Comparing performance of instrumental drift correction by linear and quadratic adjusting in inductive electromagnetic data

Electromagnetic induction (EMI) method results are shown for vertical magnetic dipole (VMD) configuration by using the EM38 equipment. Performance in the location of metallic pipes and electrical cables is compared as a function of instrumental drift correction by linear and quadratic adjusting under controlled conditions. Metallic pipes and electrical cables are buried at the IAG/USP shallow geophysical test site in Sao Paulo City. Brazil. Results show that apparent electrical conductivity and magnetic susceptibility data were affected by ambient temperature variation. In order to obtain better contrast between background and metallic targets it was necessary to correct the drift. This correction was accomplished by using linear and quadratic relation between conductivity/susceptibility and temperature intending comparative studies. The correction of temperature drift by using a quadratic relation was effective, showing that all metallic targets were located as well deeper targets were also improved. (C) 2010 Elsevier B.V. All rights reserved.

Application of thermal ion-molecule reactions in tackling spectroscopic inferences in inductively coupled plasma mass spectrometry

Part I: Ultra-trace determination of vanadium in lake sediments: a performance comparison using O2, N20, and NH3 as reaction gases in ICP-DRC-MS Thermal ion-molecule reactions, targeting removal of specific spectroscopic interference problems, have become a powerful tool for method development in quadrupole based inductively coupled plasma mass spectrometry (ICP-MS) applications. A study was conducted to develop an accurate method for the determination of vanadium in lake sediment samples by ICP-MS, coupled with a dynamic reaction cell (DRC), using two differenvchemical resolution strategies: a) direct removal of interfering C10+ and b) vanadium oxidation to VO+. The performance of three reaction gases that are suitable for handling vanadium interference in the dynamic reaction cell was systematically studied and evaluated: ammonia for C10+ removal and oxygen and nitrous oxide for oxidation. Although it was able to produce comparable results for vanadium to those using oxygen and nitrous oxide, NH3 did not completely eliminate a matrix effect, caused by the presence of chloride, and required large scale dilutions (and a concomitant increase in variance) when the sample and/or the digestion medium contained large amounts of chloride. Among the three candidate reaction gases at their optimized Eonditions, creation of VO+ with oxygen gas delivered the best analyte sensitivity and the lowest detection limit (2.7 ng L-1). Vanadium results obtained from fourteen lake sediment samples and a certified reference material (CRM031-040-1), using two different analytelinterference separation strategies, suggested that the vanadium mono-oxidation offers advantageous performance over the conventional method using NH3 for ultra-trace vanadium determination by ICP-DRC-MS and can be readily employed in relevant environmental chemistry applications that deal with ultra-trace contaminants.Part II: Validation of a modified oxidation approach for the quantification of total arsenic and selenium in complex environmental matrices Spectroscopic interference problems of arsenic and selenium in ICP-MS practices were investigated in detail. Preliminary literature review suggested that oxygen could serve as an effective candidate reaction gas for analysis of the two elements in dynamic reaction cell coupled ICP-MS. An accurate method was developed for the determination of As and Se in complex environmental samples, based on a series of modifications on an oxidation approach for As and Se previously reported. Rhodium was used as internal standard in this study to help minimize non-spectral interferences such as instrumental drift. Using an oxygen gas flow slightly higher than 0.5 mL min-I, arsenic is converted to 75 AS160+ ion in an efficient manner whereas a potentially interfering ion, 91Zr+, is completely removed. Instead of using the most abundant Se isotope, 80Se, selenium was determined by a second most abundant isotope, 78Se, in the form of 78Se160. Upon careful selection of oxygen gas flow rate and optimization ofRPq value, previous isobaric threats caused by Zr and Mo were reduced to background levels whereas another potential atomic isobar, 96Ru+, became completely harmless to the new selenium analyte. The new method underwent a strict validation procedure where the recovery of a suitable certified reference material was examined and the obtained sample data were compared with those produced by a credible external laboratory who analyzed the same set of samples using a standardized HG-ICP-AES method. The validation results were satisfactory. The resultant limits of detection for arsenic and selenium were 5 ng L-1 and 60 ng L-1, respectively.

Environmental regulation, technology adoption and structural transformation: evidence from Brazilian sugarcane industry

We estimate the effects of the adoption of mechanized agriculture led by a new environmental regulation on structural change of local labor markets within a large emerging country, Brazil. In 2002, the state of S\~{a}o Paulo passed a law outlying the timeline to end sugarcane pre-harvest burning in the state. The environmental law led to the fast adoption of mechanized harvest. We investigate if the labor intensity of sugarcane production decreases; and, if so, if it leads to structural changes in the labor market. We use satellite data containing the type of sugarcane harvesting -- manual or mechanic harvest -- paired with official labor market data.%, also geomorphometric data base for our instrumental variable correction. We find suggestive evidence that mechanization of the field led to an increase in utilization of formal workers and a reduction in formal labor intensity in the sugarcane sector. This is partially compensated by an increase in the share of workers in other agricultural crops and in the construction and services sector. Although we find a reduction in employment in the manufacturing sector, the demand generated by the new agro-industries affected positively the all sectors via an increase in workers' wage.

Comparison of homeopathic globules prepared from high and ultra-high dilutions of various starting materials by ultraviolet light spectroscopy

Objective Homeopathic globules are commonly used in clinical practice, while research focuses on liquid potencies. Sequential dilution and succussion in their production process has been proposed to change the physico-chemical properties of the solvent(s). It has been reported that aqueous potencies of various starting materials showed significant differences in ultraviolet light transmission compared to controls and between different dilution levels. The aim of the present study was to repeat and expand these experiments to homeopathic globules. Methods Globules were specially produced for this study by Spagyros AG (Gümligen, Switzerland) from 6 starting materials (Aconitum napellus, Atropa belladonna, phosphorus, sulfur, Apis mellifica, quartz) and for 6 dilution levels (6x, 12x, 30c, 200c, 200CF (centesimal discontinuous fluxion), 10,000CF). Native globules and globules impregnated with solvents were used as controls. Globules were dissolved in ultrapure water, and absorbance in the ultraviolet range was measured. The average absorbance from 200 to 340 nm was calculated and corrected for differences between measurement days and instrumental drift. Results Statistically significant differences were found for A. napellus, sulfur, and A. mellifica when normalized average absorbance of the various dilution levels from the same starting material (including control and solvent control globules) was compared. Additionally, absorbance within dilution levels was compared among the various starting materials. Statistically significant differences were found among 30c, 200c and 200CF dilutions. Conclusion This study has expanded previous findings from aqueous potencies to globules and may indicate that characteristics of aqueous high dilutions may be preserved and detectable in dissolved globules.

Pressure, tilt, temperature and conductivity monitoring within the Immerged Santorini Caldera during Jul 2012 - Sep 2013

Bottom pressure, tilt and seawater physical-properties were monitored for a year using two instruments within the immerged Santorini caldera (Greece). Piggy-backed on the CALDERA2012 cruise, this geodetic experiment was designed to monitor evolution of the 2011-2012 Santorini unrest. Conducted during a quiescent period, it allowed us to study oceanographic and atmospheric signal in our data series. We observe periodic oceanographic signals associated with tides, and seiches that are likely linked to both the caldera and Cretan basin geometries. In winter, the caldera witnesses sudden cooling events that tilt an instrument towards the Southeast, indicating cold-water influx likely originating from the north-western passage between Thirasia and Oia. We do not obtain evidence of long-term vertical seafloor deformation from the pressure signal, although it may be masked by instrumental drift. However, tilt data suggests a local seafloor tilt event ~1 year after the end of the unrest period which could be consistent with inflation under or near Nea Kameni. Seafloor geodetic data recorded at the bottom of the Santorini caldera illustrates that the oceanographic signature is an important part of the signal, which needs to be considered for monitoring volcanic or geological seafloor deformation in shallow-water and/or nearshore areas.

Ocean acidification alters the material properties of Mytilus edulis shells

Ocean acidification (OA) and the resultant changing carbonate saturation states is threatening the formation of calcium carbonate shells and exoskeletons of marine organisms. The production of biominerals in such organisms relies on the availability of carbonate and the ability of the organism to biomineralize in changing environments. To understand how biomineralizers will respond to OA the common blue mussel, Mytilus edulis, was cultured at projected levels of pCO2 (380, 550, 750, 1000 µatm) and increased temperatures (ambient, ambient plus 2°C). Nanoindentation (a single mussel shell) and microhardness testing were used to assess the material properties of the shells. Young's modulus (E), hardness (H) and toughness (KIC) were measured in mussel shells grown in multiple stressor conditions. OA caused mussels to produce shell calcite that is stiffer (higher modulus of elasticity) and harder than shells grown in control conditions. The outer shell (calcite) is more brittle in OA conditions while the inner shell (aragonite) is softer and less stiff in shells grown under OA conditions. Combining increasing ocean pCO2 and temperatures as projected for future global ocean appears to reduce the impact of increasing pCO2 on the material properties of the mussel shell. OA may cause changes in shell material properties that could prove problematic under predation scenarios for the mussels; however, this may be partially mitigated by increasing temperature.

PDR with a foot-mounted IMU and ramp detection

The localization of persons in indoor environments is nowadays an open problem. There are partial solutions based on the deployment of a network of sensors (Local Positioning Systems or LPS). Other solutions only require the installation of an inertial sensor on the person’s body (Pedestrian Dead-Reckoning or PDR). PDR solutions integrate the signals coming from an Inertial Measurement Unit (IMU), which usually contains 3 accelerometers and 3 gyroscopes. The main problem of PDR is the accumulation of positioning errors due to the drift caused by the noise in the sensors. This paper presents a PDR solution that incorporates a drift correction method based on detecting the access ramps usually found in buildings. The ramp correction method is implemented over a PDR framework that uses an Inertial Navigation algorithm (INS) and an IMU attached to the person’s foot. Unlike other approaches that use external sensors to correct the drift error, we only use one IMU on the foot. To detect a ramp, the slope of the terrain on which the user is walking, and the change in height sensed when moving forward, are estimated from the IMU. After detection, the ramp is checked for association with one of the existing in a database. For each associated ramp, a position correction is fed into the Kalman Filter in order to refine the INS-PDR solution. Drift-free localization is achieved with positioning errors below 2 meters for 1,000-meter-long routes in a building with a few ramps.

A novel near real-time quality-control procedure for radiometric profiles measured by Bio-Argo floats: protocols and performances

An array of Bio-Argo floats equipped with radiometric sensors has been recently deployed in various open ocean areas representative of the diversity of trophic and bio-optical conditions prevailing in the so-called Case 1 waters. Around solar noon and almost everyday, each float acquires 0-250 m vertical profiles of Photosynthetically Available Radiation and downward irradiance at three wavelengths (380, 412 and 490 nm). Up until now, more than 6500 profiles for each radiometric channel have been acquired. As these radiometric data are collected out of operator’s control and regardless of meteorological conditions, specific and automatic data processing protocols have to be developed. Here, we present a data quality-control procedure aimed at verifying profile shapes and providing near real-time data distribution. This procedure is specifically developed to: 1) identify main issues of measurements (i.e. dark signal, atmospheric clouds, spikes and wave-focusing occurrences); 2) validate the final data with a hierarchy of tests to ensure a scientific utilization. The procedure, adapted to each of the four radiometric channels, is designed to flag each profile in a way compliant with the data management procedure used by the Argo program. Main perturbations in the light field are identified by the new protocols with good performances over the whole dataset. This highlights its potential applicability at the global scale. Finally, the comparison with modeled surface irradiances allows assessing the accuracy of quality-controlled measured irradiance values and identifying any possible evolution over the float lifetime due to biofouling and instrumental drift.

A novel near real-time quality-control procedure for radiometric profiles measured by Bio-Argo floats: protocols and performances

An array of Bio-Argo floats equipped with radiometric sensors has been recently deployed in various open ocean areas representative of the diversity of trophic and bio-optical conditions prevailing in the so-called Case 1 waters. Around solar noon and almost everyday, each float acquires 0-250 m vertical profiles of Photosynthetically Available Radiation and downward irradiance at three wavelengths (380, 412 and 490 nm). Up until now, more than 6500 profiles for each radiometric channel have been acquired. As these radiometric data are collected out of operator’s control and regardless of meteorological conditions, specific and automatic data processing protocols have to be developed. Here, we present a data quality-control procedure aimed at verifying profile shapes and providing near real-time data distribution. This procedure is specifically developed to: 1) identify main issues of measurements (i.e. dark signal, atmospheric clouds, spikes and wave-focusing occurrences); 2) validate the final data with a hierarchy of tests to ensure a scientific utilization. The procedure, adapted to each of the four radiometric channels, is designed to flag each profile in a way compliant with the data management procedure used by the Argo program. Main perturbations in the light field are identified by the new protocols with good performances over the whole dataset. This highlights its potential applicability at the global scale. Finally, the comparison with modeled surface irradiances allows assessing the accuracy of quality-controlled measured irradiance values and identifying any possible evolution over the float lifetime due to biofouling and instrumental drift.

Drift compensation of gas sensor array data by Orthogonal Signal Correction

Drift is an important issue that impairs the reliability of gas sensing systems. Sensor aging, memory effects and environmental disturbances produce shifts in sensor responses that make initial statistical models for gas or odor recognition useless after a relatively short period (typically few weeks). Frequent recalibrations are needed to preserve system accuracy. However, when recalibrations involve numerous samples they become expensive and laborious. An interesting and lower cost alternative is drift counteraction by signal processing techniques. Orthogonal Signal Correction (OSC) is proposed for drift compensation in chemical sensor arrays. The performance of OSC is also compared with Component Correction (CC). A simple classification algorithm has been employed for assessing the performance of the algorithms on a dataset composed by measurements of three analytes using an array of seventeen conductive polymer gas sensors over a ten month period.

Gas identification with tin oxide sensor array and self-organizing maps: adaptive correction of sensor drifts

Low-cost tin oxide gas sensors are inherently nonspecific. In addition, they have several undesirable characteristics such as slow response, nonlinearities, and long-term drifts. This paper shows that the combination of a gas-sensor array together with self-organizing maps (SOM's) permit success in gas classification problems. The system is able to determine the gas present in an atmosphere with error rates lower than 3%. Correction of the sensor's drift with an adaptive SOM has also been investigated

Experiential learning instruments : an examination of the concept of the instrumental approach in experiential learning

Experiential Learning Instruments (ELls) are employed to modify the leamer's apprehension and / or comprehension in experiential learning situations, thereby improving the efficiency and effectiveness of those modalities in the learning process. They involve the learner in reciprocally interactive and determining transactions with his/her environment. Experiential Learning Instruments are used to keep experiential learning a process rather than an object. Their use is aimed at the continual refinement of the learner's knowledge and skill. Learning happens as the leamer's awareness, directed by the use of Ells, comes to experience, monitor and then use experiential feedback from living situations in a way that facilitates knmvledge/skill acquisition, self-correction and refinement. The thesis examined the literature relevant to the establishing of a theoretical experiential learning framework within which ELls can be understood. This framework included the concept that some learnings have intrinsic value-knowledge of necessary information-while others have instrumental value-knowledge of how to learn. The Kolb Learning Cycle and Kolb's six characteristics of experiential learning were used in analyzing three ELls from different fields of learning-saxophone tone production, body building and interpersonal communications. The ELls were examined to determine their learning objectives and how they work using experiential learning situations. It was noted that ELls do not transmit information but assist the learner in attending to and comprehending aspects of personal experience. Their function is to telescope the experiential learning process.

TIMS measurements of full range of natural Ca isotopes with internally consistent fractionation correction

This study presents static measurements of the Ca isotopic composition of standard reference materials SRM 915 a/b on a Triton Plus™ thermal ionization mass spectrometer with a specially developed Faraday cup array allowing simultaneous measurement of 40Ca and 48Ca. The total amount of Ca in all analyses was kept < 1 µg. With this setup the measurement uncertainties were 0.06 ‰ for 40Ca/44Ca and 0.12 ‰ for 48Ca/40Ca. Measuring all isotopes simultaneously better allows to test the internal consistency of different Ca isotope abundances reported in the literature. The exponential law was observed to correct incompletely instrumental mass fractionation. An improved fractionation correction based on the exponential law is proposed. It changes the 40Ca/44Ca ratio of SRM 915a (corrected relative to 42Ca/44Ca = 0.31221; 48Ca/44Ca = 0.08871) from 47.1635 ± 0.0028 to 47.1649 ± 0.0047. The measurements of SRM 915b were performed with different analytical conditions (runs were prolonged till complete filament load depletion). Even if the 40Ca/44Ca ratio of SRM 915b, when corrected with the simple exponential law, appears different (47.1532 ± 0.0038) from that of SRM 915a, it becomes coincident (47.1613 ± 0.0028) when corrected with a second-order refinement. This supports the use of the improved exponential law to obtain internally consistent Ca isotope ratio for natural samples.

A comparison between multi-proxy and historical data of drift-ice conditions on the East Greenland shelf

The reduction in sea ice along the SE Greenland coast during the last century has severely impacted ice-rafting to this area. In order to reconstruct ice-rafting and oceanographic conditions in the area of Denmark Strait during the last ~150 years, we conducted a multiproxy study on three short (20 cm) sediment cores from outer Kangerdlugssuaq Trough (~300 m water depth). The proxy-based data obtained have been compared with historical and instrumental data to gain a better understanding of the ice sheet-ocean interactions in the area. A robust chronology has been developed based on 210Pb and 137Cs measurements on core PO175GKC#9 (~66.2°N, 32°W) and expanded to the two adjacent cores based on correlations between calcite weight percent records. Our proxy records include sea-ice and phytoplankton biomarkers, and a variety of mineralogical determinations based on the <2 mm sediment fraction, including identification with quantitative x-ray diffraction, ice-rafted debris counts on the 63-150 µm sand fraction, and source identifications based on the composition of Fe oxides in the 45-250 µm fraction. A multivariate statistical analysis indicated significant correlations between our proxy records and historical data, especially with the mean annual temperature data from Stykkishólmur (Iceland) and the storis index (historical observations of sea-ice export via the East Greenland Current). In particular, the biological proxies (calcite weight percent, IP25, and total organic carbon %) showed significant linkage with the storis index. Our records show two distinct intervals in the recent history of the SE Greenland coast. The first of these (ad 1850-1910) shows predominantly perennial sea-ice conditions in the area, while the second (ad 1910-1990) shows more seasonally open water conditions.

Evaluación y análisis de la trazabilidad metrológica en redes para la verificación y calibración de instrumental GNSS (Global Navigation Satellite System)

Los estudios realizados hasta el momento para la determinación de la calidad de medida del instrumental geodésico han estado dirigidos, fundamentalmente, a las medidas angulares y de distancias. Sin embargo, en los últimos años se ha impuesto la tendencia generalizada de utilizar equipos GNSS (Global Navigation Satellite System) en el campo de las aplicaciones geomáticas sin que se haya establecido una metodología que permita obtener la corrección de calibración y su incertidumbre para estos equipos. La finalidad de esta Tesis es establecer los requisitos que debe satisfacer una red para ser considerada Red Patrón con trazabilidad metrológica, así como la metodología para la verificación y calibración de instrumental GNSS en redes patrón. Para ello, se ha diseñado y elaborado un procedimiento técnico de calibración de equipos GNSS en el que se han definido las contribuciones a la incertidumbre de medida. El procedimiento, que se ha aplicado en diferentes redes para distintos equipos, ha permitido obtener la incertidumbre expandida de dichos equipos siguiendo las recomendaciones de la Guide to the Expression of Uncertainty in Measurement del Joint Committee for Guides in Metrology. Asimismo, se han determinado mediante técnicas de observación por satélite las coordenadas tridimensionales de las bases que conforman las redes consideradas en la investigación, y se han desarrollado simulaciones en función de diversos valores de las desviaciones típicas experimentales de los puntos fijos que se han utilizado en el ajuste mínimo cuadrático de los vectores o líneas base. Los resultados obtenidos han puesto de manifiesto la importancia que tiene el conocimiento de las desviaciones típicas experimentales en el cálculo de incertidumbres de las coordenadas tridimensionales de las bases. Basándose en estudios y observaciones de gran calidad técnica, llevados a cabo en estas redes con anterioridad, se ha realizado un exhaustivo análisis que ha permitido determinar las condiciones que debe satisfacer una red patrón. Además, se han diseñado procedimientos técnicos de calibración que permiten calcular la incertidumbre expandida de medida de los instrumentos geodésicos que proporcionan ángulos y distancias obtenidas por métodos electromagnéticos, ya que dichos instrumentos son los que van a permitir la diseminación de la trazabilidad metrológica a las redes patrón para la verificación y calibración de los equipos GNSS. De este modo, ha sido posible la determinación de las correcciones de calibración local de equipos GNSS de alta exactitud en las redes patrón. En esta Tesis se ha obtenido la incertidumbre de la corrección de calibración mediante dos metodologías diferentes; en la primera se ha aplicado la propagación de incertidumbres, mientras que en la segunda se ha aplicado el método de Monte Carlo de simulación de variables aleatorias. El análisis de los resultados obtenidos confirma la validez de ambas metodologías para la determinación de la incertidumbre de calibración de instrumental GNSS. ABSTRACT The studies carried out so far for the determination of the quality of measurement of geodetic instruments have been aimed, primarily, to measure angles and distances. However, in recent years it has been accepted to use GNSS (Global Navigation Satellite System) equipment in the field of Geomatic applications, for data capture, without establishing a methodology that allows obtaining the calibration correction and its uncertainty. The purpose of this Thesis is to establish the requirements that a network must meet to be considered a StandardNetwork with metrological traceability, as well as the methodology for the verification and calibration of GNSS instrumental in those standard networks. To do this, a technical calibration procedure has been designed, developed and defined for GNSS equipment determining the contributions to the uncertainty of measurement. The procedure, which has been applied in different networks for different equipment, has alloweddetermining the expanded uncertainty of such equipment following the recommendations of the Guide to the Expression of Uncertainty in Measurement of the Joint Committee for Guides in Metrology. In addition, the three-dimensional coordinates of the bases which constitute the networks considered in the investigationhave been determined by satellite-based techniques. There have been several developed simulations based on different values of experimental standard deviations of the fixed points that have been used in the least squares vectors or base lines calculations. The results have shown the importance that the knowledge of experimental standard deviations has in the calculation of uncertainties of the three-dimensional coordinates of the bases. Based on high technical quality studies and observations carried out in these networks previously, it has been possible to make an exhaustive analysis that has allowed determining the requirements that a standard network must meet. In addition, technical calibration procedures have been developed to allow the uncertainty estimation of measurement carried outby geodetic instruments that provide angles and distances obtained by electromagnetic methods. These instruments provide the metrological traceability to standard networks used for verification and calibration of GNSS equipment. As a result, it has been possible the estimation of local calibration corrections for high accuracy GNSS equipment in standardnetworks. In this Thesis, the uncertainty of calibration correction has been calculated using two different methodologies: the first one by applying the law of propagation of uncertainty, while the second has applied the propagation of distributions using the Monte Carlo method. The analysis of the obtained results confirms the validity of both methodologies for estimating the calibration uncertainty of GNSS equipment.