Determination of the absolute accuracy of UK chamber facilities used in measuring methane emissions from livestock

Respiration chambers are one of the primary sources of data on methane emissions from livestock. This paper describes the results from a coordinated set of chamber validation experiments which establishes the absolute accuracy of the methane emission rates measured by the chambers, and for the first time provides metrological traceability to international standards, assesses the impact of both analyser and chamber response times on measurement uncertainty and establishes direct comparability between measurements made across different facilities with a wide range of chamber designs. As a result of the validation exercise the estimated combined uncertainty associated with the overall capability across all facilities reduced from 25.7% (k = 2, 95% confidence) before the validation to 2.1% (k = 2, 95% confidence) when the validation results are applied to the facilities’ data.

Heteroscedastic controlled calibration model applied to analytical chemistry

In chemical analyses performed by laboratories, one faces the problem of determining the concentration of a chemical element in a sample. In practice, one deals with the problem using the so-called linear calibration model, which considers that the errors associated with the independent variables are negligible compared with the former variable. In this work, a new linear calibration model is proposed assuming that the independent variables are subject to heteroscedastic measurement errors. A simulation study is carried out in order to verify some properties of the estimators derived for the new model and it is also considered the usual calibration model to compare it with the new approach. Three applications are considered to verify the performance of the new approach. Copyright (C) 2010 John Wiley & Sons, Ltd.

Uma metodologia para redução de incertezas em sistema de medição de vazão de óleo e gás

The objective of this research is to discuss about the need for implementation of new alternatives for the implementation on the metrological control: on the findings of initial and subsequent measurements, the control procedures of measurement uncertainty applied in assessing the loss or remains found in handling operations of bulk liquids, when used turbine meters used in measuring the tax on the business of Petrobras, due to the current environment of legal metrology and scientific, both domestic and international. We aim, with these alternatives: standardizing the minimization of random and systematic errors, the estimate of the remaining errors, as well as the management control of metrological calibration procedures, control of measurement uncertainty, and contribute to the change in the form of performance of legal metrology and scientific disseminating new information to change management of metrological control, objectively focused on aspects of supervision in implementing these activities in the control of the uncertainties of measurement used in our processes in the fiscal measurement system Petrobras. Results are presented, information and comments on the influence of measurement uncertainty in the current results of the fiscal and transfer of custody. This will emphasize the need, among other things, improvement and expansion of metrological control monitored by setting a better meet demand, calibration equipment and measuring instruments for Petrobras. Finally, we intend to establish the need for improving the method of evaluation of the data meter applied to the current management control of measurement uncertainty by proposing a methodology for addressing the problem, as well as highlighting the expected results.

Qualidade de dados fluviométricos obtidos através de perfilamento acústico

Acoustic Doppler current profilers are currently the main option for flow measurement and hydrodynamic monitoring of streams, replacing traditional methods. The spread of such equipment is mainly due to their operational advantages ranging from speed measurement to the greatest detail and amount of information generated about the hydrodynamics of hydrometric sections. As in the use of traditional methods and equipments, the use of acoustic Doppler profilers should be guided by the pursuit of data quality, since these are the basis for project and management of water resources constructions and systems. In this sense, the paper presents an analysis of measurement uncertainties of a hydrometric campaign held in Sapucaí River (Piranguinho-MG), using two different Doppler profilers - a Rio Grande ADCP 1200 kHz and a Qmetrix Qliner. 10 measurements were performed with each equipment consecutively, following the literature quality protocols, and later, a Type A uncertainty analysis (statistical analysis of several independent observations of the input under the same conditions). The measurements of the ADCP and Qliner presented, respectively, standard uncertainties of 0.679% and 0.508% compared with the averages. These results are satisfactory and acceptable when compared to references in the literature, indicating that the use of Doppler profilers is valid for expansion and upgrade of streamflow measurement networks and generation of hydrological data.

Chlorine isotope composition in chlorofluorocarbons CFC-11, CFC-12 and CFC-113 in firn, stratospheric and tropospheric air

The stratospheric degradation of chlorofluorocarbons (CFCs) releases chlorine, which is a major contributor to the destruction of stratospheric ozone (O3). A recent study reported strong chlorine isotope fractionation during the breakdown of the most abundant CFC (CFC-12, CCl2F2, Laube et al., 2010a), similar to effects seen in nitrous oxide (N2O). Using air archives to obtain a long-term record of chlorine isotope ratios in CFCs could help to identify and quantify their sources and sinks. We analyse the three most abundant CFCs and show that CFC-11 (CCl3F) and CFC-113 (CClF2CCl2F) exhibit significant stratospheric chlorine isotope fractionation, in common with CFC-12. The apparent isotope fractionation (ϵapp) for mid- and high-latitude stratospheric samples are respectively −2.4 (0.5) and −2.3 (0.4) ‰ for CFC-11, −12.2 (1.6) and −6.8 (0.8) ‰ for CFC-12 and −3.5 (1.5) and −3.3 (1.2) ‰ for CFC-113, where the number in parentheses is the numerical value of the standard uncertainty expressed in per mil. Assuming a constant isotope composition of emissions, we calculate the expected trends in the tropospheric isotope signature of these gases based on their stratospheric 37Cl enrichment and stratosphere–troposphere exchange. We compare these projections to the long-term δ (37Cl) trends of all three CFCs, measured on background tropospheric samples from the Cape Grim air archive (Tasmania, 1978–2010) and tropospheric firn air samples from Greenland (North Greenland Eemian Ice Drilling (NEEM) site) and Antarctica (Fletcher Promontory site). From 1970 to the present day, projected trends agree with tropospheric measurements, suggesting that within analytical uncertainties, a constant average emission isotope delta (δ) is a compatible scenario. The measurement uncertainty is too high to determine whether the average emission isotope δ has been affected by changes in CFC manufacturing processes or not. Our study increases the suite of trace gases amenable to direct isotope ratio measurements in small air volumes (approximately 200 mL), using a single-detector gas chromatography–mass spectrometry (GC–MS) system.

DEVELOPMENT AND IMPLEMENTATION OF A REMOTE AUDIT TOOL FOR HIGH DOSE RATE (HDR) 192IR BRACHYTHERAPY USING OPTICALLY STIMULATED LUMINESCENCE DOSIMETRY

This work aimed to create a mailable and OSLD-based phantom with accuracy suitable for RPC audits of HDR brachytherapy sources at institutions participating in NCI-funded cooperative clinical trials. An 8 × 8 × 10 cm3 prototype with two slots capable of holding nanoDot Al2O3:C OSL dosimeters (Landauer, Glenwood, IL) was designed and built. The phantom has a single channel capable of accepting all 192Ir HDR brachytherapy sources in current clinical use in the United States. Irradiations were performed with an 192Ir HDR source to determine correction factors for linearity with dose, dose rate, and the combined effect of irradiation energy and phantom construction. The uncertainties introduced by source positioning in the phantom and timer resolution limitations were also investigated. It was found that the linearity correction factor was where dose is in cGy, which differed from that determined by the RPC for the same batch of dosimeters under 60Co irradiation. There was no significant dose rate effect. Separate energy+block correction factors were determined for both models of 192Ir sources currently in clinical use and these vendor-specific correction factors differed by almost 2.6%. For Nucletron sources, this correction factor was 1.026±0.004 (99% Confidence Interval) and for Varian sources it was 1.000±0.007 (99% CI). Reasonable deviations in source positioning within the phantom and the limited resolution of the source timer had insignificant effects on the ability to measure dose. Overall measurement uncertainty of the system was estimated to be ±2.5% for both Nucletron and Varian source audits (95% CI). This uncertainty was sufficient to establish a ±5% acceptance criterion for source strength audits under a formal RPC audit program. Trial audits of eight participating institutions resulted in an average RPC-to-institution dose ratio of 1.000 with a standard deviation of 0.011.

A comprehensive analysis of tidal notches in the Mediterranean Sea

Recent works (Evelpidou et al., 2012) suggest that the modern tidal notch is disappearing worldwide due sea level rise over the last century. In order to assess this hypothesis, we measured modern tidal notches in several of sites along the Mediterranean coasts. We report observations on tidal notches cut along carbonate coasts from 73 sites from Italy, France, Croatia, Montenegro, Greece, Malta and Spain, plus additional observations carried outside the Mediterranean. At each site, we measured notch width and depth, and we described the characteristics of the biological rim at the base of the notch. We correlated these parameters with wave energy, tide gauge datasets and rock lithology. Our results suggest that, considering 'the development of tidal notches the consequence of midlittoral bioerosion' (as done in Evelpidou et al., 2012) is a simplification that can lead to misleading results, such as stating that notches are disappearing. Important roles in notch formation can be also played by wave action, rate of karst dissolution, salt weathering and wetting and drying cycles. Of course notch formation can be augmented and favoured also by bioerosion which can, in particular cases, be the main process of notch formation and development. Our dataset shows that notches are carved by an ensemble rather than by a single process, both today and in the past, and that it is difficult, if not impossible, to disentangle them and establish which one is prevailing. We therefore show that tidal notches are still forming, challenging the hypothesis that sea level rise has drowned them.

Economical analysis for investment on measuring systems

Metrology processes contribute to entire manufacturing systems that can have a considerable impact on financial investment in coordinate measuring systems. However, there is a lack of generic methodologies to quantify their economical value in today’s industry. To solve this problem, a mathematical model is proposed in this paper by statistical deductive reasoning. This is done through defining the relationships between Process Capability Index, measurement uncertainty and tolerance band. The correctness of the mathematical model is proved by a case study. Finally, several comments and suggestions on evaluating and maximizing the benefits of metrology investment are given.

Ultra-long range distributed fibre sensing using virtually transparent propagation

Distributed fibre sensors provide unique capabilities for monitoring large infrastructures with high resolution. Practically, all these sensors are based on some kind of backscattering interaction. A pulsed activating signal is launched on one side of the sensing fibre and the backscattered signal is read as a function of the time of flight of the pulse along the fibre. A key limitation in the measurement range of all these sensors is introduced by fibre attenuation. As the pulse travels along the fibre, the losses in the fibre cause a drop of signal contrast and consequently a growth in the measurement uncertainty. In typical single-mode fibres, attenuation imposes a range limit of less than 30km, for resolutions in the order of 1-2 meters. An interesting improvement in this performance can be considered by using distributed amplification along the fibre [1]. Distributed amplification allows having a more homogeneous signal power along the sensing fibre, which also enables reducing the signal power at the input and therefore avoiding nonlinearities. However, in long structures (≥ 50 km), plain distributed amplification does not perfectly compensate the losses and significant power variations along the fibre are to be expected, leading to inevitable limitations in the measurements. From this perspective, it is simple to understand intuitively that the best possible solution for distributed sensors would be offered by a virtually transparent fibre, i.e. a fibre exhibiting effectively zero attenuation in the spectral region of the pulse. In addition, it can be shown that lossless transmission is the working point that allows the minimization of the amplified spontaneous emission (ASE) noise build-up. © 2011 IEEE.

Determining the change of Brillouin frequency shift by using the similarity matching method

We have proposed a similarity matching method (SMM) to obtain the change of Brillouin frequency shift (BFS), in which the change of BFS can be determined from the frequency difference between detecting spectrum and selected reference spectrum by comparing their similarity. We have also compared three similarity measures in the simulation, which has shown that the correlation coefficient is more accurate to determine the change of BFS. Compared with the other methods of determining the change of BFS, the SMM is more suitable for complex Brillouin spectrum profiles. More precise result and much faster processing speed have been verified in our simulation and experiments. The experimental results have shown that the measurement uncertainty of the BFS has been improved to 0.72 MHz by using the SMM, which is almost one-third of that by using the curve fitting method, and the speed of deriving the BFS change by the SMM is 120 times faster than that by the curve fitting method.

KOSMOS Finland 2012 mesocosm study: primary production and respiration

Anthropogenic carbon dioxide (CO2) emissions are reducing the pH in the world's oceans. The plankton community is a key component driving biogeochemical fluxes, and the effect of increased CO2 on plankton is critical for understanding the ramifications of ocean acidification on global carbon fluxes. We determined the plankton community composition and measured primary production, respiration rates and carbon export (defined here as carbon sinking out of a shallow, coastal area) during an ocean acidification experiment. Mesocosms (~ 55 m3) were set up in the Baltic Sea with a gradient of CO2 levels initially ranging from ambient (~ 240 µatm), used as control, to high CO2 (up to ~ 1330 µatm). The phytoplankton community was dominated by dinoflagellates, diatoms, cyanobacteria and chlorophytes, and the zooplankton community by protozoans, heterotrophic dinoflagellates and cladocerans. The plankton community composition was relatively homogenous between treatments. Community respiration rates were lower at high CO2 levels. The carbon-normalized respiration was approximately 40 % lower in the high CO2 environment compared with the controls during the latter phase of the experiment. We did not, however, detect any effect of increased CO2 on primary production. This could be due to measurement uncertainty, as the measured total particular carbon (TPC) and combined results presented in this special issue suggest that the reduced respiration rate translated into higher net carbon fixation. The percent carbon derived from microscopy counts (both phyto- and zooplankton), of the measured total particular carbon (TPC) decreased from ~ 26 % at t0 to ~ 8 % at t31, probably driven by a shift towards smaller plankton (< 4 µm) not enumerated by microscopy. Our results suggest that reduced respiration lead to increased net carbon fixation at high CO2. However, the increased primary production did not translate into increased carbon export, and did consequently not work as a negative feedback mechanism for increasing atmospheric CO2 concentration.

Avaliação da incerteza de medição no Setor Médico-hospitalar

This study aims to evaluate the uncertainty associated with measurements made by aneroid sphygmomanometer, neonatal electronic balance and electrocautery. Therefore, were performing repeatability tests on all devices for the subsequent execution of normality tests using Shapiro-Wilk; identification of influencing factors that affect the measurement result of each measurement; proposition of mathematical models to calculate the measurement uncertainty associated with measuring evaluated for all equipament and calibration for neonatal electronic balance; evaluation of the measurement uncertainty; and development of a computer program in Java language to systematize the calibration uncertainty of estimates and measurement uncertainty. It was proposed and carried out 23 factorial design for aneroid sphygmomanometer order to investigate the effect of temperature factors, patient and operator and another 32 planning for electrocautery, where it investigated the effects of temperature factors and output electrical power. The expanded uncertainty associated with the measurement of blood pressure significantly reduced the extent of the patient classification tracks. In turn, the expanded uncertainty associated with the mass measurement with neonatal balance indicated a variation of about 1% in the dosage of medication to neonates. Analysis of variance (ANOVA) and the Turkey test indicated significant and indirectly proportional effects of temperature factor in cutting power values and clotting indicated by electrocautery and no significant effect of factors investigated for aneroid sphygmomanometer.

Experimental and analytical investigation of refrigerant and lubricant migration

The off-cycle refrigerant mass migration has a direct influence on the on-cycle performance since compressor energy is necessary to redistribute the refrigerant mass. No studies, as of today, are available in the open literature which experimentally measured the lubricant migration within a refrigeration system during cycling or stop/start transients. Therefore, experimental procedures measuring the refrigerant and lubricant migration through the major components of a refrigeration system during stop/start transients were developed and implemented. Results identifying the underlying physics are presented. The refrigerant and lubricant migration of an R134a automotive A/C system-utilizing a fixed orifice tube, minichannel condenser, plate and fin evaporator, U-tube type accumulator and fixed displacement compressor-was measured across five sections divided by ball valves. Using the Quick-Closing Valve Technique (QCVT) combined with the Remove and Weigh Technique (RWT) using liquid nitrogen as the condensing agent resulted in a measurement uncertainty of 0.4 percent regarding the total refrigerant mass in the system. The determination of the lubricant mass distribution was achieved by employing three different techniques-Remove and Weigh, Mix and Sample, and Flushing. To employ the Mix and Sample Technique a device-called the Mix and Sample Device-was built. A method to separate the refrigerant and lubricant was developed with an accuracy-after separation-of 0.04 grams of refrigerant left in the lubricant. When applying the three techniques, the total amount of lubricant mass in the system was determined to within two percent. The combination of measurement results-infrared photography and high speed and real time videography-provide unprecedented insight into the mechanisms of refrigerant and lubricant migration during stop-start operation. During the compressor stop period, the primary refrigerant mass migration is caused by, and follows, the diminishing pressure difference across the expansion device. The secondary refrigerant migration is caused by a pressure gradient as a result of thermal nonequilibrium within the system and causes only vapor phase refrigerant migration. Lubricant migration is proportional to the refrigerant mass during the primary refrigerant mass migration. During the secondary refrigerant mass migration lubricant is not migrating. The start-up refrigerant mass migration is caused by an imbalance of the refrigerant mass flow rates across the compressor and expansion device. The higher compressor refrigerant mass flow rate was a result of the entrainment of foam into the U-tube of the accumulator. The lubricant mass migration during the start-up was not proportional to the refrigerant mass migration. The presence of water condensate on the evaporator affected the refrigerant mass migration during the compressor stop period. Caused by an evaporative cooling effect the evaporator held 56 percent of the total refrigerant mass in the system after three minutes of compressor stop time-compared to 25 percent when no water condensate was present on the evaporator coil. Foam entrainment led to a faster lubricant and refrigerant mass migration out of the accumulator than liquid entrainment through the hole at the bottom of the U-tube. The latter was observed for when water condensate was present on the evaporator coil because-as a result of the higher amount of refrigerant mass in the evaporator before start-up-the entrainment of foam into the U-tube of the accumulator ceased before the steady state refrigerant mass distribution was reached.

Optimal Budget-Constrained Sample Allocation for Selection Decisions with Multiple Uncertain Attributes

A decision-maker, when faced with a limited and fixed budget to collect data in support of a multiple attribute selection decision, must decide how many samples to observe from each alternative and attribute. This allocation decision is of particular importance when the information gained leads to uncertain estimates of the attribute values as with sample data collected from observations such as measurements, experimental evaluations, or simulation runs. For example, when the U.S. Department of Homeland Security must decide upon a radiation detection system to acquire, a number of performance attributes are of interest and must be measured in order to characterize each of the considered systems. We identified and evaluated several approaches to incorporate the uncertainty in the attribute value estimates into a normative model for a multiple attribute selection decision. Assuming an additive multiple attribute value model, we demonstrated the idea of propagating the attribute value uncertainty and describing the decision values for each alternative as probability distributions. These distributions were used to select an alternative. With the goal of maximizing the probability of correct selection we developed and evaluated, under several different sets of assumptions, procedures to allocate the fixed experimental budget across the multiple attributes and alternatives. Through a series of simulation studies, we compared the performance of these allocation procedures to the simple, but common, allocation procedure that distributed the sample budget equally across the alternatives and attributes. We found the allocation procedures that were developed based on the inclusion of decision-maker knowledge, such as knowledge of the decision model, outperformed those that neglected such information. Beginning with general knowledge of the attribute values provided by Bayesian prior distributions, and updating this knowledge with each observed sample, the sequential allocation procedure performed particularly well. These observations demonstrate that managing projects focused on a selection decision so that the decision modeling and the experimental planning are done jointly, rather than in isolation, can improve the overall selection results.

Desenvolvimento de método para determinação de resíduos de sedativos e B-bloqueadores em rim por LC-MS/MS

O desenvolvimento de métodos adequados que permitam o monitoramento de resíduos e contaminantes em alimentos é de suma importância pois é a única forma de garantir a segurança dos alimentos evitando danos à saúde do consumidor. Para isso, fazse necessário que estes métodos sejam rápidos, fáceis e de baixo custo, capazes de detectar a presença de resíduos em concentrações baixas e em diferentes matrizes. Este trabalho consistiu no desenvolvimento de método para determinação de 5 sedativos e 14 β-bloqueadores em amostras de rim suíno e posterior análise por Cromatografia Líquida Acoplada à Espectrometria de Massas em Série (LC-MS/MS). O procedimento de extração que melhor se adequou para análise destes compostos consistiu na pesagem de 2 g de amostra e adição de 10 mL de acetonitrila seguida de homogeneização com auxílio de Ultra-Turrax e mesa agitadora. Após extração, as amostras foram submetidas a duas técnicas de clean-up, sendo elas, congelamento do extrato à baixa temperatura e extração em fase sólida dispersiva (d-SPE) utilizando como sorvente Celite® 545. Uma etapa de concentração foi realizada com auxílio de concentrador de amostras sob fluxo de N2 e temperatura controlada. As amostras secas foram retomadas com metanol e analisadas utilizando sistema LC-MS/MS com Ionização por Eletrospray (ESI), operando no modo MRM positivo, coluna Poroshell 120 EC-C18 (3,0 x 50 mm, 2,7 μm) para separação dos analitos, e gradiente de fase móvel composta por (A) solução aquosa acidificada com 0,1% de ácido fórmico (v/v) e (B) metanol 0,1% ácido fórmico (v/v). Os parâmetros de validação avaliados foram linearidade, seletividade, efeito matriz, precisão, veracidade, recuperação, limite de decisão, capacidade de detecção, incerteza da medição, robustez, limite de detecção e de quantificação. Além disso foram observados os critérios de desempenho aplicáveis à detecção por espectrometria de massas e estabilidade dos compostos. A recuperação foi avaliada em 10 μg kg-1 e a veracidade em 5, 10 e 15 μg kg-1 apresentando resultados satisfatórios entre 70 - 85% e 90 - 101%, respectivamente. O limite de quantificação determinado foi de 2,5 μg kg-1 , exceto para carazolol que foi de 1,25 μg kg- 1 . O estudo de linearidade foi realizado entre 0 e 20 μg kg-1 apresentando coeficientes de determinação superiores a 0,98. Estes procedimentos foram realizados através de análise de matriz branca fortificada. Além disso, o presente método foi utilizado para analisar carazolol, azaperone e azaperol em amostras de ensaio colaborativo de rim suíno, apresentando resultados muito próximos aos reais. Portanto, é possível concluir que o método desenvolvido é adequado para análise de sedativos e β-bloqueadores através de extração dos compostos e limpeza do extrato eficientes utilizando procedimentos rápidos, fáceis e de baixo custo, garantindo resultados seguros e confiáveis.