based decomposition methods for risk-averse multistage stochastic convex programs

We consider a class of sampling-based decomposition methods to solve risk-averse multistage stochastic convex programs. We prove a formula for the computation of the cuts necessary to build the outer linearizations of the recourse functions. This formula can be used to obtain an efficient implementation of Stochastic Dual Dynamic Programming applied to convex nonlinear problems. We prove the almost sure convergence of these decomposition methods when the relatively complete recourse assumption holds. We also prove the almost sure convergence of these algorithms when applied to risk-averse multistage stochastic linear programs that do not satisfy the relatively complete recourse assumption. The analysis is first done assuming the underlying stochastic process is interstage independent and discrete, with a finite set of possible realizations at each stage. We then indicate two ways of extending the methods and convergence analysis to the case when the process is interstage dependent.

Long-term facial artery catheter implantation for serial arterial blood sampling and invasive arterial blood pressure measurement in horses

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Soil sampling intensity and spatial distribution pattern of soils attributes and corn yield in no-tillage system

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Effects of different sampling intervals on apparent protein and energy digestibility of common feed ingredients by juvenile oscar fish (Astronotus ocellatus)

O presente estudo avaliou a digestibilidade aparente da proteína e da energia de ingredientes (farelo de soja, farinha de peixe, farelo de trigo e milho) por juvenis de apaiari (Astronotus ocellatus) usando dois diferentes intervalos de coleta (30 min. e 12h). Os 160 juvenis de apaiari utilizados (22,37 ± 3,06 g de peso corporal) foram divididos em quatro tanques rede plásticos e cilíndricos, cada um colocado em um tanque de alimentação de 1.000 L. O experimento foi inteiramente casualizado em esquema fatorial 2 x 4 (2 intervalos de coleta de fezes e 4 ingredientes foram) com quatro repetições. Os testes estatísticos não detectaram efeito da interação entre o intervalo de coleta e tipo de ingrediente nos coeficientes de digestibilidade. O intervalo de coleta não afetou a digestibilidade da proteína e da energia. As características físicas das fezes dos juvenis de apaiari aparentemente as tornam menos sensíveis à perda de nutrientes por lixiviação, permitindo intervalos de coleta maiores. A digestibilidade da proteína dos ingredientes avaliados foi semelhante, mostrando que a digestibilidade aparente de ingredientes animais e vegetais por juvenis de apaiari é eficiente. Os coeficientes de digestibilidade da energia foram maiores para a farinha de peixe e o farelo de soja comparado a farelo de trigo e milho. Ingredientes ricos em carboidratos (farelo de trigo e milho) apresentaram os piores coeficientes de digestibilidade da energia e, portanto, não são usados eficientemente pelos juvenis de apaiari.

Spatial variability of soil penetration resistance influenced by season of sampling

O objetivo deste trabalho foi analizar a distribuição espacial da compactação do solo e a influência da umidade do solo na resistência à penetração. Esta última variável foi descrita pelo índice de cone. O solo estudado foi Nitossolo e os dados de índice de cone foram obtidos usando um penetrômetro. A resistência do solo foi avaliada a 5 profundidades diferentes, 0-10 cm, 10-20 cm, 20-30 cm, 30-40 cm e mais de 40 cm, porém o conteúdo de umidade do solo foi medido a 0-20 cm e 20-40 cm. As condições hídricas do solo variaram nas diferentes amostragems. Os coeficientes de variação para o índice de cone foram 16,5% a 45,8% e os do conteúdo de umidade do solo variaram entre 8,96% e 21,38%. Os resultados sugeriram elevada correlação entre a resistência do solo, estimada pelo índice de cone e a profundidade do solo. Sem embargo, a relação esperada com a umidade do solo não foi apreciada. Observou-se dependência espacial em 31 de 35 séries de dados de índice de cone e umidade do solo. Esta dependência foi ajustada por modelos exponenciais com efeito pepita variável de 0 a 90% o valor do patamar. em séries de dados o comportamento foi aleatório. Portanto, a técnica das distâncias inversas foi utilizada para cartografar a distribuição das variáveis que não tiveram estrutura espacial. Na krigagem constatou-se uma suavização dos mapas comparados com esses das distâncias inversas. A krigagem indicadora foi utilizada para cartografar a variabilidade espacial do índice de cone e recomendar melhor manejo do solo.

Stratified Sampling Applied to Estimation of the Volumetric Fraction of Alumina in Cast Metal Matrix Composites

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Determination of Population Size of Glass-like Carbon Sampling Used in Weibull Analysis

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)