BOX-COX TRANSFORMATIONS IN THE ANALYSIS OF COMPOSITIONAL DATA

The statistical analysis of compositional data is of fundamental importance to practitioners in generaland to chemists in particular.The existing methodology is principally due to Aitchison,who effectivelyuses two transformations,a ratio followed by the logarithmic,to create a useful,coherent theory thatin principle allows the plethora of normal-based multivariate techniques to be used on the transformeddata.This paper suggests that the well-known class of Box-Cox transformations can be employed inplace of the logarithmic to significantly improve the existing methodology.This is supported in part byshowing that one of the most basic problems that Aitchison managed to overcome,namely thespecification of an interpretable covariance structure for compositional data,can be resolved,or nearlyresolved,once the ratio transformation has been applied.Hence the resolution is not directly dependenton the logarithmic transformation.It is then verified that access to the general Box-Cox family will allowa more accurate use of the normal-based multivariate techniques,simply because better fits to normalitycan be achieved.Finally,maximum likelihood estimation and some associated asymptotics are employedto construct confidence intervals for ratios of the true,unknown compositional constituents.Heretoforethis had not been done even in the context of the logarithmic transformation.Applications to real dataare presented.     

SCALING TECHNIQUES IN THE ANALYSIS OF ENVIRONMENTAL COGNITION DATA∗

The utility of nonmetric, multidimensional-scaling techniques is demonstrated for the analysis and collection of environmental-cognition data. By comparing the multidimensional-scaling solutions of a real-setting map to scaling solutions for sketch maps and two psychophysical, distance-scaling procedures, we demonstrate that magnitude estimation of actual interpoint distances is comparable in accuracy to sketch maps when produced without constraints, or when subjects are given a specified list of landmarks to include on their maps. Triadic comparisons of actual interpoint distances were less accurate than the three other techniques.     

RESIDUAL BILINEARIZATION.PART 2:APPLICATION TO HPLC-DIODE ARRAY DATA AND COMPARISON WITH RANK ANNIHILATION FACTOR ANALYSIS

The partial least squares-residual bilinearization(PLS-RBL)approach to background correctionpresented in Part 1 of this work is demonstrated with an example from HPLC with diode array detection.Data are also evaluated with generalized rank annihilation factor analysis(GRAFA)and results arecompared.     

COMPRESSION OF nth-ORDER DATA ARRAYS BY B-SPLINES.PART 1:THEORY

For efficient handling of very large data arrays,pretreatment by compression is mandatory.In the presentpaper B-spline methods are described as good candidates for such data array compression.Themathematical relation between the maximum entropy method for compression of data tables andthe B-spline of zeroth degree is described together with the generalization of B-spline compression tonth-order data array tables in matrix and tensor algebra.     

PRINCIPAL COMPONENT ANALYSIS APPLIED TO THE STUDY OF SUCCESSIVE COMPLEX FORMATION DATA IN CU(II)-ETHANOLAMINE SYSTEMS

Application of principal component analysis to Cu(II)-ethanolamine complex formation data is shown.Determination of the number of complex species is obtained from the rank of the matrix of spectral datausing either Gauss elimination or factorial analysis.Relevant information concerning species distributionversus pH is obtained from the plot of the signficant factors upsurging from the evolution of spectraltitration data.     

MECHANISM OF THE HYDROLYSIS OF ADENOSINE 5＇-TRIPHOSPHATE: A REGRESSION ANALYSIS OF KINETIC DATA

Data of the hydrolysis of adenosine 5'-triphosphate have been re-evaluated using a computer program thatnumerically integrates the differential rate equations within a routine that optimizes rate coefficients givena suitable model and concentration versus time data. The model is tested by calculation of Hamilton R-values, the Fisher F-statistic, a sensitivity analysis,the standard errors on the rate coefficients and by constructing contour maps of the objective functionversus two rate coefficients. An optimization using only phosphate concentration data cannot distinguish between a model in whichadenosine 5'-monophosphate is formed predominantly directly with a molecule of pyrophosphate, andone in which it is formed via adenosine 5'-diphosphate. A more accurate set of rate coefficients iscalculated from existing data and the relative importance of the two paths determined.     

THE START AND EARLY HISTORY OF CHEMOMETRICS:SELECTED INTERVIEWS.PART 2

This is a first foray into the historical start and early years of chemometrics from about 1972 onwards.We have gathered interviews with three originators(Kowalski,Wold and Massart)as well as with aselected group of six other well-known chemometricians who gradually became active in the 1970s(Christie,Clementi,Hopke,Martens,Brown and Deming).The interviews include amongst a host ofsubjective recollections a succinct record of the key historical literature as highlighted by the interviewees'own rankings of‘earliest’and‘best’.A discussion of the most general commonalities in these interviews together with other historicalmaterial is presented in the second part of the paper.     

THE START AND EARLY HISTORY OF CHEMOMETRICS:SELECTED INTERVIEWS.PART 1

This is a first foray into the historical start and early years of chemometrics from about 1972 onwards.We have gathered interviews with three originators(Kowalski,Wold and Massart)as well as with aselected group of six other well-known chemometricians who gradually became active in the 1970s(Christie,Clementi,Hopke,Martens,Brown and Deming).The interviews include amongst a host ofsubjective recollections a succinct record of the key historical literature as highlighted by the interviewees'own rankings of‘earliest’and‘best’.A discussion of the most general commonalities in these interviews together with other historicalmaterial is presented in the second part of the paper.     

LOCAL LABOR MARKETS: THEORIES AND POLICIES IN THE U.S. DURING THE 1970s∗

Local labor market policies of the federal government are critically evaluated with respect to their target efficiency and underlying theoretical assumptions. Policies of the Economic Development Administration are considered to be target inefficient compared to those of the Comprehensive Employment Training Act. Experimental mobility policies of the Department of Labor appear to be have questionable impact locally as opposed to nationally. Some local hybrid programs offer improved place and people targeting.     

PREDICTIVE ABILITY OF REGRESSION MODELS.PART Ⅱ:SELECTION OF THE BEST PREDICTIVE PLS MODEL

A procedure called GOLPE is suggested in order to detect those variables which increase the predictivityof PLS models.The procedure is based on evaluating the predictive power of a number of PLS modelsbuilt by different combinations of variables selected according to a factorial design strategy.Examplesare given of the efficiency of this variable selection procedure,which shows how these predictive PLSmodels are better than those obtained by all variables and better than the corresponding ordinaryregression models.     

CHEMICAL INFORMATION FROM ELECTROANALYTICAL DATA.PART 1—DETERMINATION OF SYSTEM PARAMETERS FOR QUASI-REVERSIBLE ELECTRON TRANSFER REACTIONS FROM CYCLIC VOLTAMMETRIC TEST DATA AND DATA FOR THE REDUCTION OF CERIUM(Ⅳ)BIS(OCTAETHYLPORPHYRINATE)

Values of the peak potential,the peak current function and the peak potential difference are extractedfrom simulated cyclic voltammograms of a quasi-reversible electron transfer reaction.Variations of thefeature values are described by empirical functions of the model parameters α(transfer coefficient)andψ'(dimensionless form of the heterogeneous electron transfer rate constant k_s)using multiple linearregression.These functions are used to determine the system parameters α and k_s from test data sets offeature values.The predictive power of the features is discussed.It is shown that several features can beused simultaneously in the analysis.Also,α,k_s,the formal potential E~0 and the diffusion coefficient Dcan be estimated simultaneously.Experimental data from the metal-centered one-electron reduction ofcerium(Ⅳ)bis(octaethylporphyrinate),Ce(OEP)_2,are analyzed using the technique,and values of thesystem parameters for this electrochemical reaction are determined.     

A review of: “National Transfer Format,Release 1.0, January, 1987.” By THE WORKING PARTY TO PRODUCE NATIONAL STANDARDS FOR THE TRANSFER OF NATIONAL DIGITAL MAP DATA. (Southampton: The NTF Secretariat,Ordnance Survey, 1987. [Pp. 191: appendices and looseleaf annex.]

Metonymically used location names (toponyms) refer to other, related entities and thus possess a meaning different from their literal, geographic sense. Metonymic uses are to be treated differently to improve the performance of geographic information retrieval (GIR). Statistics on toponym senses show that 75.06% of all location names are used in their literal sense, 17.05% are used metonymically, and 7.89% have a mixed sense. This article presents a method for disambiguating location names in texts between literal and metonymic senses, based on shallow features.

The evaluation of this method is two‐fold. First, we use a memory‐based learner (TiMBL) to train a classifier and determine standard evaluation measures such as F‐score and accuracy. The classifier achieved an F‐score of 0.842 and an accuracy of 0.846 for identifying toponym senses in a subset of the CoNLL (Conference on Natural Language Learning) data.

Second, we perform retrieval experiments based on the GeoCLEF data (newspaper article corpus and queries) from 2005 and 2006. We compare searching location names in a database index containing both their literal and metonymic senses with searching in an index containing their literal senses only. Evaluation results indicate that removing metonymic senses from the index yields a higher mean average precision (MAP) for GIR. In total, we observed a significant gain in MAP: an increase from 0.0704 to 0.0715 MAP for the GeoCLEF 2005 data, and an increase from 0.1944 to 0.2100 MAP for the GeoCLEF 2006 data.