Target transformation factor analysis method

Because of peak overlappings in the first- and second-derivative spectra, conventional spectrophotometry cannot be applied satisfactorily for quantitative analysis, and the interpretation cannot be resolved by the zero-crossing technique. A chemometric approach improves precision and predictability, e.g., by the application of classical least sqnares (CLS), principal component regression (PCR), partial least squares (PLS), and iterative target transformation factor analysis (ITTFA), appropriate interpretations were found from the direct and first- and second-derivative absorption spectra. When five colorant combinations of sixteen mixtures of colorants from commercial food products were evaluated, the results were compared by the application of different chemometric approaches. The ITTFA analysis offered better precision than CLS, PCR, and PLS, and calibrations based on first-derivative data provided some advantages for all four methods. ... 

ALS should more correctly be called Alternating Linear Least-Squares as every step in the iterative cycle is a linear least-squares calculation followed by some correction of the results. The main advantage and strength of ALS is the ease with which any conceivable constraint can be implemented its main weakness is the inherent poor convergence. This is a property ALS shares with the very similar methods of Iterative Target Transform Factor Analysis, TTTFA and Iterative Refinement of the Concentration Profiles, discussed in Chapters 5.2.2 and 5.3.3. 

PLS (partial least squares) multiple regression technique is used to estimate contributions of various polluting sources in ambient aerosol composition. The characteristics and performance of the PLS method are compared to those of chemical mass balance regression model (CMB) and target transformation factor analysis model (TTFA). Results on the Quail Roost Data, a synthetic data set generated as a basis to compare various receptor models, is reported. PLS proves to be especially useful when the elemental compositions of both the polluting sources and the aerosol samples are measured with noise and there is a high correlation in both blocks. 

In this paper the PLS method was introduced as a new tool in calculating statistical receptor models. It was compared with the two most popular methods currently applied to aerosol data Chemical Mass Balance Model and Target Transformation Factor Analysis. The characteristics of the PLS solution were discussed and its advantages over the other methods were pointed out. PLS is especially useful, when both the predictor and response variables are measured with noise and there is high correlation in both blocks. It has been proved in several other chemical applications, that its performance is equal to or better than multiple, stepwise, principal component and ridge regression. Our goal was to create a basis for its environmental chemical application. 

Among the multivariate statistical techniques that have been used as source-receptor models, factor analysis is the most widely employed. The basic objective of factor analysis is to allow the variation within a set of data to determine the number of independent causalities, i.e. sources of particles. It also permits the combination of the measured variables into new axes for the system that can be related to specific particle sources. The principles of factor analysis are reviewed and the principal components method is illustrated by the reanalysis of aerosol composition results from Charleston, West Virginia. An alternative approach to factor analysis. Target Transformation Factor Analysis, is introduced and its application to a subset of particle composition data from the Regional Air Pollution Study (RAPS) of St. Louis, Missouri is presented. 

There are two general types of aerosol source apportionment methods dispersion models and receptor models. Receptor models are divided into microscopic methods and chemical methods. Chemical mass balance, principal component factor analysis, target transformation factor analysis, etc. are all based on the same mathematical model and simply represent different approaches to solution of the fundamental receptor model equation. All require conservation of mass, as well as source composition information for qualitative analysis and a mass balance for a quantitative analysis. Each interpretive approach to the receptor model yields unique information useful in establishing the credibility of a study s final results. Source apportionment sutdies using the receptor model should include interpretation of the chemical data set by both multivariate methods. 

Multivariate methods, on the other hand, resolve the major sources by analyzing the entire ambient data matrix. Factor analysis, for example, examines elemental and sample correlations in the ambient data matrix. This analysis yields the minimum number of factors required to reproduce the ambient data matrix, their relative chemical composition and their contribution to the mass variability. A major limitation in common and principal component factor analysis is the abstract nature of the factors and the difficulty these methods have in relating these factors to real world sources. Hopke, et al. (13.14) have improved the methods ability to associate these abstract factors with controllable sources by combining source data from the F matrix, with Malinowski s target transformation factor analysis program. (15) Hopke, et al. (13,14) as well as Klelnman, et al. (10) have used the results of factor analysis along with multiple regression to quantify the source contributions. Their approach is similar to the chemical mass balance approach except they use a least squares fit of the total mass on different filters Instead of a least squares fit of the chemicals on an individual filter. 

The factor analysis technique used was unable to distinguish separate soil and road sources. Ca appeared with Al, Si, K, Ti, and Fe on a factor that can be characterized only as "crustal," including both soil and road materials. It appears that a chemical element balance should always be used as a check on factor analysis results, at least until a more sophisticated factor analysis method, such as target transformation factor analysis (14), can be shown not to require it. 

The next subsection deals first with aspects common to all resolution methods. These include (1) issues related to the initial estimates, i.e., how to obtain the profiles used as the starting point in the iterative optimization, and (2) issues related to the use of mathematical and chemical information available about the data set in the form of so-called constraints. The last part of this section describes two of the most widely used iterative methods iterative target transformation factor analysis (ITTFA) and multivariate curve resolution-alternating least squares (MCR-ALS). 

Varimax rotation is a commonly used and widely available factor rotation technique, but other methods have been proposed for interpreting factors from analytical chemistry data. We could rotate the axes in order that they align directly with factors from expected components. These axes, referred to as test vectors, would be physically significant in terms of interpretation and the rotation procedure is referred to as target transformation. Target transformation factor analysis has proved to be a valuable technique in chemo-metrics. The number of components in mixture spectra can be identified and the rotated factor loadings in terms of test data relating to standard, known spectra, can be interpreted. 

Hopke PK (1988) Target transformation factor analysis as an aerosol mass apportionment method a review and sensitivity study. Atmos Environ 22 1777-1792. 

To transform the abstract factors determined in the first step into interpretable factors, rotation methods are applied. If definite target vectors can be assumed to be contained in the data, for example, a spectrum under a spectrochromatogram, the rotation of data is performed by using a target. This technique is known as target-transform factor analysis TTFA, c Example 5.6). 

The first study on curve resolution, carried out by Kaiser [1] in 1958, proposed the varimax method, wherein factor rotation was used in factor analysis. Studies by Lawton and Sylvestre of Kodak clearly picked up on curve resolution technology as a means of reaction analysis in chemistry (1971, 1974) [2]. The idea of employing rotating matrices was first used in iterative target transformation factor analysis... 

Factor analysis extracts information from the sample data set (e.g., IR spectra) and does not rely on reference minerals. However, because abstract factors have no physical meaning, reference minerals may be needed in target transformations or other procedures to extract mineralogical information. One valuable piece of information obtainable without the use of extraneous data is the number of components required to represent the data within experimental error. Reported applications of factor analysis to mineralogy by FTIR are few (12). However, one commercial laboratory is offering routine FTIR mineral analyses to the petroleum industry, based on related methods (22). 

Recent efforts of the authors resulted in development of a munerical method for the analysis of reaction mechanisms, based on their Hamiltonian systematization with marking out target characteristics of reactions and with the kinetic comprehension of conjugate variables. The core factor of this approach is the ability to calculate numerically the dynamics of value magnitudes, which characterize the systenuc kinetic significances of the chemical species of a reaction and its individual steps. Such information makes it possible to realize chemically the mechanism of a complex transformation, and particularly, to carry out the purposeful selection of efficient ways to control the reactions. 

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