Multivariate quality control studies applied to Ca(II) and Mg(II) determination by a portable method

A portable or field test method for simultaneous spectrophotometric determination of calcium and magnesium in water using multivariate partial least squares (PLS) calibration methods is proposed. The method is based on the reaction between the analytes and methylthymol blue at pH 11. The spectral information was used as the X-block, and the Ca(II) and Mg(II) concentrations obtained by a reference technique (ICP-AES) were used as the Y-block. Two series of analyses were performed, with a month's difference between them. The first series was used as the calibration set and the second one as the validation set. Multivariate statistical process control (MSPC) techniques, based on statistics from principal component models, were used to study the features and evolution with time of the spectral signals. Signal standardization was used to correct the deviations between series. Method validation was performed by comparing the predictions of the PLS model with the reference Ca(II) and Mg(II) concentrations determined by ICP-AES using the joint interval test for the slope and intercept of the regression line with errors in both axes. (C) 1998 John Wiley & Sons, Ltd.

Uma nova abordagem para interpretação de anomalias gravimétricas regionais e residuais aplicada ao estudo da organização crustal: exemplo da Região Norte do Piauí e Noroeste do Ceará

A interpretação de anomalias gravimétricas é de grande importância no estudo de feições geológicas que ocorrem na crosta terrestre. Esta interpretação é, no entanto, dificultada pelo fato das anomalias gravimétricas serem resultantes da soma total dos efeitos produzidos por todos os contrastes de densidades de subsuperfície. Desse modo, com o intuito de separar efeitos de feições mais profundas de efeitos de feições mais rasas, bem como a caracterização da geometria desses dois conjuntos de feições, apresentamos um método de separação das componentes regional e residual do campo e a subsequente interpretação de cada componente. A separação regional-residual de dados gravimétricos é efetuada através da aproximação do campo regional por um polinômio ajustado ao campo observado por um método robusto. Este método é iterativo e usa como aproximação inicial a solução obtida através do ajuste polinomial pelo método dos mínimos quadrados. O método empregado minimiza a influência de observações contendo forte contribuição do campo residual no ajuste do campo regional. A componente regional obtida a partir da separação regional-residual é transformada em um mapa de distâncias verticais em relação a um nível de referência. Esta transformação compreende duas etapas. A primeira consiste na obtenção da continuação para baixo da componente regional, que é pressuposta ser causada por uma interface suave separando dois meios homogêneos, representando a interface crosta-manto, cujo contraste de densidade é supostamente conhecido. A segunda consiste na transformação do mapa de continuação para baixo em um mapa de distâncias verticais entre o nível de continuação (tomado como nível de referência) e a interface. Este método apresenta duas dificuldades. A primeira está ligada à instabilidade, havendo portanto a necessidade do emprego de um estabilizador o que acarreta a perda de resolução das feições que se desejam mapear. A segunda, inerente ao método gravimétrico, consiste na impossibilidade da determinação das profundidades absolutas da interface em cada ponto, bastando entretanto o conhecimento da profundidade absoluta em um ponto, através de informação independente, para que todas as outras profundidades absolutas sejam conhecidas. A componente residual obtida a partir da separação regional-residual é transformada em um mapa de contrastes de densidade aparente. Esta transformação consiste no cálculo do contraste de densidade de várias fontes prismáticas através de uma inversão linear pressupondo que as fontes reais estejam das a uma placa horizontal, com contrastes de densidade variando apenas nas direções horizontais. O desempenho do método de separação regional-residual apresentado foi avaliado, através de testes empregando dados sintéticos, fornecendo resultados superiores em relação aos métodos dos mínimos quadrados e da análise espectral. O método de interpretação da componente regional teve seu desempenho avaliado em testes com dados sintéticos onde foram produzidos mapeamentos de interfaces bem próximas das estruturas reais. O limite de resolução das feições que se desejam mapear depende não só do grau do polinômio ajustante, como também da própria limitação inerente ao método gravimétrico. Na interpretação da componente residual é necessário que se postule ou tenha informação a priori sobre a profundidade do topo e espessura da placa onde as fontes estão supostamente confinadas. No entanto, a aplicação do método em dados sintéticos, produziu estimativas razoáveis para os limites laterais das fontes, mesmo na presença de fontes interferentes, e pressupondo-se valores para profundidade do topo e espessura da placa, diferentes dos valores verdadeiros. A ambiguidade envolvendo profundidade do topo, espessura e densidade pode ser visualizada através de gráficos de valores de densidade aparente contra profundidade do topo presumida para a placa para vários valores postulados para a espessura da placa. Estes mesmos gráficos permitem, pelo aspecto das curvas, a elaboração de uma interpretação semi-quantitativa das profundidades das fontes reais. A seqüência dos três métodos desenvolvidos neste trabalho foi aplicada a dados gravimétricos da região norte do Piauí e noroeste do Ceará levando a um modelo de organização crustal que compreende espessamentos e adelgaçamentos crustais associados a um evento compressivo que possibilitou a colocação de rochas densas da base da crosta a profundidades rasas. Este modelo ê compatível com os dados geológicos de superfície. É ainda sugerida a continuidade, por mais 200 km em direção a sudoeste, do Cinturão de Cisalhamento Noroeste do Ceará por sob os sedimentos da Bacia do Parnaíba, com base nas evidências fornecidas pela interpretação da anomalia residual. Embora esta seqüência de métodos tenha sido desenvolvida com vistas ao estudo de feições crustais de porte continental, ela também pode ser aplicada ao estudo de feições mais localizadas como por exemplo no mapeamento do relevo do embasamento de/bacias sedimentares onde os sedimentos são cortados por rochas intrusivas mais densas.

A Multivariate Calibration Procedure for UV/VIS Spectrometric Monitoring of BHK-21 Cell Metabolism and Growth

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

Direct Determination of Sugar Cane Quality Parameters by X-ray Spectrometry and Multivariate Analysis

Current methods for quality control of sugar cane are performed in extracted juice using several methodologies, often requiring appreciable time and chemicals (eventually toxic), making the methods not green and expensive. The present study proposes the use of X-ray spectrometry together with chemometric methods as an innovative and alternative technique for determining sugar cane quality parameters, specifically sucrose concentration, POL, and fiber content. Measurements in stem, leaf, and juice were performed, and those applied directly in stem provided the best results. Prediction models for sugar cane stem determinations with a single 60 s irradiation using portable X-ray fluorescence equipment allows estimating the % sucrose, % fiber, and POL simultaneously. Average relative deviations in the prediction step of around 8% are acceptable if considering that field measurements were done. These results may indicate the best period to cut a particular crop as well as for evaluating the quality of sugar cane for the sugar and alcohol industries.

Determination of chlorine in food samples via the AlCl molecule using high-resolution continuum source molecular absorption spectrometry in a graphite furnace

Determination of chlorine using the molecular absorption of aluminum mono-chloride (AlCl) at the 261.418 nm wavelength was accomplished by high-resolution continuum source molecular absorption spectrometry using a transversely heated graphite tube furnace with an integrated platform. For the analysis. 10 mu L of the sample followed by 10 mu L of a solution containing Al-Ag-Sr modifier, (1 g L-1 each), were directly injected onto the platform. A spectral interference due to the use of Al-Ag-Sr as mixed modifier was easily corrected by the least-squares algorithm present in the spectrometer software. The pyrolysis and vaporization temperatures were 500 degrees C and 2200 degrees C, respectively. To evaluate the feasibility of a simple procedure for the determination of chlorine in food samples present in our daily lives, two different digestion methods were applied, namely (A) an acid digestion method using HNO3 only at room temperature, and (B) a digestion method with Ag, HNO3 and H2O2, where chlorine is precipitated as a low-solubility salt (AgCl), which is then dissolved with ammonia solution. The experimental results obtained with method B were in good agreement with the certified values and demonstrated that the proposed method is more accurate than method A. This is because the formation of silver chloride prevented analyte losses by volatilization. The limit of detection (LOD, 3 sigma/s) for Cl in methods A and B was 18 mu g g(-1) and 9 mu g g(-1), respectively, 1.7 and 3.3 times lower compared to published work using inductively coupled plasma optical emission spectrometry, and absolute LODs were 2.4 and 1.2 ng, respectively. (C) 2012 Elsevier B.V. All rights reserved.

Biochemistry in healthy and neoplastic human tissues: metabolic alteration revealed by HR-MAS nuclear magnetic resonance spectroscopy

This thesis is focused on the metabolomic study of human cancer tissues by ex vivo High Resolution-Magic Angle Spinning (HR-MAS) nuclear magnetic resonance (NMR) spectroscopy. This new technique allows for the acquisition of spectra directly on intact tissues (biopsy or surgery), and it has become very important for integrated metabonomics studies. The objective is to identify metabolites that can be used as markers for the discrimination of the different types of cancer, for the grading, and for the assessment of the evolution of the tumour. Furthermore, an attempt to recognize metabolites, that although involved in the metabolism of tumoral tissues in low concentration, can be important modulators of neoplastic proliferation, was performed. In addition, NMR data was integrated with statistical techniques in order to obtain semi-quantitative information about the metabolite markers. In the case of gliomas, the NMR study was correlated with gene expression of neoplastic tissues. Chapter 1 begins with a general description of a new “omics” study, the metabolomics. The study of metabolism can contribute significantly to biomedical research and, ultimately, to clinical medical practice. This rapidly developing discipline involves the study of the metabolome: the total repertoire of small molecules present in cells, tissues, organs, and biological fluids. Metabolomic approaches are becoming increasingly popular in disease diagnosis and will play an important role on improving our understanding of cancer mechanism. Chapter 2 addresses in more detail the basis of NMR Spectroscopy, presenting the new HR-MAS NMR tool, that is gaining importance in the examination of tumour tissues, and in the assessment of tumour grade. Some advanced chemometric methods were used in an attempt to enhance the interpretation and quantitative information of the HR-MAS NMR data are and presented in chapter 3. Chemometric methods seem to have a high potential in the study of human diseases, as it permits the extraction of new and relevant information from spectroscopic data, allowing a better interpretation of the results. Chapter 4 reports results obtained from HR-MAS NMR analyses performed on different brain tumours: medulloblastoma, meningioms and gliomas. The medulloblastoma study is a case report of primitive neuroectodermal tumor (PNET) localised in the cerebellar region by Magnetic Resonance Imaging (MRI) in a 3-year-old child. In vivo single voxel 1H MRS shows high specificity in detecting the main metabolic alterations in the primitive cerebellar lesion; which consist of very high amounts of the choline-containing compounds and of very low levels of creatine derivatives and N-acetylaspartate. Ex vivo HR-MAS NMR, performed at 9.4 Tesla on the neoplastic specimen collected during surgery, allows the unambiguous identification of several metabolites giving a more in-depth evaluation of the metabolic pattern of the lesion. The ex vivo HR-MAS NMR spectra show higher detail than that obtained in vivo. In addition, the spectroscopic data appear to correlate with some morphological features of the medulloblastoma. The present study shows that ex vivo HR-MAS 1H NMR is able to strongly improve the clinical possibility of in vivo MRS and can be used in conjunction with in vivo spectroscopy for clinical purposes. Three histological subtypes of meningiomas (meningothelial, fibrous and oncocytic) were analysed both by in vivo and ex vivo MRS experiments. The ex vivo HR-MAS investigations are very helpful for the assignment of the in vivo resonances of human meningiomas and for the validation of the quantification procedure of in vivo MR spectra. By using one- and two dimensional experiments, several metabolites in different histological subtypes of meningiomas, were identified. The spectroscopic data confirmed the presence of the typical metabolites of these benign neoplasms and, at the same time, that meningomas with different morphological characteristics have different metabolic profiles, particularly regarding macromolecules and lipids. The profile of total choline metabolites (tCho) and the expression of the Kennedy pathway genes in biopsies of human gliomas were also investigated using HR-MAS NMR, and microfluidic genomic cards. 1H HR-MAS spectra, allowed the resolution and relative quantification by LCModel of the resonances from choline (Cho), phosphorylcholine (PC) and glycerolphorylcholine (GPC), the three main components of the combined tCho peak observed in gliomas by in vivo 1H MRS spectroscopy. All glioma biopsies depicted an increase in tCho as calculated from the addition of Cho, PC and GPC HR-MAS resonances. However, the increase was constantly derived from augmented GPC in low grade NMR gliomas or increased PC content in the high grade gliomas, respectively. This circumstance allowed the unambiguous discrimination of high and low grade gliomas by 1H HR-MAS, which could not be achieved by calculating the tCho/Cr ratio commonly used by in vivo 1H MR spectroscopy. The expression of the genes involved in choline metabolism was investigated in the same biopsies. The present findings offer a convenient procedure to classify accurately glioma grade using 1H HR-MAS, providing in addition the genetic background for the alterations of choline metabolism observed in high and low gliomas grade. Chapter 5 reports the study on human gastrointestinal tract (stomach and colon) neoplasms. The human healthy gastric mucosa, and the characteristics of the biochemical profile of human gastric adenocarcinoma in comparison with that of healthy gastric mucosa were analyzed using ex vivo HR-MAS NMR. Healthy human mucosa is mainly characterized by the presence of small metabolites (more than 50 identified) and macromolecules. The adenocarcinoma spectra were dominated by the presence of signals due to triglycerides, that are usually very low in healthy gastric mucosa. The use of spin-echo experiments enable us to detect some metabolites in the unhealthy tissues and to determine their variation with respect to the healthy ones. Then, the ex vivo HR-MAS NMR analysis was applied to human gastric tissue, to obtain information on the molecular steps involved in the gastric carcinogenesis. A microscopic investigation was also carried out in order to identify and locate the lipids in the cellular and extra-cellular environments. Correlation of the morphological changes detected by transmission (TEM) and scanning (SEM) electron microscopy, with the metabolic profile of gastric mucosa in healthy, gastric atrophy autoimmune diseases (AAG), Helicobacter pylori-related gastritis and adenocarcinoma subjects, were obtained. These ultrastructural studies of AAG and gastric adenocarcinoma revealed lipid intra- and extra-cellularly accumulation associated with a severe prenecrotic hypoxia and mitochondrial degeneration. A deep insight into the metabolic profile of human healthy and neoplastic colon tissues was gained using ex vivo HR-MAS NMR spectroscopy in combination with multivariate methods: Principal Component Analysis (PCA) and Partial Least Squares Discriminant Analysis (PLS-DA). The NMR spectra of healthy tissues highlight different metabolic profiles with respect to those of neoplastic and microscopically normal colon specimens (these last obtained at least 15 cm far from the adenocarcinoma). Furthermore, metabolic variations are detected not only for neoplastic tissues with different histological diagnosis, but also for those classified identical by histological analysis. These findings suggest that the same subclass of colon carcinoma is characterized, at a certain degree, by metabolic heterogeneity. The statistical multivariate approach applied to the NMR data is crucial in order to find metabolic markers of the neoplastic state of colon tissues, and to correctly classify the samples. Significant different levels of choline containing compounds, taurine and myoinositol, were observed. Chapter 6 deals with the metabolic profile of normal and tumoral renal human tissues obtained by ex vivo HR-MAS NMR. The spectra of human normal cortex and medulla show the presence of differently distributed osmolytes as markers of physiological renal condition. The marked decrease or disappearance of these metabolites and the high lipid content (triglycerides and cholesteryl esters) is typical of clear cell renal carcinoma (RCC), while papillary RCC is characterized by the absence of lipids and very high amounts of taurine. This research is a contribution to the biochemical classification of renal neoplastic pathologies, especially for RCCs, which can be evaluated by in vivo MRS for clinical purposes. Moreover, these data help to gain a better knowledge of the molecular processes envolved in the onset of renal carcinogenesis.

Charakterisierung von plasmafunktionalisierten Oberflächen mittels ToF-SIMS und multivariaten Analysemethoden

Die grundlegenden Prinzipien und Möglichkeiten der Oberflächencharakterisierung mittels ToF-SIMS (Flugzeit-Sekundärionen Massenspektrometrie) werden an ausgewählten Beispielen aus einem aktuell laufenden und vom BMBF geförderten Verbundforschungsprojekt (Fkz: 03N8022A) zum Thema Nanofunktionalisierung von Grenzflächen vorgestellt. Ein Schwerpunkt innerhalb des Projekts stellen die nichtgeschlossenen Schichtsysteme dar, die entweder über Domänenstrukturen oder einer definierten Einzelfunktionalisierung neuartige funktionelle Oberflächen bereitstellen. Mithilfe der sehr oberflächensensitiven ToF-SIMS Methode sowie der Möglichkeit einer graphischen Darstellung lateraler Molekülionenverteilungen auf funktionalisierten Oberflächen können Informationen über Struktur und Belegungsdichte der Funktionsschicht gewonnen werden. Die Kombination des ToF-SIMS Experimentes und eines multivariaten Algorithmus (partial least squares, PLS) liefert eine interessante Möglichkeit zur quantitativen und simultanen Bestimmung von Oberflächeneigenschaften (Element- und molekulare Konzentrationen sowie Kontaktwinkelwerte). Da das ToF-SIMS Spektrum einer plasmafunktionalisierten Oberfläche im Allgemeinen eine Vielzahl unterschiedlicher Fragmentsignale enthält, lässt eine einfache eindimensionale Korrelation (z.B. CF3 - Fragmentintensität ßà CF3-Konzentration) den größten Teil der im Spektrum prinzipiell enthaltenen Information unberücksichtigt. Aufgrund der großen Anzahl von atomaren und molekularen Signalen, die repräsentativ für die chemische Struktur der analysierten Oberflächen sind, ist es sinnvoll, diese Fülle von Informationen zur Quantifizierung der Oberflächeneigenschaften (Elementkonzentrationen, Kontaktwinkel etc.) zu verwenden. Zusätzlich ermöglicht diese Methode eine quantitative Bestimmung der Oberflächeneigenschaften auf nur µm-großen Bereichen. Das ist vorteilhaft für Untersuchungen chemisch strukturierter Oberflächen, da die Größe der Strukturierung für viele Anwendungen in einem Bereich von mehreren µm liegt. Anhand eines Beispieles aus dem biologisch-medizinischen Fachgebiet, soll der erfolgreiche Einsatz multivariater Modelle aufgezeigt werden. In diesem Experiment wurden menschlichen Bindegewebs- (Fibroblasten) und Pankreaszellen auf plasmafunktionalisiserten Oberflächen kultiviert, um die Beeinflussung der Funktionalisierung auf das Zellwachstum zu untersuchen. Die plasmabehandelten Oberflächen wurden durch die Verwendung von TEM-Gittern mit µm-großen Öffnungen chemisch strukturiert und das Wachstumsverhalten der Zellen beobachtet. Jedem dieser µm-großen Bereiche können mithilfe der multivariaten Modelle quantitative Größen zugeordnet werden (Konzentrationen und Kontaktwinkelwerte), die zur Interpretation des Wachstumsverhaltens der Zellen beitragen.

Valutazione della qualità ed autenticità di prodotti oleari e lattiero caseari mediante metodi fisici di analisi accoppiati a tecniche statistiche multivariate

Questa tesi descrive alcuni studi di messa a punto di metodi di analisi fisici accoppiati con tecniche statistiche multivariate per valutare la qualità e l’autenticità di oli vegetali e prodotti caseari. L’applicazione di strumenti fisici permette di abbattere i costi ed i tempi necessari per le analisi classiche ed allo stesso tempo può fornire un insieme diverso di informazioni che possono riguardare tanto la qualità come l’autenticità di prodotti. Per il buon funzionamento di tali metodi è necessaria la costruzione di modelli statistici robusti che utilizzino set di dati correttamente raccolti e rappresentativi del campo di applicazione. In questo lavoro di tesi sono stati analizzati oli vegetali e alcune tipologie di formaggi (in particolare pecorini per due lavori di ricerca e Parmigiano-Reggiano per un altro). Sono stati utilizzati diversi strumenti di analisi (metodi fisici), in particolare la spettroscopia, l’analisi termica differenziale, il naso elettronico, oltre a metodiche separative tradizionali. I dati ottenuti dalle analisi sono stati trattati mediante diverse tecniche statistiche, soprattutto: minimi quadrati parziali; regressione lineare multipla ed analisi discriminante lineare.

Younger Dryas and Allerød summer temperatures at Gerzensee (Switzerland) inferred from fossil pollen and cladoceran assemblages

Linear- and unimodal-based inference models for mean summer temperatures (partial least squares, weighted averaging, and weighted averaging partial least squares models) were applied to a high-resolution pollen and cladoceran stratigraphy from Gerzensee, Switzerland. The time-window of investigation included the Allerød, the Younger Dryas, and the Preboreal. Characteristic major and minor oscillations in the oxygen-isotope stratigraphy, such as the Gerzensee oscillation, the onset and end of the Younger Dryas stadial, and the Preboreal oscillation, were identified by isotope analysis of bulk-sediment carbonates of the same core and were used as independent indicators for hemispheric or global scale climatic change. In general, the pollen-inferred mean summer temperature reconstruction using all three inference models follows the oxygen-isotope curve more closely than the cladoceran curve. The cladoceran-inferred reconstruction suggests generally warmer summers than the pollen-based reconstructions, which may be an effect of terrestrial vegetation not being in equilibrium with climate due to migrational lags during the Late Glacial and early Holocene. Allerød summer temperatures range between 11 and 12°C based on pollen, whereas the cladoceran-inferred temperatures lie between 11 and 13°C. Pollen and cladocera-inferred reconstructions both suggest a drop to 9–10°C at the beginning of the Younger Dryas. Although the Allerød–Younger Dryas transition lasted 150–160 years in the oxygen-isotope stratigraphy, the pollen-inferred cooling took 180–190 years and the cladoceran-inferred cooling lasted 250–260 years. The pollen-inferred summer temperature rise to 11.5–12°C at the transition from the Younger Dryas to the Preboreal preceded the oxygen-isotope signal by several decades, whereas the cladoceran-inferred warming lagged. Major discrepancies between the pollen- and cladoceran-inference models are observed for the Preboreal, where the cladoceran-inference model suggests mean summer temperatures of up to 14–15°C. Both pollen- and cladoceran-inferred reconstructions suggest a cooling that may be related to the Gerzensee oscillation, but there is no evidence for a cooling synchronous with the Preboreal oscillation as recorded in the oxygen-isotope record. For the Gerzensee oscillation the inferred cooling was ca. 1 and 0.5°C based on pollen and cladocera, respectively, which lies well within the inherent prediction errors of the inference models.

Multivariate methods for correlated effects sizes

Current statistical methods for estimation of parametric effect sizes from a series of experiments are generally restricted to univariate comparisons of standardized mean differences between two treatments. Multivariate methods are presented for the case in which effect size is a vector of standardized multivariate mean differences and the number of treatment groups is two or more. The proposed methods employ a vector of independent sample means for each response variable that leads to a covariance structure which depends only on correlations among the $p$ responses on each subject. Using weighted least squares theory and the assumption that the observations are from normally distributed populations, multivariate hypotheses analogous to common hypotheses used for testing effect sizes were formulated and tested for treatment effects which are correlated through a common control group, through multiple response variables observed on each subject, or both conditions.^ The asymptotic multivariate distribution for correlated effect sizes is obtained by extending univariate methods for estimating effect sizes which are correlated through common control groups. The joint distribution of vectors of effect sizes (from $p$ responses on each subject) from one treatment and one control group and from several treatment groups sharing a common control group are derived. Methods are given for estimation of linear combinations of effect sizes when certain homogeneity conditions are met, and for estimation of vectors of effect sizes and confidence intervals from $p$ responses on each subject. Computational illustrations are provided using data from studies of effects of electric field exposure on small laboratory animals. ^

Paleomagnetic of lower Cretaceous sediments from the Argo and Gascoyne Abyssal Plain

Lower Cretaceous sediments were sampled for magnetostratigraphy at three sites. ODP Site 765 and DSDP Site 261, in the Argo Abyssal Plain, consist primarily of brownish-red to gray claystone having hematite and magnetite carriers of characteristic magnetization. ODP Site 766, in the Gascoyne Abyssal Plain, consists mainly of dark greenish-gray volcaniclastic turbidites with magnetite as the carrier of characteristic magnetization. Progressive thermal demagnetization (Sites 765 and 261) or alternating field demagnetization (Site 766) yielded well-defined polarity zones and a set of reliable paleolatitudes. Magnetic polarity chrons were assigned to polarity zones using biostratigraphic correlations. Late Aptian chron M"-1"r, a brief reversed-polarity chron younger than MOr, is a narrow, 40-cm feature delimited in Hole 765C. Early Aptian reversed-polarity chron MOr is also present in Hole 765C. Polarity chrons Mir through M3r were observed in the Barremian of all three sites. Valanginian and Hauterivian polarity chrons can be tentatively assigned to polarity zones only in Hole 766A. The paleolatitude of this region remained at 35° to 37°S from the Berriasian through the Aptian. During this interval, there was approximately 16° of clockwise rotation, with the oriented sample suites of Site 765 displaying a Berriasian declination of 307° to an Aptian declination of 323°. These results are consistent with the interpolated Early Cretaceous apparent polar wander for Australia, but indicate that this region was approximately 5? farther north than predicted.

Consolidation properties and permeability values of sediments from three ODP Leg 205 sites

Vertical permeability and sediment consolidation measurements were taken on seven whole-round drill cores from Sites 1253 (three samples), 1254 (one sample), and 1255 (three samples) drilled during Ocean Drilling Program Leg 205 in the Middle America Trench off of Costa Rica's Pacific Coast. Consolidation behavior including slopes of elastic rebound and virgin compression curves (Cc) was measured by constant rate of strain tests. Permeabilities were determined from flow-through experiments during stepped-load tests and by using coefficient of consolidation (Cv) values continuously while loading. Consolidation curves and the Casagrande method were used to determine maximum preconsolidation stress. Elastic slopes of consolidation curves ranged from 0.097 to 0.158 in pelagic sediments and 0.0075 to 0.018 in hemipelagic sediments. Cc values ranged from 1.225 to 1.427 for pelagic carbonates and 0.504 to 0.826 for hemipelagic clay-rich sediments. In samples consolidated to an axial stress of ~20 MPa, permeabilities determined by flow-through experiments ranged from a low value of 7.66 x 10**-20 m**2 in hemipelagic sediments to a maximum value of 1.03 x 10**-16 m**2 in pelagic sediments. Permeabilities calculated from Cv values in the hemipelagic sediments ranged from 4.81 x 10**-16 to 7.66 x 10**-20 m**2 for porosities 49.9%-26.1%.

Winter sea surface temperature reconstruction from planktic foraminiferal transfer functions in the northeastern Arabian Sea over the last two millennia

The Indian monsoon system is an important climate feature of the northern Indian Ocean. Small variations of the wind and precipitation patterns have fundamental influence on the societal, agricultural, and economic development of India and its neighboring countries. To understand current trends, sensitivity to forcing, or natural variation, records beyond the instrumental period are needed. However, high-resolution archives of past winter monsoon variability are scarce. One potential archive of such records are marine sediments deposited on the continental slope in the NE Arabian Sea, an area where present-day conditions are dominated by the winter monsoon. In this region, winter monsoon conditions lead to distinctive changes in surface water properties, affecting marine plankton communities that are deposited in the sediment. Using planktic foraminifera as a sensitive and well-preserved plankton group, we first characterize the response of their species distribution on environmental gradients from a dataset of surface sediment samples in the tropical and sub-tropical Indian Ocean. Transfer functions for quantitative paleoenvironmental reconstructions were applied to a decadal-scale record of assemblage counts from the Pakistan Margin spanning the last 2000?years. The reconstructed temperature record reveals an intensification of winter monsoon intensity near the year 100 CE. Prior to this transition, winter temperatures were >1.5°C warmer than today. Conditions similar to the present seem to have established after 450 CE, interrupted by a singular event near 950 CE with warmer temperatures and accordingly weak winter monsoon. Frequency analysis revealed significant 75-, 40-, and 37-year cycles, which are known from decadal- to centennial-scale resolution records of Indian summer monsoon variability and interpreted as solar irradiance forcing. Our first independent record of Indian winter monsoon activity confirms that winter and summer monsoons were modulated on the same frequency bands and thus indicates that both monsoon systems are likely controlled by the same driving force.

Multivariate Techniques in Biomechanical Analysis

This work outlines the theoretical advantages of multivariate methods in biomechanical data, validates the proposed methods and outlines new clinical findings relating to knee osteoarthritis that were made possible by this approach. New techniques were based on existing multivariate approaches, Partial Least Squares (PLS) and Non-negative Matrix Factorization (NMF) and validated using existing data sets. The new techniques developed, PCA-PLS-LDA (Principal Component Analysis – Partial Least Squares – Linear Discriminant Analysis), PCA-PLS-MLR (Principal Component Analysis – Partial Least Squares –Multiple Linear Regression) and Waveform Similarity (based on NMF) were developed to address the challenging characteristics of biomechanical data, variability and correlation. As a result, these new structure-seeking technique revealed new clinical findings. The first new clinical finding relates to the relationship between pain, radiographic severity and mechanics. Simultaneous analysis of pain and radiographic severity outcomes, a first in biomechanics, revealed that the knee adduction moment’s relationship to radiographic features is mediated by pain in subjects with moderate osteoarthritis. The second clinical finding was quantifying the importance of neuromuscular patterns in brace effectiveness for patients with knee osteoarthritis. I found that brace effectiveness was more related to the patient’s unbraced neuromuscular patterns than it was to mechanics, and that these neuromuscular patterns were more complicated than simply increased overall muscle activity, as previously thought.

Compositional data analysis of Holocene sediments from the West Bengal Sundarbans, India: Geochemical proxies for grain-size variability in a delta environment

This paper is part of a special issue of Applied Geochemistry focusing on reliable applications of compositional multivariate statistical methods. This study outlines the application of compositional data analysis (CoDa) to calibration of geochemical data and multivariate statistical modelling of geochemistry and grain-size data from a set of Holocene sedimentary cores from the Ganges-Brahmaputra (G-B) delta. Over the last two decades, understanding near-continuous records of sedimentary sequences has required the use of core-scanning X-ray fluorescence (XRF) spectrometry, for both terrestrial and marine sedimentary sequences. Initial XRF data are generally unusable in ‘raw-format’, requiring data processing in order to remove instrument bias, as well as informed sequence interpretation. The applicability of these conventional calibration equations to core-scanning XRF data are further limited by the constraints posed by unknown measurement geometry and specimen homogeneity, as well as matrix effects. Log-ratio based calibration schemes have been developed and applied to clastic sedimentary sequences focusing mainly on energy dispersive-XRF (ED-XRF) core-scanning. This study has applied high resolution core-scanning XRF to Holocene sedimentary sequences from the tidal-dominated Indian Sundarbans, (Ganges-Brahmaputra delta plain). The Log-Ratio Calibration Equation (LRCE) was applied to a sub-set of core-scan and conventional ED-XRF data to quantify elemental composition. This provides a robust calibration scheme using reduced major axis regression of log-ratio transformed geochemical data. Through partial least squares (PLS) modelling of geochemical and grain-size data, it is possible to derive robust proxy information for the Sundarbans depositional environment. The application of these techniques to Holocene sedimentary data offers an improved methodological framework for unravelling Holocene sedimentation patterns.