IMPROVED SAMPLE INTRODUCTION SYSTEMS FOR INDUCTIVELY COUPLED PLASMA OPTICAL EMISSION SPECTROMETRY AND THEIR APPLICATION TO THE ANALYSIS OF SIMPLE AND COMPLEX MATRICES

The objective of this thesis is to explore new and improved methods for greater sample introduction efficiency and enhanced analytical performance with inductively coupled plasma optical emission spectrometry (ICP-OES). Three projects are discussed in which the capabilities and applications of ICP-OES are expanded: 1. In the first project, a conventional ultrasonic nebuliser was modified to replace the heater/condenser with an infrared heated pre-evaporation tube. In continuation from previous works with pre-evaporation, the current work investigated the effects of heating with infrared block and rope heaters on two different ICP-OES instruments. Comparisons were made between several methods and setups in which temperatures were varied. By monitoring changes to sensitivity, detection limit, precision, and robustness, and analyzing two certified reference materials, a method with improved sample introduction efficiency and comparable analytical performance to a previous method was established. 2. The second project involved improvements to a previous work in which a multimode sample introduction system (MSIS) was modified by inserting a pre-evaporation tube between the MSIS and torch. The new work focused on applying an infrared heated ceramic rope for pre-evaporation. This research was conducted in all three MSIS modes (nebulisation mode, hydride generation mode, and dual mode) and on two different ICP-OES instruments, and comparisons were made between conventional setups in terms of sensitivity, detection limit, precision, and robustness. By tracking both hydride-forming and non-hydride forming elements, the effects of heating in combination with hydride generation were probed. Finally, optimal methods were validated by analysis of two certified reference materials. 3. A final project was completed in collaboration with ZincNyx Energy Solutions. This project sought to develop a method for the overall analysis of a 12 M KOH zincate fuel, which is used in green energy backup systems. By employing various techniques including flow injection analysis and standard additions, a final procedure was formulated for the verification of K concentration, as well as the measurement of additives (Al, Fe, Mg, In, Si), corrosion products (such C from CO₃²¯), and Zn particles both in and filtered from solution. Furthermore, the effects of exposing the potassium zincate electrolyte fuel to air were assessed.

Baran: an interaction-centred user monitoring framework

User Quality of Experience (QoE) is a subjective entity and difficult to measure. One important aspect of it, User Experience (UX), corresponds to the sensory and emotional state of a user. For a user interacting through a User Interface (UI), precise information on how they are using the UI can contribute to understanding their UX, and thereby understanding their QoE. As well as a user’s use of the UI such as clicking, scrolling, touching, or selecting, other real-time digital information about the user such as from smart phone sensors (e.g. accelerometer, light level) and physiological sensors (e.g. heart rate, ECG, EEG) could contribute to understanding UX. Baran is a framework that is designed to capture, record, manage and analyse the User Digital Imprint (UDI) which, is the data structure containing all user context information. Baran simplifies the process of collecting experimental information in Human and Computer Interaction (HCI) studies, by recording comprehensive real-time data for any UI experiment, and making the data available as a standard UDI data structure. This paper presents an overview of the Baran framework, and provides an example of its use to record user interaction and perform some basic analysis of the interaction.

User interaction monitoring and analysis framework

An overview is given of a user interaction monitoring and analysis framework called BaranC. Monitoring and analysing human-digital interaction is an essential part of developing a user model as the basis for investigating user experience. The primary human-digital interaction, such as on a laptop or smartphone, is best understood and modelled in the wider context of the user and their environment. The BaranC framework provides monitoring and analysis capabilities that not only records all user interaction with a digital device (e.g. smartphone), but also collects all available context data (such as from sensors in the digital device itself, a fitness band or a smart appliances). The data collected by BaranC is recorded as a User Digital Imprint (UDI) which is, in effect, the user model and provides the basis for data analysis. BaranC provides functionality that is useful for user experience studies, user interface design evaluation, and providing user assistance services. An important concern for personal data is privacy, and the framework gives the user full control over the monitoring, storing and sharing of their data.

Tourism and arctic observation systems : Exploring the relationships

The Arctic is affected by global environmental change and also by diverse interests from many economic sectors and industries. Over the last decade, various actors have attempted to explore the options for setting up integrated and comprehensive trans-boundary systems for monitoring and observing these impacts. These Arctic Observation Systems (AOS) contribute to the planning, implementation, monitoring and evaluation of environmental change and responsible social and economic development in the Arctic. The aim of this article is to identify the two-way relationship between AOS and tourism. On the one hand, tourism activities account for diverse changes across a broad spectrum of impact fields. On the other hand, due to its multiple and diverse agents and far-reaching activities, tourism is also well-positioned to collect observational data and participate as an actor in monitoring activities. To accomplish our goals, we provide an inventory of tourism-embedded issues and concerns of interest to AOS from a range of destinations in the circumpolar Arctic region, including Alaska, Arctic Canada, Iceland, Svalbard, the mainland European Arctic and Russia. The article also draws comparisons with the situation in Antarctica. On the basis of a collective analysis provided by members of the International Polar Tourism Research Network from across the polar regions, we conclude that the potential role for tourism in the development and implementation of AOS is significant and has been overlooked.

Multi-Scale Governance of Sustainable Natural Resource Use—Challenges and Opportunities for Monitoring and Institutional Development at the National and Global Level

In a globalized economy, the use of natural resources is determined by the demand of modern production and consumption systems, and by infrastructure development. Sustainable natural resource use will require good governance and management based on sound scientific information, data and indicators. There is a rich literature on natural resource management, yet the national and global scale and macro-economic policy making has been underrepresented. We provide an overview of the scholarly literature on multi-scale governance of natural resources, focusing on the information required by relevant actors from local to global scale. Global natural resource use is largely determined by national, regional, and local policies. We observe that in recent decades, the development of public policies of natural resource use has been fostered by an “inspiration cycle” between the research, policy and statistics community, fostering social learning. Effective natural resource policies require adequate monitoring tools, in particular indicators for the use of materials, energy, land, and water as well as waste and GHG emissions of national economies. We summarize the state-of-the-art of the application of accounting methods and data sources for national material flow accounts and indicators, including territorial and product-life-cycle based approaches. We show how accounts on natural resource use can inform the Sustainable Development Goals (SDGs) and argue that information on natural resource use, and in particular footprint indicators, will be indispensable for a consistent implementation of the SDGs. We recognize that improving the knowledge base for global natural resource use will require further institutional development including at national and international levels, for which we outline options.

Above ground biomass estimation in Mediterranean multiple use systems with high spatial resolution satellite images

Forest biomass has been having an increasing importance in the world economy and in the evaluation of the forests development and monitoring. It was identified as a global strategic reserve, due to its applications in bioenergy, bioproduct development and issues related to reducing greenhouse gas emissions. The estimation of above ground biomass is frequently done with allometric functions per species with plot inventory data. An adequate sampling design and intensity for an error threshold is required. The estimation per unit area is done using an extrapolation method. This procedure is labour demanding and costly. The mail goal of this study is the development of allometric functions for the estimation of above ground biomass with ground cover as independent variable, for forest areas of holm aok (Quercus rotundifolia), cork oak (Quercus suber) and umbrella pine (Pinus pinea) in multiple use systems. Ground cover per species was derived from crown horizontal projection obtained by processing high resolution satellite images, orthorectified, geometrically and atmospheric corrected, with multi-resolution segmentation method and object oriented classification. Forest inventory data were used to estimate plot above ground biomass with published allometric functions at tree level. The developed functions were fitted for monospecies stands and for multispecies stands of Quercus rotundifolia and Quercus suber, and Quercus suber and Pinus pinea. The stand composition was considered adding dummy variables to distinguish monospecies from multispecies stands. The models showed a good performance. Noteworthy is that the dummy variables, reflecting the differences between species, originated improvements in the models. Significant differences were found for above ground biomass estimation with the functions with and without the dummy variables. An error threshold of 10% corresponds to stand areas of about 40 ha. This method enables the overall area evaluation, not requiring extrapolation procedures, for the three species, which occur frequently in multispecies stands.

Above ground biomass functions with vegetation indices for multiple use systems of two evergreen oaks

Remote sensing is a promising approach for above ground biomass estimation, as forest parameters can be obtained indirectly. The analysis in space and time is quite straight forward due to the flexibility of the method to determine forest crown parameters with remote sensing. It can be used to evaluate and monitoring for example the development of a forest area in time and the impact of disturbances, such as silvicultural practices or deforestation. The vegetation indices, which condense data in a quantitative numeric manner, have been used to estimate several forest parameters, such as the volume, basal area and above ground biomass. The objective of this study was the development of allometric functions to estimate above ground biomass using vegetation indices as independent variables. The vegetation indices used were the Normalized Difference Vegetation Index (NDVI), Enhanced Vegetation Index (EVI), Simple Ratio (SR) and Soil-Adjusted Vegetation Index (SAVI). QuickBird satellite data, with 0.70 m of spatial resolution, was orthorectified, geometrically and atmospheric corrected, and the digital number were converted to top of atmosphere reflectance (ToA). Forest inventory data and published allometric functions at tree level were used to estimate above ground biomass per plot. Linear functions were fitted for the monospecies and multispecies stands of two evergreen oaks (Quercus suber and Quercus rotundifolia) in multiple use systems, montados. The allometric above ground biomass functions were fitted considering the mean and the median of each vegetation index per grid as independent variable. Species composition as a dummy variable was also considered as an independent variable. The linear functions with better performance are those with mean NDVI or mean SR as independent variable. Noteworthy is that the two better functions for monospecies cork oak stands have median NDVI or median SR as independent variable. When species composition dummy variables are included in the function (with stepwise regression) the best model has median NDVI as independent variable. The vegetation indices with the worse model performance were EVI and SAVI.

Monitoring pasture variability: optical OptRx® crop sensor versus Grassmaster II capacitance probe

Estimation of pasture productivity is an important step for the farmer in terms of planning animal stocking, organizing animal lots, and determining supplementary feeding needs throughout the year. The main objective of this work was to evaluate technologies which have potential for monitoring aspects related to spatial and temporal variability of pasture green and dry matter yield (respectively, GM and DM, in kg/ha) and support to decision making for the farmer. Two types of sensors were evaluated: an active optical sensor(OptRx®, which measures the NDVI, Normalized Difference Vegetation Index) and a capacitance probe (GrassMaster II which estimates plant mass). The results showed the potential of NDVI for monitoring the evolution of spatial and temporal patterns of vegetative growth of biodiverse pasture. Higher NDVI values were registered as pasture approached its greatest vegetative vigor, with a significant fall in the measured NDVI at the end of Spring, when the pasture began to dry due to the combination of higher temperatures and lower soil moisture content. This index was also effective for identifying different plant species (grasses/legumes) and variability in pasture yield. Furthermore, it was possible to develop calibration equations between the capacitance and the NDVI (R2 = 0.757; p < 0.01), between capacitance and GM (R2 = 0.799; p<0.01), between capacitance and DM (R2 = 0.630; p<0.01), between NDVI and GM (R2=0.745; p < 0.01), and between capacitance and DM (R2=0.524; p<0.01). Finally, a direct relationship was obtained between NDVI and pasture moisture content (PMC, in %) and between capacitance and PMC (respectively, R2 = 0.615; p<0.01 and R2=0.561; p <0.01) in Alentejo dryland farming systems.

Effect of trees in the soil nutrient concentration and pasture produtivity in Mediterranean silvo-pastoral systems

Silvo-pastoral are mixed systems of trees and grass, which have been proposed as a means to extend the benefits of forest to farmed land. Agro-forestry systems under semi-arid Mediterranean conditions, called montados in Portugal and dehesas in Spain, cover substantial areas in the world. These silvo-pastoral systems are the most extensive European agro-forestry system, as they cover 3.5–4.0 Mha in Spain and Portugal. Long-term studies are essential to assess the magnitude of the temporal nutrient flow dynamics in terrestrial ecosystems and to understand the response of these systems to fertilizer management. In order to implement the conservation task and recovery of resources through silvo-pastoral systems it is necessary to know and correct potential limiting factors, especially the soil factor, and this requires agronomic knowledge as well as the implmentation of the available new technologies. In this context, this task aims at a better understanding of the contribution of the two components of montado ecosystem (trees and herbaceous vegetation) on the soil nutrient and water dynamics, that allow for the interpretation of the variability of pasture dry matter yield and help the farmer in the management of tree density. Collaterally the task will evaluate and calibrate new technologies that simplify the monitoring of soil, grassland, trees and grazing animals.

Evaluation of DUALEM, OptRx and Grassmaster II sensors for monitoring the spatial variability and the temporal stability of a Mediterranean pasture

Site-specific management (SSM) is a form of precision agriculture whereby decisions on resource application and agronomic practices are improved to better match soil and crop requirements as they vary in the field. SSM enables the identification of regions (homogeneous management zones) within the area delimited by field boundaries. These subfield regions constitute areas that have similar permanent characteristics. Traditional soil and pasture sampling and the necessary laboratory analysis are time-consuming, labour-intensive and cost prohibitive, not viable from a SSM perspective because it needs a large number of soil and pasture samples in order to achieve a good representation of soil properties, nutrient levels and pasture quality and productivity. The main objective of this work was to evaluate technologies which have potential for monitoring aspects related to spatial and temporal variability of soil nutrients and pasture green and dry matter yield (respectively, GM and DM, in kg/ha) and support to decision making for the farmer. Three types of sensors were evaluated in a 7ha pasture experimental field: an electromagnetic induction sensor (“DUALEM 1S”, which measures the soil apparent electrical conductivity, ECa), an active optical sensor ("OptRx®", which measures the NDVI, “Normalized Difference Vegetation Index”) and a capacitance probe ("GrassMaster II" which estimates plant mass). The results indicate the possibility of using a soil electrical conductivity probe as, probably, the best tool for monitoring not only some of the characteristics of the soil, but also those of the pasture, which could represent an important help in simplifying the process of sampling and support SSM decision making, in precision agriculture projects. On the other hand, the significant and very strong correlations obtained between capacitance and NDVI and between any of these parameters and the pasture productivity shows the potential of these tools for monitoring the evolution of spatial and temporal patterns of the vegetative growth of biodiverse pasture, for identifying different plant species and variability in pasture yield in Alentejo dry-land farming systems. These results are relevant for the selection of an adequate sensing system for a particular application and open new perspectives for other works that would allow the testing, calibration and validation of the sensors in a wider range of pasture production conditions, namely the extraordinary diversity of botanical species that are characteristic of the Mediterranean region at the different periods of the year.

Comparison of multitemporal MODIS-EVI smoothing algorithms and its contribution to crop monitoring.

Crop monitoring and more generally land use change detection are of primary importance in order to analyze spatio-temporal dynamics and its impacts on environment. This aspect is especially true in such a region as the State of Mato Grosso (south of the Brazilian Amazon Basin) which hosts an intensive pioneer front. Deforestation in this region as often been explained by soybean expansion in the last three decades. Remote sensing techniques may now represent an efficient and objective manner to quantify how crops expansion really represents a factor of deforestation through crop mapping studies. Due to the special characteristics of the soybean productions' farms in Mato Grosso (area varying between 1000 hectares and 40000 hectares and individual fields often bigger than 100 hectares), the Moderate Resolution Imaging Spectroradiometer (MODIS) data with a near daily temporal resolution and 250 m spatial resolution can be considered as adequate resources to crop mapping. Especially, multitemporal vegetation indices (VI) studies have been currently used to realize this task [1] [2]. In this study, 16-days compositions of EVI (MODQ13 product) data are used. However, although these data are already processed, multitemporal VI profiles still remain noisy due to cloudiness (which is extremely frequent in a tropical region such as south Amazon Basin), sensor problems, errors in atmospheric corrections or BRDF effect. Thus, many works tried to develop algorithms that could smooth the multitemporal VI profiles in order to improve further classification. The goal of this study is to compare and test different smoothing algorithms in order to select the one which satisfies better to the demand which is classifying crop classes. Those classes correspond to 6 different agricultural managements observed in Mato Grosso through an intensive field work which resulted in mapping more than 1000 individual fields. The agricultural managements above mentioned are based on combination of soy, cotton, corn, millet and sorghum crops sowed in single or double crop systems. Due to the difficulty in separating certain classes because of too similar agricultural calendars, the classification will be reduced to 3 classes : Cotton (single crop), Soy and cotton (double crop), soy (single or double crop with corn, millet or sorghum). The classification will use training data obtained in the 2005-2006 harvest and then be tested on the 2006-2007 harvest. In a first step, four smoothing techniques are presented and criticized. Those techniques are Best Index Slope Extraction (BISE) [3], Mean Value Iteration (MVI) [4], Weighted Least Squares (WLS) [5] and Savitzky-Golay Filter (SG) [6] [7]. These techniques are then implemented and visually compared on a few individual pixels so that it allows doing a first selection between the five studied techniques. The WLS and SG techniques are selected according to criteria proposed by [8]. Those criteria are: ability in eliminating frequent noises, conserving the upper values of the VI profiles and keeping the temporality of the profiles. Those selected algorithms are then programmed and applied to the MODIS/TERRA EVI data (16-days composition periods). Tests of separability are realized based on the Jeffries-Matusita distance in order to see if the algorithms managed in improving the potential of differentiation between the classes. Those tests are realized on the overall profile (comprising 23 MODIS images) as well as on each MODIS sub-period of the profile [1]. This last test is a double interest process because it allows comparing the smoothing techniques and also enables to select a set of images which carries more information on the separability between the classes. Those selected dates can then be used to realize a supervised classification. Here three different classifiers are tested to evaluate if the smoothing techniques as a particular effect on the classification depending on the classifiers used. Those classifiers are Maximum Likelihood classifier, Spectral Angle Mapper (SAM) classifier and CHAID Improved Decision tree. It appears through the separability tests on the overall process that the smoothed profiles don't improve efficiently the potential of discrimination between classes when compared with the original data. However, the same tests realized on the MODIS sub-periods show better results obtained with the smoothed algorithms. The results of the classification confirm this first analyze. The Kappa coefficients are always better with the smoothing techniques and the results obtained with the WLS and SG smoothed profiles are nearly equal. However, the results are different depending on the classifier used. The impact of the smoothing algorithms is much better while using the decision tree model. Indeed, it allows a gain of 0.1 in the Kappa coefficient. While using the Maximum Likelihood end SAM models, the gain remains positive but is much lower (Kappa improved of 0.02 only). Thus, this work's aim is to prove the utility in smoothing the VI profiles in order to improve the final results. However, the choice of the smoothing algorithm has to be made considering the original data used and the classifier models used. In that case the Savitzky-Golay filter gave the better results.