Univariate statistical techniques

Principal Component Analysis (PCA) is performed on a human monitoring data base to assess its ability to identify relationships between variables and to assess the overall quality of the data. The analysis uncovers two unusual events that led to further investigation of the data. One, unusually high levels of chlordane related compounds were observed at one specific collection site. Two, a programming error is uncovered. Both events had gone unnoticed after conventional univariate statistical techniques were applied. These results Illustrate the usefulness of PCA in the reduction of multi-dimensioned data bases to allow for the visual inspection of data in a two dimensional plot. 

Data have been collected since 1970 on the prevalence and levels of various chemicals in human adipose (fat) tissue. These data are stored on a mainframe computer and have undergone routine quality assurance/quality control checks using univariate statistical methods. Upon completion of the development of a new analysis file, multivariate statistical techniques are applied to the data. The purpose of this analysis is to determine the utility of pattern recognition techniques in assessing the quality of the data and its ability to assist in their interpretation. 

As concerns the former, statistical tests on the measured data are usually adopted to detect any abnormal behavior. In other words, an industrial process is considered as a stochastic system and the measured data are considered as different realizations of the stochastic process. The distribution of the observations in normal operating conditions is different from those related to the faulty process. Early statistical approaches are based on univariate statistical techniques, i.e., the distribution of a monitored variable is taken into account. For instance, if the monitored variable follows a normal distribution, the parameters of interest are the mean and standard deviation that, in faulty conditions, may deviate from their nominal values. Therefore, fault diagnosis can be reformulated as the problem of detecting changes in the parameters of a stochastic variable [3, 30],... 

In addition to univariate statistical analysis, the data were also examined by means of multivariate statistical techniques. In particular, R-mode factor analysis was used, which is a very effective tool to interpret anomalies and to help identify their sources. Factor analysis allows grouping of anomalies by compatible geochemical associations from a geologic-mineralogical point of view, the presence of mineralizing processes, or processes connected to the surface environment. Based on this analysis, six meaningful chemical associations were identified (Fig. 15.8). 

Py-MS data analysis with univariate statistical techniques. 

Univariate statistical techniques are not appropriate for multivariate structures. Repeated ANOVAs are not warranted and can even be misleading. 

The book follows a rational presentation structure, starting with the fundamentals of univariate statistical techniques and a discussion on the implementation issues in Chapter 2. After stating the limitations of univariate techniques, Chapter 3 focuses on a number of multivariate statistical techniques that permit the evaluation of process performance and provide diagnostic insight. To exploit the information content of process measurements even further. Chapter 4 introduces several modeling strategies that are based on the utilization of input-output process data. Chapter 5 provides statistical process monitoring techniques for continuous processes and three case studies that demonstrate the techniques. 

In the era of single-loop control systems in chemical processing plants, there was little infrastructure for monitoring multivariable processes by using multivariate statistical techniques. A limited number of process and quality variables were measured in most plants, and use of univariate SPM tools for monitoring critical process and quality variables seemed appropriate. The installation of computerized data acquisition and storage systems, the availability of inexpensive sensors for typical process variables such as temperature, flow rate, and pressure, and the development of advanced chemical analysis systems that can provide reliable information on quality variables at high frequencies increased the number of variables measured at... 

PCA is a method based on the Karhunen-Loeve transformation (KL transformation) of the data points in the feature space. In KL transformation, the data points in the feature space are rotated such that the new coordinates of the sample points become the linear combination of the original coordinates. And the first principal component is chosen to be the direction with largest variation of the distribution of sample points. After the KL transformation and the neglect of the components with minor variation of coordinates of sample points, we can make dimension reduction without significant loss of the information about the distribution of sample points in the feature space. Up to now PCA is probably the most widespread multivariate statistical technique used in chemometrics. Within the chemical community the first major application of PCA was reported in 1970s, and form the foundation of many modem chemometric methods. Conventional approaches are univariate in which only one independent variable is used per sample, but this misses much information for the multivariate problem of SAR, in which many descriptors are available on a number of candidate compounds. PCA is one of several multivariate methods that allow us to explore patterns in multivariate data, answering questions about similarity and classification of samples on the basis of projection based on principal components. 

Sediment analyses are useful for characterization of pollution over a long period [MULLER, 1981]. Assessment of the state of a river and of the interactions between the components can be made by application of multivariate statistical methods only, because the strongly scattering territorial and temporal courses [FORSTNER and MULLER, 1974 FORSTNER and WITTMANN, 1983] are not compatible with many univariate techniques. FA shall serve as a tool for the recognition of variable structures and for the differentiated evaluation of the pollution of both river water and sediment [GEISS and EINAX, 1991 1992],... 

Lavagnini, I. and Magno, F. (2007) A statistical overview on univariate calibration, inverse regression and detection limits. Application to gas chromatography/mass spectrometry technique, Mass Spectrom. Rev., 26(1), 1-18. 

Some statistics concepts such as mean, range, and variance, test of hypothesis, and Type I and Type II errors are introduced in Section 2.1. Various univariate SPM techniques are presented in Section 2.2. The critical assumptions in these techniques include independence and identical distribution [iid) of data. The independence assumption is violated if data are autocorrelated. Section 2.3 illustrates the pitfalls of using such SPM techniques with strongly autocorrelated data and outlines SPM techniques for autocorrelated data. Section 2.4 presents the shortcomings of using univariate SPM techniques for multivariate data. 

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