Development of error correction techniques for nitrate-N load estimation models

Excess nutrient loads carried by streams and rivers are a great concern for environmental resource managers. In agricultural regions, excess loads are transported downstream to receiving water bodies, potentially causing algal blooms, which could lead to numerous ecological problems. To better understand nutrient load transport, and to develop appropriate water management plans, it is important to have accurate estimates of annual nutrient loads. This study used a Monte Carlo sub-sampling method and error-corrected statistical models to estimate annual nitrate-N loads from two watersheds in central Illinois. The performance of three load estimation methods (the seven-parameter log-linear model, the ratio estimator, and the flow-weighted averaging estimator) applied at one-, two-, four-, six-, and eight-week sampling frequencies were compared. Five error correction techniques; the existing composite method, and four new error correction techniques developed in this study; were applied to each combination of sampling frequency and load estimation method. On average, the most accurate error reduction technique, (proportional rectangular) resulted in 15% and 30% more accurate load estimates when compared to the most accurate uncorrected load estimation method (ratio estimator) for the two watersheds. Using error correction methods, it is possible to design more cost-effective monitoring plans by achieving the same load estimation accuracy with fewer observations. Finally, the optimum combinations of monitoring threshold and sampling frequency that minimizes the number of samples required to achieve specified levels of accuracy in load estimation were determined. For one- to three-weeks sampling frequencies, combined threshold/fixed-interval monitoring approaches produced the best outcomes, while fixed-interval-only approaches produced the most accurate results for four- to eight-weeks sampling frequencies.

Discontinuous Galerkin Methods for Advection-Diffusion-Reaction Problems on Anisotropically Refined Meshes

In this paper we consider the a posteriori and a priori error analysis of discontinuous Galerkin interior penalty methods for second-order partial differential equations with nonnegative characteristic form on anisotropically refined computational meshes. In particular, we discuss the question of error estimation for linear target functionals, such as the outflow flux and the local average of the solution. Based on our a posteriori error bound we design and implement the corresponding adaptive algorithm to ensure reliable and efficient control of the error in the prescribed functional to within a given tolerance. This involves exploiting both local isotropic and anisotropic mesh refinement. The theoretical results are illustrated by a series of numerical experiments.

Discontinuous Galerkin Methods for the Biharmonic Problem

This work is concerned with the design and analysis of hp-version discontinuous Galerkin (DG) finite element methods for boundary-value problems involving the biharmonic operator. The first part extends the unified approach of Arnold, Brezzi, Cockburn & Marini (SIAM J. Numer. Anal. 39, 5 (2001/02), 1749-1779) developed for the Poisson problem, to the design of DG methods via an appropriate choice of numerical flux functions for fourth order problems; as an example we retrieve the interior penalty DG method developed by Suli & Mozolevski (Comput. Methods Appl. Mech. Engrg. 196, 13-16 (2007), 1851-1863). The second part of this work is concerned with a new a-priori error analysis of the hp-version interior penalty DG method, when the error is measured in terms of both the energy-norm and L2-norm, as well certain linear functionals of the solution, for elemental polynomial degrees $p\ge 2$. Also, provided that the solution is piecewise analytic in an open neighbourhood of each element, exponential convergence is also proven for the p-version of the DG method. The sharpness of the theoretical developments is illustrated by numerical experiments.

Adaptive discontinuous Galerkin methods for eigenvalue problems arising in incompressible fluid flows

In this article we consider the a posteriori error estimation and adaptive mesh refinement of discontinuous Galerkin finite element approximations of the hydrodynamic stability problem associated with the incompressible Navier-Stokes equations. Particular attention is given to the reliable error estimation of the eigenvalue problem in channel and pipe geometries. Here, computable a posteriori error bounds are derived based on employing the generalization of the standard Dual-Weighted-Residual approach, originally developed for the estimation of target functionals of the solution, to eigenvalue/stability problems. The underlying analysis consists of constructing both a dual eigenvalue problem and a dual problem for the original base solution. In this way, errors stemming from both the numerical approximation of the original nonlinear flow problem, as well as the underlying linear eigenvalue problem are correctly controlled. Numerical experiments highlighting the practical performance of the proposed a posteriori error indicator on adaptively refined computational meshes are presented.

Error estimation and adaptive mesh refinement for aerodynamic flows

This lecture course covers the theory of so-called duality-based a posteriori error estimation of DG finite element methods. In particular, we formulate consistent and adjoint consistent DG methods for the numerical approximation of both the compressible Euler and Navier-Stokes equations; in the latter case, the viscous terms are discretized based on employing an interior penalty method. By exploiting a duality argument, adjoint-based a posteriori error indicators will be established. Moreover, application of these computable bounds within automatic adaptive finite element algorithms will be developed. Here, a variety of isotropic and anisotropic adaptive strategies, as well as $hp$-mesh refinement will be investigated.

High-order hp-adaptive discontinuous Galerkin finite element methods for compressible fluid flows

This article is concerned with the construction of general isotropic and anisotropic adaptive strategies, as well as hp-mesh refinement techniques, in combination with dual-weighted-residual a posteriori error indicators for the discontinuous Galerkin finite element discretization of compressible fluid flow problems.

Modern Computational Chemistry Methods for Prediction of Ground- and Excited-State Properties in Open-Shell Systems

The main goal of the research presented in this work is to provide some important insights about computational modeling of open-shell species. Such projects are: the investigation of the size-extensivity error in Equation-of-Motion Coupled Cluster methods, the analysis of the Long-Range corrected scheme in predicting UV-Vis spectra of Cu(II) complexes with the 4-imidazole acetate and its ethylated derivative, and the exploration of the importance of choosing a proper basis set for the description of systems such as the lithium monoxide anion. The most significant findings of this research are: (i) The contribution of the left operator to the size-extensivity error of the CR-EOMCC(2,3) approach, (ii) The cause of d-d shifts when varying the range-separation parameter and the amount of the exact exchange arising from the imbalanced treatment of localized vs. delocalized orbitals via the "tuned" CAM-B3LYP* functional, (iii) The proper acidity trend of the first-row hydrides and their lithiated analogs that may be reversed if the basis sets are not correctly selected.

From the traditional verification approach to the spatial methods: a study of applicability of the SAL metric in the framework of the WMO project MesoVICT

Increasing in resolution of numerical weather prediction models has allowed more and more realistic forecasts of atmospheric parameters. Due to the growing variability into predicted fields the traditional verification methods are not always able to describe the model ability because they are based on a grid-point-by-grid-point matching between observation and prediction. Recently, new spatial verification methods have been developed with the aim of show the benefit associated to the high resolution forecast. Nested in among of the MesoVICT international project, the initially aim of this work is to compare the newly tecniques remarking advantages and disadvantages. First of all, the MesoVICT basic examples, represented by synthetic precipitation fields, have been examined. Giving an error evaluation in terms of structure, amplitude and localization of the precipitation fields, the SAL method has been studied more thoroughly respect to the others approaches with its implementation in the core cases of the project. The verification procedure has concerned precipitation fields over central Europe: comparisons between the forecasts performed by the 00z COSMO-2 model and the VERA (Vienna Enhanced Resolution Analysis) have been done. The study of these cases has shown some weaknesses of the methodology examined; in particular has been highlighted the presence of a correlation between the optimal domain size and the extention of the precipitation systems. In order to increase ability of SAL, a subdivision of the original domain in three subdomains has been done and the method has been applied again. Some limits have been found in cases in which at least one of the two domains does not show precipitation. The overall results for the subdomains have been summarized on scatter plots. With the aim to identify systematic errors of the model the variability of the three parameters has been studied for each subdomain.

Evaluation of the Evidential Value of the Elemental Composition of Glass, Ink and Paper by Laser-Based Micro-Spectrochemical Methods

Elemental analysis can become an important piece of evidence to assist the solution of a case. The work presented in this dissertation aims to evaluate the evidential value of the elemental composition of three particular matrices: ink, paper and glass. In the first part of this study, the analytical performance of LIBS and LA-ICP-MS methods was evaluated for paper, writing inks and printing inks. A total of 350 ink specimens were examined including black and blue gel inks, ballpoint inks, inkjets and toners originating from several manufacturing sources and/or batches. The paper collection set consisted of over 200 paper specimens originating from 20 different paper sources produced by 10 different plants. Micro-homogeneity studies show smaller variation of elemental compositions within a single source (i.e., sheet, pen or cartridge) than the observed variation between different sources (i.e., brands, types, batches). Significant and detectable differences in the elemental profile of the inks and paper were observed between samples originating from different sources (discrimination of 87 – 100% of samples, depending on the sample set under investigation and the method applied). These results support the use of elemental analysis, using LA-ICP-MS and LIBS, for the examination of documents and provide additional discrimination to the currently used techniques in document examination. In the second part of this study, a direct comparison between four analytical methods (µ-XRF, solution-ICP-MS, LA-ICP-MS and LIBS) was conducted for glass analyses using interlaboratory studies. The data provided by 21 participants were used to assess the performance of the analytical methods in associating glass samples from the same source and differentiating different sources, as well as the use of different match criteria (confidence interval (±6s, ±5s, ±4s, ±3s, ±2s), modified confidence interval, t-test (sequential univariate, p=0.05 and p=0.01), t-test with Bonferroni correction (for multivariate comparisons), range overlap, and Hotelling’s T2 tests. Error rates (Type 1 and Type 2) are reported for the use of each of these match criteria and depend on the heterogeneity of the glass sources, the repeatability between analytical measurements, and the number of elements that were measured. The study provided recommendations for analytical performance-based parameters for µ-XRF and LA-ICP-MS as well as the best performing match criteria for both analytical techniques, which can be applied now by forensic glass examiners.

The sensitivity of mapping methods to reference data quality:training supervised image classifications with imperfect reference data

The accuracy of a map is dependent on the reference dataset used in its construction. Classification analyses used in thematic mapping can, for example, be sensitive to a range of sampling and data quality concerns. With particular focus on the latter, the effects of reference data quality on land cover classifications from airborne thematic mapper data are explored. Variations in sampling intensity and effort are highlighted in a dataset that is widely used in mapping and modelling studies; these may need accounting for in analyses. The quality of the labelling in the reference dataset was also a key variable influencing mapping accuracy. Accuracy varied with the amount and nature of mislabelled training cases with the nature of the effects varying between classifiers. The largest impacts on accuracy occurred when mislabelling involved confusion between similar classes. Accuracy was also typically negatively related to the magnitude of mislabelled cases and the support vector machine (SVM), which has been claimed to be relatively insensitive to training data error, was the most sensitive of the set of classifiers investigated, with overall classification accuracy declining by 8% (significant at 95% level of confidence) with the use of a training set containing 20% mislabelled cases.

Autonomous formation flying: unified control and collision avoidance methods for close manoeuvring spacecraft

The idea of spacecraft formations, flying in tight configurations with maximum baselines of a few hundred meters in low-Earth orbits, has generated widespread interest over the last several years. Nevertheless, controlling the movement of spacecraft in formation poses difficulties, such as in-orbit high-computing demand and collision avoidance capabilities, which escalate as the number of units in the formation is increased and complicated nonlinear effects are imposed to the dynamics, together with uncertainty which may arise from the lack of knowledge of system parameters. These requirements have led to the need of reliable linear and nonlinear controllers in terms of relative and absolute dynamics. The objective of this thesis is, therefore, to introduce new control methods to allow spacecraft in formation, with circular/elliptical reference orbits, to efficiently execute safe autonomous manoeuvres. These controllers distinguish from the bulk of literature in that they merge guidance laws never applied before to spacecraft formation flying and collision avoidance capacities into a single control strategy. For this purpose, three control schemes are presented: linear optimal regulation, linear optimal estimation and adaptive nonlinear control. In general terms, the proposed control approaches command the dynamical performance of one or several followers with respect to a leader to asymptotically track a time-varying nominal trajectory (TVNT), while the threat of collision between the followers is reduced by repelling accelerations obtained from the collision avoidance scheme during the periods of closest proximity. Linear optimal regulation is achieved through a Riccati-based tracking controller. Within this control strategy, the controller provides guidance and tracking toward a desired TVNT, optimizing fuel consumption by Riccati procedure using a non-infinite cost function defined in terms of the desired TVNT, while repelling accelerations generated from the CAS will ensure evasive actions between the elements of the formation. The relative dynamics model, suitable for circular and eccentric low-Earth reference orbits, is based on the Tschauner and Hempel equations, and includes a control input and a nonlinear term corresponding to the CAS repelling accelerations. Linear optimal estimation is built on the forward-in-time separation principle. This controller encompasses two stages: regulation and estimation. The first stage requires the design of a full state feedback controller using the state vector reconstructed by means of the estimator. The second stage requires the design of an additional dynamical system, the estimator, to obtain the states which cannot be measured in order to approximately reconstruct the full state vector. Then, the separation principle states that an observer built for a known input can also be used to estimate the state of the system and to generate the control input. This allows the design of the observer and the feedback independently, by exploiting the advantages of linear quadratic regulator theory, in order to estimate the states of a dynamical system with model and sensor uncertainty. The relative dynamics is described with the linear system used in the previous controller, with a control input and nonlinearities entering via the repelling accelerations from the CAS during collision avoidance events. Moreover, sensor uncertainty is added to the control process by considering carrier-phase differential GPS (CDGPS) velocity measurement error. An adaptive control law capable of delivering superior closed-loop performance when compared to the certainty-equivalence (CE) adaptive controllers is finally presented. A novel noncertainty-equivalence controller based on the Immersion and Invariance paradigm for close-manoeuvring spacecraft formation flying in both circular and elliptical low-Earth reference orbits is introduced. The proposed control scheme achieves stabilization by immersing the plant dynamics into a target dynamical system (or manifold) that captures the desired dynamical behaviour. They key feature of this methodology is the addition of a new term to the classical certainty-equivalence control approach that, in conjunction with the parameter update law, is designed to achieve adaptive stabilization. This parameter has the ultimate task of shaping the manifold into which the adaptive system is immersed. The performance of the controller is proven stable via a Lyapunov-based analysis and Barbalat’s lemma. In order to evaluate the design of the controllers, test cases based on the physical and orbital features of the Prototype Research Instruments and Space Mission Technology Advancement (PRISMA) are implemented, extending the number of elements in the formation into scenarios with reconfigurations and on-orbit position switching in elliptical low-Earth reference orbits. An extensive analysis and comparison of the performance of the controllers in terms of total Δv and fuel consumption, with and without the effects of the CAS, is presented. These results show that the three proposed controllers allow the followers to asymptotically track the desired nominal trajectory and, additionally, those simulations including CAS show an effective decrease of collision risk during the performance of the manoeuvre.

Data-driven and data-oriented methods for materials science and technologies

The discovery of new materials and their functions has always been a fundamental component of technological progress. Nowadays, the quest for new materials is stronger than ever: sustainability, medicine, robotics and electronics are all key assets which depend on the ability to create specifically tailored materials. However, designing materials with desired properties is a difficult task, and the complexity of the discipline makes it difficult to identify general criteria. While scientists developed a set of best practices (often based on experience and expertise), this is still a trial-and-error process. This becomes even more complex when dealing with advanced functional materials. Their properties depend on structural and morphological features, which in turn depend on fabrication procedures and environment, and subtle alterations leads to dramatically different results. Because of this, materials modeling and design is one of the most prolific research fields. Many techniques and instruments are continuously developed to enable new possibilities, both in the experimental and computational realms. Scientists strive to enforce cutting-edge technologies in order to make progress. However, the field is strongly affected by unorganized file management, proliferation of custom data formats and storage procedures, both in experimental and computational research. Results are difficult to find, interpret and re-use, and a huge amount of time is spent interpreting and re-organizing data. This also strongly limit the application of data-driven and machine learning techniques. This work introduces possible solutions to the problems described above. Specifically, it talks about developing features for specific classes of advanced materials and use them to train machine learning models and accelerate computational predictions for molecular compounds; developing method for organizing non homogeneous materials data; automate the process of using devices simulations to train machine learning models; dealing with scattered experimental data and use them to discover new patterns.

Evaluation Of Different Treatment Methods Against Denture Stomatitis: A Randomized Clinical Study.

The aim of this clinical study was to determine the efficacy of Uncaria tomentosa (cat's claw) against denture stomatitis (DS). Fifty patients with DS were randomly assigned into 3 groups to receive 2% miconazole, placebo, or 2% U tomentosa gel. DS level was recorded immediately, after 1 week of treatment, and 1 week after treatment. The clinical effectiveness of each treatment was measured using Newton's criteria. Mycologic samples from palatal mucosa and prosthesis were obtained to determinate colony forming units per milliliter (CFU/mL) and fungal identification at each evaluation period. Candida species were identified with HiCrome Candida and API 20C AUX biochemical test. DS severity decreased in all groups (P < .05). A significant reduction in number of CFU/mL after 1 week (P < .05) was observed for all groups and remained after 14 days (P > .05). C albicans was the most prevalent microorganism before treatment, followed by C tropicalis, C glabrata, and C krusei, regardless of the group and time evaluated. U tomentosa gel had the same effect as 2% miconazole gel. U tomentosa gel is an effective topical adjuvant treatment for denture stomatitis.

Estimated Disability-adjusted Life Years Averted By Long-term Provision Of Long Acting Contraceptive Methods In A Brazilian Clinic.

What is the contribution of the provision, at no cost for users, of long acting reversible contraceptive methods (LARC; copper intrauterine device [IUD], the levonorgestrel-releasing intrauterine system [LNG-IUS], contraceptive implants and depot-medroxyprogesterone [DMPA] injection) towards the disability-adjusted life years (DALY) averted through a Brazilian university-based clinic established over 30 years ago. Over the last 10 years of evaluation, provision of LARC methods and DMPA by the clinic are estimated to have contributed to DALY averted by between 37 and 60 maternal deaths, 315-424 child mortalities, 634-853 combined maternal morbidity and mortality and child mortality, and 1056-1412 unsafe abortions averted. LARC methods are associated with a high contraceptive effectiveness when compared with contraceptive methods which need frequent attention; perhaps because LARC methods are independent of individual or couple compliance. However, in general previous studies have evaluated contraceptive methods during clinical studies over a short period of time, or not more than 10 years. Furthermore, information regarding the estimation of the DALY averted is scarce. We reviewed 50 004 medical charts from women who consulted for the first time looking for a contraceptive method over the period from 2 January 1980 through 31 December 2012. Women who consulted at the Department of Obstetrics and Gynaecology, University of Campinas, Brazil were new users and users switching contraceptive, including the copper IUD (n = 13 826), the LNG-IUS (n = 1525), implants (n = 277) and DMPA (n = 9387). Estimation of the DALY averted included maternal morbidity and mortality, child mortality and unsafe abortions averted. We obtained 29 416 contraceptive segments of use including 25 009 contraceptive segments of use from 20 821 new users or switchers to any LARC method or DMPA with at least 1 year of follow-up. The mean (± SD) age of the women at first consultation ranged from 25.3 ± 5.7 (range 12-47) years in the 1980s, to 31.9 ± 7.4 (range 16-50) years in 2010-2011. The most common contraceptive chosen at the first consultation was copper IUD (48.3, 74.5 and 64.7% in the 1980s, 1990s and 2000s, respectively). For an evaluation over 20 years, the cumulative pregnancy rates (SEM) were 0.4 (0.2), 2.8 (2.1), 4.0 (0.4) and 1.3 (0.4) for the LNG-IUS, the implants, copper IUD and DMPA, respectively and cumulative continuation rates (SEM) were 15.1 (3.7), 3.9 (1.4), 14.1 (0.6) and 7.3 (1.7) for the LNG-IUS, implants, copper IUD and DMPA, respectively (P < 0.001). Over the last 10 years of evaluation, the estimation of the contribution of the clinic through the provision of LARC methods and DMPA to DALY averted was 37-60 maternal deaths; between 315 and 424 child mortalities; combined maternal morbidity and mortality and child mortality of between 634 and 853, and 1056-1412 unsafe abortions averted. The main limitations are the number of women who never returned to the clinic (overall 14% among the four methods under evaluation); consequently the pregnancy rate could be different. Other limitations include the analysis of two kinds of copper IUD and two kinds of contraceptive implants as the same IUD or implant, and the low number of users of implants. In addition, the DALY calculation relies on a number of estimates, which may vary in different parts of the world. LARC methods and DMPA are highly effective and women who were well-counselled used these methods for a long time. The benefit of averting maternal morbidity and mortality, child mortality, and unsafe abortions is an example to health policy makers to implement more family planning programmes and to offer contraceptive methods, mainly LARC and DMPA, at no cost or at affordable cost for the underprivileged population. This study received partial financial support from the Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP), grant # 2012/12810-4 and from the National Research Council (CNPq), grant #573747/2008-3. B.F.B., M.P.G., and V.M.C. were fellows from the scientific initiation programme from FAPESP. Since the year 2001, all the TCu380A IUD were donated by Injeflex, São Paulo, Brazil, and from the year 2006 all the LNG-IUS were donated by the International Contraceptive Access Foundation (ICA), Turku, Finland. Both donations are as unrestricted grants. The authors declare that there are no conflicts of interest associated with this study.

Evaluation Of The Effect Of Different Methods Of Microabrasion And Polishing On Surface Roughness Of Dental Enamel.

The microabrasion technique of enamel consists of selectively abrading the discolored areas or causing superficial structural changes in a selective way. In microabrasion technique, abrasive products associated with acids are used, and the evaluation of enamel roughness after this treatment, as well as surface polishing, is necessary. This in-vitro study evaluated the enamel roughness after microabrasion, followed by different polishing techniques. Roughness analyses were performed before microabrasion (L1), after microabrasion (L2), and after polishing (L3).Thus, 60 bovine incisive teeth divided into two groups were selected (n=30): G1- 37% phosphoric acid (37%) (Dentsply) and pumice; G2- hydrochloric acid (6.6%) associated with silicon carbide (Opalustre - Ultradent). Thereafter, the groups were divided into three sub-groups (n=10), according to the system of polishing: A - Fine and superfine granulation aluminum oxide discs (SofLex 3M); B - Diamond Paste (FGM) associated with felt discs (FGM); C - Silicone tips (Enhance - Dentsply). A PROC MIXED procedure was applied after data exploratory analysis, as well as the Tukey-Kramer test (5%). No statistical differences were found between G1 and G2 groups. L2 differed statistically from L1 and showed superior amounts of roughness. Differences in the amounts of post-polishing roughness for specific groups (1A, 2B, and 1C) arose, which demonstrated less roughness in L3 and differed statistically from L2 in the polishing system. All products increased enamel roughness, and the effectiveness of the polishing systems was dependent upon the abrasive used.