LC-MS based methods for phytosterols determination in oenological matrices. Targeted metabolomic study of Rioja grape varieties

221 p.+ anexos

Species compositions of elasmobranchs caught by three different commercial fishing methods off southwestern Australia, and biological data for four abundant bycatch species

Commercial catches taken in southwestern Australian waters by trawl fisheries targeting prawns and scallops and from gillnet and longline fisheries targeting sharks were sampled at different times of the year between 2002 and 2008. This sampling yielded 33 elasmobranch species representing 17 families. Multivariate statistics elucidated the ways in which the species compositions of elasmobranchs differed among fishing methods and provided benchmark data for detecting changes in the elasmobranch fauna in the future. Virtually all elasmobranchs caught by trawling, which consisted predominantly of rays, were discarded as bycatch, as were approximately a quarter of the elasmobranchs caught by both gillnetting and longlining. The maximum lengths and the lengths at maturity of four abundant bycatch species, Heterodontus portusjacksoni, Aptychotrema vincentiana, Squatina australis, and Myliobatis australis, were greater for females than males. The L50 determined for the males of these species at maturity by using full clasper calcification as the criterion of maturity did not differ significantly from the corresponding L50 derived by using gonadal data as the criterion for maturity. The proportions of the individuals of these species with lengths less than those at which 50% reach maturity were far greater in trawl samples than in gillnet and longline samples. This result was due to differences in gear selectivity and to trawling being undertaken in shallow inshore waters that act as nursery areas for these species. Sound quantitative data on the species compositions of elasmobranchs caught by commercial fisheries and the biological characteristics of the main elasmobranch bycatch species are crucial for developing strategies for conserving these important species and thus the marine ecosystems of which they are part.

Assessing trends in the density of Atlantic croaker (Micropogonias undulatus): a comparison of passive acoustic and trawl methods

Using data collected simultaneously from a trawl and a hydrophone, we found that temporal and spatial trends in densities of juvenile Atlantic croaker (Micropogonias undulatus) in the Neuse River estuary in North Carolina can be identified by monitoring their sound production. Multivariate analysis of covariance (MA NCOVA) revealed that catch per unit of effort (CPUE) of Atlantic croaker had a significant relationship with the dependent variables of sound level and peak frequency of Atlantic croaker calls. Tests of between-subject correspondence failed to detect relationships between CPUE and either of the call parameters, but statistical power was low. Williamson’s index of spatial overlap indicated that call detection rate (expressed by a 0–3 calling index) was correlated in time and space with Atlantic croaker CPUE. The correspondence between acoustic parameters and trawl catch rates varied by month and by habitat. In general, the calling index had a higher degree of overlap with this species’ density than did the received sound level of their calls. Classification and regression tree analysis identified calling index as the strongest correlate of CPUE. Passive acoustics has the potential to be an inexpensive means of identifying spatial and temporal trends in abundance for soniferous fish species.

Stable multivariate rational interpolation for parameter-dependent aerospace models

A multivariate, robust, rational interpolation method for propagating uncertainties in several dimensions is presented. The algorithm for selecting numerator and denominator polynomial orders is based on recent work that uses a singular value decomposition approach. In this paper we extend this algorithm to higher dimensions and demonstrate its efficacy in terms of convergence and accuracy, both as a method for response suface generation and interpolation. To obtain stable approximants for continuous functions, we use an L2 error norm indicator to rank optimal numerator and denominator solutions. For discontinous functions, a second criterion setting an upper limit on the approximant value is employed. Analytical examples demonstrate that, for the same stencil, rational methods can yield more rapid convergence compared to pseudospectral or collocation approaches for certain problems. © 2012 AIAA.

Multivariate optimization in micellar electrokinetic capillary chromatography

The optimization of the organic modifier concentration in micellar electrokinetic capillary chromatography (MECC) has been achieved by a uniform design and iterative optimization method, which has been developed for the optimization of composition of the mobile phase in high performance liquid chromatography. According to the proposed method, the uniform design technique has been applied to design the starting experiments, which can reduce the number of experiments compared with traditional simultaneous methods, such as the orthano design. The hierarchical chromatographic response function has been modified to evaluate the separation quality of a chromatogram in MECC. An iterative procedure has been adopted to search the optimal concentration of organic modifiers for improving the accuracy of retention predicted and the quality of the chromatogram. Validity of the optimization method has been proved by the separation of 31 aromatic compounds in MECC. (C) 2000 John Wiley & Sons, Inc.

MULTIVARIATE CLASSIFICATION BASED ON METAL CONTENTS IN HUMAN SENILE CATARACT LENSES

Multivariate classification methods were used to evaluate data on the concentrations of eight metals in human senile lenses measured by atomic absorption spectrometry. Principal components analysis and hierarchical clustering separated senile cataract lenses, nuclei from cataract lenses, and normal lenses into three classes on the basis of the eight elements. Stepwise discriminant analysis was applied to give discriminant functions with five selected variables. Results provided by the linear learning machine method were also satisfactory; the k-nearest neighbour method was less useful.

On classical and other methods of discriminant analysis and estimation of log-odds

For two multinormal populations with equal covariance matrices the likelihood ratio discriminant function, an alternative allocation rule to the sample linear discriminant function when n1 ≠ n2 ,is studied analytically. With the assumption of a known covariance matrix its distribution is derived and the expectation of its actual and apparent error rates evaluated and compared with those of the sample linear discriminant function. This comparison indicates that the likelihood ratio allocation rule is robust to unequal sample sizes. The quadratic discriminant function is studied, its distribution reviewed and evaluation of its probabilities of misclassification discussed. For known covariance matrices the distribution of the sample quadratic discriminant function is derived. When the known covariance matrices are proportional exact expressions for the expectation of its actual and apparent error rates are obtained and evaluated. The effectiveness of the sample linear discriminant function for this case is also considered. Estimation of true log-odds for two multinormal populations with equal or unequal covariance matrices is studied. The estimative, Bayesian predictive and a kernel method are compared by evaluating their biases and mean square errors. Some algebraic expressions for these quantities are derived. With equal covariance matrices the predictive method is preferable. Where it derives this superiority is investigated by considering its performance for various levels of fixed true log-odds. It is also shown that the predictive method is sensitive to n1 ≠ n2. For unequal but proportional covariance matrices the unbiased estimative method is preferred. Product Normal kernel density estimates are used to give a kernel estimator of true log-odds. The effect of correlation in the variables with product kernels is considered. With equal covariance matrices the kernel and parametric estimators are compared by simulation. For moderately correlated variables and large dimension sizes the product kernel method is a good estimator of true log-odds.

Local examination of skin diffusion using FTIR spectroscopic imaging and multivariate target factor analysis

In the context of trans-dermal drug delivery it is very important to have mechanistic insight into the barrier function of the skin's stratum corneum and the diffusion mechanisms of topically applied drugs. Currently spectroscopic imaging techniques are evolving which enable a spatial examination of various types of samples in a dynamic way. ATR-FTIR imaging opens up the possibility to monitor spatial diffusion profiles across the stratum corneum of a skin sample. Multivariate data analyses methods based on factor analysis are able to provide insight into the large amount of spectroscopically complex and highly overlapping signals generated. Multivariate target factor analysis was used for spectral resolution and local diffusion profiles with time through stratum corneum. A model drug, 4-cyanophenol in polyethylene glycol 600 and water was studied. Results indicate that the average diffusion profiles between spatially different locations show similar profiles despite the heterogeneous nature of the biological sample and the challenging experimental set-up.

Assessing marine plankton community structure from long-term monitoring data with multivariate autoregressive (MAR) models: a comparison of fixed station versus spatially distributed sampling data

We examined how marine plankton interaction networks, as inferred by multivariate autoregressive (MAR) analysis of time-series, differ based on data collected at a fixed sampling location (L4 station in the Western English Channel) and four similar time-series prepared by averaging Continuous Plankton Recorder (CPR) datapoints in the region surrounding the fixed station. None of the plankton community structures suggested by the MAR models generated from the CPR datasets were well correlated with the MAR model for L4, but of the four CPR models, the one most closely resembling the L4 model was that for the CPR region nearest to L4. We infer that observation error and spatial variation in plankton community dynamics influenced the model performance for the CPR datasets. A modified MAR framework in which observation error and spatial variation are explicitly incorporated could allow the analysis to better handle the diverse time-series data collected in marine environments.

Statistical Monitoring of Dynamic Multivariate Processes: Part II: Identifying Fault Magnitude and Signature

This paper builds on work presented in the first paper, Part 1 [1] and is of equal significance. The paper proposes a novel compensation method to preserve the integrity of step-fault signatures prevalent in various processes that can be masked during the removal of both auto- and cross correlation. Using industrial data, the paper demonstrates the benefit of the proposed method, which is applicable to chemical, electrical, and mechanical process monitoring. This paper, (and Part 1 [1]), has led to further work supported by EPSRC grant GR/S84354/01 involving kernel PCA methods.

The impact of biomarkers in multivariate algorithms for bladder cancer diagnosis in patients with hematuria

BACKGROUND: We appraised 23 biomarkers previously associated with urothelial cancer in a case-control study. Our aim was to determine whether single biomarkers and/or multivariate algorithms significantly improved on the predictive power of an algorithm based on demographics for prediction of urothelial cancer in patients presenting with hematuria. METHODS: Twenty-two biomarkers in urine and carcinoembryonic antigen (CEA) in serum were evaluated using enzyme-linked immunosorbent assays (ELISAs) and biochip array technology in 2 patient cohorts: 80 patients with urothelial cancer, and 77 controls with confounding pathologies. We used Forward Wald binary logistic regression analyses to create algorithms based on demographic variables designated prior predicted probability (PPP) and multivariate algorithms, which included PPP as a single variable. Areas under the curve (AUC) were determined after receiver-operator characteristic (ROC) analysis for single biomarkers and algorithms. RESULTS: After univariate analysis, 9 biomarkers were differentially expressed (t test; P

Optimizing the balance between false positive and false negative error probabilities of confirmatory methods for the detection of veterinary drug residues

GC-MS data on veterinary drug residues in bovine urine are used for controlling the illegal practice of fattening cattle. According to current detection criteria, peak patterns of preferably four ions should agree within 10 or 20% from a corresponding standard pattern. These criteria are rigid, rather arbitrary and do not match daily practice. A new model, based on multivariate modeling of log peak abundance ratios, provides a theoretical basis for the identification of analytes and optimizes the balance between the avoidance of false positives and false negatives. The performance of the model is demonstrated on data provided by five laboratories, each supplying GC-MS measurements on the detection of clenbuterol, dienestrol and 19 beta-nortestosterone in urine. The proposed model shows a better performance than confirmation by using the current criteria and provides a statistical basis for inspection criteria in terms of error probabilities.

Do obesity and sleep problems cluster in the workplace?:A multivariate, multilevel study

OBJECTIVES: The aim of this study was to examine the co-occurrence of obesity and sleep problems among employees and workplaces. METHODS: We obtained data from 39 873 men and women working in 3040 workplaces in 2000-2002 (the Finnish Public Sector Study). Individual- and workplace-level characteristics were considered as correlates of obesity and sleep problems, which were modelled simultaneously using a multivariate, multilevel approach. RESULTS: Of the participants, 11% were obese and 23% reported sleep problems. We found a correlation between obesity and sleep problems at both the individual [correlation coefficient 0.048, covariance 0.047, standard error (SE) 0.005) and workplace (correlation coefficient 0.619, covariance 0.068, SE 0.011) level. The latter, but not the former, correlation remained after adjustment for individual- and workplace-level confounders, such as age, sex, socioeconomic status, shift work, alcohol consumption, job strain, and proportion of temporary employees and manual workers at the workplace. CONCLUSIONS: Obese employees and those with sleep problems tend to cluster in the same workplaces, suggesting that, in addition to targeting individuals at risk, interventions to reduce obesity and sleep problems might benefit from identifying "risky" workplaces.

An Examination of Transformation Techniques to Investigate and Interpret Multivariate Geochemical Data Analysis: Tellus Case Study

This research aims to use the multivariate geochemical dataset, generated by the Tellus project, to investigate the appropriate use of transformation methods to maintain the integrity of geochemical data and inherent constrained behaviour in multivariate relationships. The widely used normal score transform is compared with the use of a stepwise conditional transform technique. The Tellus Project, managed by GSNI and funded by the Department of Enterprise Trade and Development and the EU’s Building Sustainable Prosperity Fund, involves the most comprehensive geological mapping project ever undertaken in Northern Ireland. Previous study has demonstrated spatial variability in the Tellus data but geostatistical analysis and interpretation of the datasets requires use of an appropriate methodology that reproduces the inherently complex multivariate relations. Previous investigation of the Tellus geochemical data has included use of Gaussian-based techniques. However, earth science variables are rarely Gaussian, hence transformation of data is integral to the approach. The multivariate geochemical dataset generated by the Tellus project provides an opportunity to investigate the appropriate use of transformation methods, as required for Gaussian-based geostatistical analysis. In particular, the stepwise conditional transform is investigated and developed for the geochemical datasets obtained as part of the Tellus project. The transform is applied to four variables in a bivariate nested fashion due to the limited availability of data. Simulation of these transformed variables is then carried out, along with a corresponding back transformation to original units. Results show that the stepwise transform is successful in reproducing both univariate statistics and the complex bivariate relations exhibited by the data. Greater fidelity to multivariate relationships will improve uncertainty models, which are required for consequent geological, environmental and economic inferences.