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Chemometrics in
Chromatography
CHROMATOGRAPHIC SCIENCE SERIES

A Series of Textbooks and Reference Books

Editor:
Nelu Grinberg

Founding Editor:
Jack Cazes

1. Dynamics of Chromatography: Principles and Theory, J. Calvin Giddings


2. Gas Chromatographic Analysis of Drugs and Pesticides, Benjamin J. Gudzinowicz
3. Principles of Adsorption Chromatography: The Separation of Nonionic Organic Compounds,
Lloyd R. Snyder
4. Multicomponent Chromatography: Theory of Interference, Friedrich Helfferich and Gerhard
Klein
5. Quantitative Analysis by Gas Chromatography, Josef Novák
6. High-Speed Liquid Chromatography, Peter M. Rajcsanyi and Elisabeth Rajcsanyi
7. Fundamentals of Integrated GC-MS (in three parts), Benjamin J. Gudzinowicz, Michael J.
Gudzinowicz, and Horace F. Martin
8. Liquid Chromatography of Polymers and Related Materials, Jack Cazes
9. GLC and HPLC Determination of Therapeutic Agents (in three parts), Part 1 edited by
Kiyoshi Tsuji and Walter Morozowich, Parts 2 and 3 edited by Kiyoshi Tsuji
10. Biological/Biomedical Applications of Liquid Chromatography, edited by Gerald L. Hawk
11. Chromatography in Petroleum Analysis, edited by Klaus H. Altgelt and T. H. Gouw
12. Biological/Biomedical Applications of Liquid Chromatography II, edited by Gerald L. Hawk
13. Liquid Chromatography of Polymers and Related Materials II, edited by Jack Cazes and
Xavier Delamare
14. Introduction to Analytical Gas Chromatography: History, Principles, and Practice, John A.
Perry
15. Applications of Glass Capillary Gas Chromatography, edited by Walter G. Jennings
16. Steroid Analysis by HPLC: Recent Applications, edited by Marie P. Kautsky
17. Thin-Layer Chromatography: Techniques and Applications, Bernard Fried and Joseph
Sherma
18. Biological/Biomedical Applications of Liquid Chromatography III, edited by Gerald L.
Hawk
19. Liquid Chromatography of Polymers and Related Materials III, edited by Jack Cazes
20. Biological/Biomedical Applications of Liquid Chromatography, edited by Gerald L. Hawk
21. Chromatographic Separation and Extraction with Foamed Plastics and Rubbers, G. J. Moody
and J. D. R. Thomas
22. Analytical Pyrolysis: A Comprehensive Guide, William J. Irwin
23. Liquid Chromatography Detectors, edited by Thomas M. Vickrey
24. High-Performance Liquid Chromatography in Forensic Chemistry, edited by Ira S. Lurie and
John D. Wittwer, Jr.
25. Steric Exclusion Liquid Chromatography of Polymers, edited by Josef Janca
26. HPLC Analysis of Biological Compounds: A Laboratory Guide, William S. Hancock and
James T. Sparrow
27. Affinity Chromatography: Template Chromatography of Nucleic Acids and Proteins, Herbert
Schott
28. HPLC in Nucleic Acid Research: Methods and Applications, edited by Phyllis R. Brown
29. Pyrolysis and GC in Polymer Analysis, edited by S. A. Liebman and E. J. Levy
30. Modern Chromatographic Analysis of the Vitamins, edited by André P. De Leenheer, Willy
E. Lambert, and Marcel G. M. De Ruyter
31. Ion-Pair Chromatography, edited by Milton T. W. Hearn
32. Therapeutic Drug Monitoring and Toxicology by Liquid Chromatography, edited by Steven
H. Y. Wong
33. Affinity Chromatography: Practical and Theoretical Aspects, Peter Mohr and Klaus
Pommerening
34. Reaction Detection in Liquid Chromatography, edited by Ira S. Krull
35. Thin-Layer Chromatography: Techniques and Applications, Second Edition, Revised and
Expanded, Bernard Fried and Joseph Sherma
36. Quantitative Thin-Layer Chromatography and Its Industrial Applications, edited by Laszlo R.
Treiber
37. Ion Chromatography, edited by James G. Tarter
38. Chromatographic Theory and Basic Principles, edited by Jan Åke Jönsson
39. Field-Flow Fractionation: Analysis of Macromolecules and Particles, Josef Janca
40. Chromatographic Chiral Separations, edited by Morris Zief and Laura J. Crane
41. Quantitative Analysis by Gas Chromatography, Second Edition, Revised and Expanded,
Josef Novák
42. Flow Perturbation Gas Chromatography, N. A. Katsanos
43. Ion-Exchange Chromatography of Proteins, Shuichi Yamamoto, Kazuhiro Naka-nishi, and
Ryuichi Matsuno
44. Countercurrent Chromatography: Theory and Practice, edited by N. Bhushan Man-dava and
Yoichiro Ito
45. Microbore Column Chromatography: A Unified Approach to Chromatography, edited by
Frank J. Yang
46. Preparative-Scale Chromatography, edited by Eli Grushka
47. Packings and Stationary Phases in Chromatographic Techniques, edited by Klaus K. Unger
48. Detection-Oriented Derivatization Techniques in Liquid Chromatography, edited by Henk
Lingeman and Willy J. M. Underberg
49. Chromatographic Analysis of Pharmaceuticals, edited by John A. Adamovics
50. Multidimensional Chromatography: Techniques and Applications, edited by Hernan Cortes
51. HPLC of Biological Macromolecules: Methods and Applications, edited by Karen M.
Gooding and Fred E. Regnier
52. Modern Thin-Layer Chromatography, edited by Nelu Grinberg
53. Chromatographic Analysis of Alkaloids, Milan Popl, Jan Fähnrich, and Vlastimil Tatar
54. HPLC in Clinical Chemistry, I. N. Papadoyannis
55. Handbook of Thin-Layer Chromatography, edited by Joseph Sherma and Bernard Fried
56. Gas–Liquid–Solid Chromatography, V. G. Berezkin
57. Complexation Chromatography, edited by D. Cagniant
58. Liquid Chromatography–Mass Spectrometry, W. M. A. Niessen and Jan van der Greef
59. Trace Analysis with Microcolumn Liquid Chromatography, Milos KrejcI
60. Modern Chromatographic Analysis of Vitamins: Second Edition, edited by André P. De
Leenheer, Willy E. Lambert, and Hans J. Nelis
61. Preparative and Production Scale Chromatography, edited by G. Ganetsos and P. E. Barker
62. Diode Array Detection in HPLC, edited by Ludwig Huber and Stephan A. George
63. Handbook of Affinity Chromatography, edited by Toni Kline
64. Capillary Electrophoresis Technology, edited by Norberto A. Guzman
65. Lipid Chromatographic Analysis, edited by Takayuki Shibamoto
66. Thin-Layer Chromatography: Techniques and Applications: Third Edition, Revised and
Expanded, Bernard Fried and Joseph Sherma
67. Liquid Chromatography for the Analyst, Raymond P. W. Scott
68. Centrifugal Partition Chromatography, edited by Alain P. Foucault
69. Handbook of Size Exclusion Chromatography, edited by Chi-San Wu
70. Techniques and Practice of Chromatography, Raymond P. W. Scott
71. Handbook of Thin-Layer Chromatography: Second Edition, Revised and Expanded, edited
by Joseph Sherma and Bernard Fried
72. Liquid Chromatography of Oligomers, Constantin V. Uglea
73. Chromatographic Detectors: Design, Function, and Operation, Raymond P. W. Scott
74. Chromatographic Analysis of Pharmaceuticals: Second Edition, Revised and Expanded,
edited by John A. Adamovics
75. Supercritical Fluid Chromatography with Packed Columns: Techniques and Applications,
edited by Klaus Anton and Claire Berger
76. Introduction to Analytical Gas Chromatography: Second Edition, Revised and Expanded,
Raymond P. W. Scott
77. Chromatographic Analysis of Environmental and Food Toxicants, edited by Takayuki
Shibamoto
78. Handbook of HPLC, edited by Elena Katz, Roy Eksteen, Peter Schoenmakers, and Neil
Miller
79. Liquid Chromatography–Mass Spectrometry: Second Edition, Revised and Expanded,
Wilfried Niessen
80. Capillary Electrophoresis of Proteins, Tim Wehr, Roberto Rodríguez-Díaz, and Mingde Zhu
81. Thin-Layer Chromatography: Fourth Edition, Revised and Expanded, Bernard Fried and
Joseph Sherma
82. Countercurrent Chromatography, edited by Jean-Michel Menet and Didier Thiébaut
83. Micellar Liquid Chromatography, Alain Berthod and Celia García-Alvarez-Coque
84. Modern Chromatographic Analysis of Vitamins: Third Edition, Revised and Expanded,
edited by André P. De Leenheer, Willy E. Lambert, and Jan F. Van Bocxlaer
85. Quantitative Chromatographic Analysis, Thomas E. Beesley, Benjamin Buglio, and Raymond
P. W. Scott
86. Current Practice of Gas Chromatography–Mass Spectrometry, edited by W. M. A. Niessen
87. HPLC of Biological Macromolecules: Second Edition, Revised and Expanded, edited by
Karen M. Gooding and Fred E. Regnier
88. Scale-Up and Optimization in Preparative Chromatography: Principles and Bio-pharmaceutical
Applications, edited by Anurag S. Rathore and Ajoy Velayudhan
89. Handbook of Thin-Layer Chromatography: Third Edition, Revised and Expanded, edited by
Joseph Sherma and Bernard Fried
90. Chiral Separations by Liquid Chromatography and Related Technologies, Hassan Y. Aboul-
Enein and Imran Ali
91. Handbook of Size Exclusion Chromatography and Related Techniques: Second Edition,
edited by Chi-San Wu
92. Handbook of Affinity Chromatography: Second Edition, edited by David S. Hage
93. Chromatographic Analysis of the Environment: Third Edition, edited by Leo M. L. Nollet
94. Microfluidic Lab-on-a-Chip for Chemical and Biological Analysis and Discovery, Paul C.H. Li
95. Preparative Layer Chromatography, edited by Teresa Kowalska and Joseph Sherma
96. Instrumental Methods in Metal Ion Speciation, Imran Ali and Hassan Y. Aboul-Enein
97. Liquid Chromatography–Mass Spectrometry: Third Edition, Wilfried M. A. Niessen
98. Thin Layer Chromatography in Chiral Separations and Analysis, edited by Teresa Kowalska
and Joseph Sherma
99. Thin Layer Chromatography in Phytochemistry, edited by Monika Waksmundzka-Hajnos,
Joseph Sherma, and Teresa Kowalska
100. Chiral Separations by Capillary Electrophoresis, edited by Ann Van Eeckhaut and Yvette
Michotte
101. Handbook of HPLC: Second Edition, edited by Danilo Corradini and consulting editor Terry
M. Phillips
102. High Performance Liquid Chromatography in Phytochemical Analysis, edited by Monika
Waksmundzka-Hajnos and Joseph Sherma
103. Hydrophilic Interaction Liquid Chromatography (HILIC) and Advanced Applications, edited
by Perry G. Wang and Weixuan He
104. Hyphenated and Alternative Methods of Detection in Chromatography, edited by R. Andrew
Shalliker
105. LC-NMR: Expanding the Limits of Structure Elucidation, Nina C. Gonnella
106. Thin Layer Chromatography in Drug Analysis, edited by Łukasz Komsta, Monika
Waksmundzka-Hajnos, and Joseph Sherma
107. Pharmaceutical Industry Practices on Genotoxic Impurities, edited by Heewon Lee
108. Advanced Separations by Specialized Sorbents, edited by Ecaterina Stela Dragan
109. Performance Liquid Chromatography in Pesticide Residue Analysis, edited by Tomasz
Tuzimski and Joseph Sherma
110. Planar Chromatography-Mass Spectrometry, edited by Teresa Kowalska, Mieczysław
Sajewicz, and Joseph Sherma
111. Chemometrics in Chromatography, edited by Łukasz Komsta, Yvan Vander Heyden, and
Joseph Sherma
Chemometrics in
Chromatography

Edited by
Łukasz Komsta
Yvan Vander Heyden
Joseph Sherma
MATLAB® is a trademark of The MathWorks, Inc. and is used with permission. The MathWorks does not warrant the accuracy
of the text or exercises in this book. This book’s use or discussion of MATLAB® software or related products does not constitute
endorsement or sponsorship by The MathWorks of a particular pedagogical approach or particular use of the MATLAB® software.

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Library of Congress Cataloging-in-Publication Data

Names: Komsta, Łukasz, editor. | Vander Heyden, Yvan, editor. | Sherma,


Joseph, editor.
Title: Chemometrics in chromatography / editors, Łukasz Komsta, Yvan Vander
Heyden, Joseph Sherma.
Description: Boca Raton : CRC Press, 2018. | Series: Chromatographic science
series | Includes bibliographical references.
Identifiers: LCCN 2017037096 | ISBN 9781498772532 (hardback : alk. paper)
Subjects: LCSH: Chemometrics. | Chromatographic analysis.
Classification: LCC QD75.4.C45 C48448 2018 | DDC 543.01/5195--dc23
LC record available at https://lccn.loc.gov/2017037096

Visit the Taylor & Francis Web site at


http://www.taylorandfrancis.com

and the CRC Press Web site at


http://www.crcpress.com
We dedicate this book to Prof. Yi-Zeng Liang, an excellent chemometrician
and chromatographer who also contributed to this book. He passed away
on October 14, 2016, after suffering from an incurable disease. The chapter
he coauthored for this book is one of his last scientific contributions.
Yi-Zeng Liang was professor at the Central South University in Changsha,
China, where he was working at the Research Center for Modernization
of Chinese Medicines. His chromatographic work thus was often related
to the analysis of traditional Chinese medicines, for which fingerprint
chromatograms were developed from herbal samples. The entire fingerprint
profiles then were multivariately analyzed using chemometric methods.
Prof. Liang was the best known Chinese chemometrician for many years. In
1997, he organized the first Chinese Conference on Chemometrics, together
with his Norwegian friend Olav Kvalheim. For many years, he tried to get an
important chemometrics conference—Chemometrics in Analytical Chemistry
(CAC)—to China. Finally, he succeeded, and in 2015 the conference was
organized in Changsha. At that moment, he already was suffering from the
disease of which he finally lost the battle. The year after his organization, during
the 2016 CAC meeting in Barcelona, Spain, he was awarded the CAC Lifetime
Achievement Award for his contributions to chemometrics. Unfortunately, his
health prevented him to travel to Europe to personally receive the award.
His legacy includes, besides many good memories to those who have known
him, a long list of PhD students and also more than 400 research papers in
English. Including his Chinese contributions raises that number to almost
1000 papers. For many years, until the very end of his life, he also served as
editor of the Chemometrics and Intelligent Laboratory Systems journal.
Dedicating this book to his remembrance hopefully will trigger some readers
to shortly think back, from time to time, about this remarkable scientist.

— Łukasz Komsta, Yvan Vander Heyden, and Joseph Sherma


Contents
Preface...............................................................................................................................................xv
Contributors....................................................................................................................................xvii

Section I  Method Development and Optimization

Chapter 1 Experimental Design in Chromatographic Method Development and Validation........3


Łukasz Komsta and Yvan Vander Heyden

Chapter 2 Chromatographic Response Functions........................................................................25


Regina M.B.O. Duarte, João T.V. Matos, and Armando C. Duarte

Chapter 3 Chemometric Strategies to Characterize, Classify, and Rank Chromatographic


Stationary Phases and Systems...................................................................................45
Charlene Muscat Galea, Debby Mangelings, and Yvan Vander Heyden

Section II  Univariate Analysis

Chapter 4 Chromatographic Applications of Genetic Algorithms...............................................63


Mohammad Goodarzi and Yvan Vander Heyden

Chapter 5 Statistics in Validation of Quantitative Chromatographic Methods............................77


Eliangiringa Kaale, Danstan Hipolite Shewiyo, and David Jenkins

Chapter 6 Calibration Curves in Chromatography......................................................................99


Sven Declerck, Johan Viaene, Ines Salsinha, and Yvan Vander Heyden

Section III  Data Preprocessing and Unsupervised Analysis

Chapter 7 Introduction to Multivariate Data Treatment.............................................................117


Łukasz Komsta and Yvan Vander Heyden

Chapter 8 Introduction to Exploratory and Clustering Techniques...........................................127


Ivana Stanimirova and Michał Daszykowski

xi
xii Contents

Chapter 9 Denoising of Signals, Signal Enhancement, and Baseline Correction


in Chromatographic Science.....................................................................................137
Zhi-Min Zhang, Hong-Mei Lu, and Yi-Zeng Liang

Chapter 10 Alignment of One- and Two-Dimensional Chromatographic Signals......................171


Michał Daszykowski

Chapter 11 Peak Purity and Resolution of Chromatographic Data.............................................183


Sílvia Mas and Anna de Juan

Chapter 12 Modeling of Peak Shape and Asymmetry.................................................................217


José Ramón Torres-Lapasió, Juan José Baeza-Baeza,
and María Celia García-Álvarez-Coque

Chapter 13 Missing and Censored Data in Chromatography......................................................239


Ivana Stanimirova

Section IV Classification, Discrimination, and Calibration

Chapter 14 Linear Supervised Techniques...................................................................................255


Łukasz Komsta and Yvan Vander Heyden

Chapter 15 Discriminant Analysis and Classification of Chromatographic Data........................267


Alessandra Biancolillo and Federico Marini

Chapter 16 Nonlinear Supervised Techniques.............................................................................285


Geert Postma, Lionel Blanchet, Frederik-Jan van Schooten, and Lutgarde Buydens

Section V Retention Modeling

Chapter 17 Introduction to Quantitative Structure–Retention Relationships..............................303


Krzesimir Ciura, Piotr Kawczak, Joanna Nowakowska, and Tomasz Ba˛czek

Chapter 18 Topological Indices in Modeling of Chromatographic Retention.............................319


Małgorzata Dołowy, Katarzyna Bober, and Alina Pyka-Paja˛k
Contents xiii

Section VI  Application Overviews

Chapter 19 Introduction to Herbal Fingerprinting by Chromatography......................................351


Johan Viaene and Yvan Vander Heyden

Chapter 20 Chemometric Strategies in Analysis of Chromatographic–Mass Spectrometry


Data...........................................................................................................................371
Samantha Riccadonna and Pietro Franceschi

Chapter 21 Chemometric Strategies in Chromatographic Analysis of Pharmaceuticals.............381


Erdal Dinç

Section VII  Miscellaneous

Chapter 22 Bayesian Methods in Chromatographic Science.......................................................417


David Brynn Hibbert

Chapter 23 Multiway Methods in Chromatography....................................................................435


Łukasz Komsta and Yvan Vander Heyden

Chapter 24 Recurrent Relationships in Separation Science.........................................................449


Igor Zenkevich

Chapter 25 Chemometrics and Image Processing in Thin-Layer Chromatography....................469


Bahram Hemmateenejad, Elaheh Talebanpour Bayat, Elmira Rafatmah,
Zahra Shojaeifard, Nabiollah Mobaraki, and Saeed Yousefinejad

Index...............................................................................................................................................495
Preface
Recalling memories of the near past (1980s), when an average home computer was equipped with
64 or 128 kB of memory together with a CPU clocked with several MHz, one can conclude that 30
years was sufficient time to make the science fiction come true. Nowadays, an average smartphone
has better computational abilities than many scientific supercomputers in the past. Adding to this
fact the development of high-quality open-source software, an average data-handling scientist does
not have to bear many significant costs to perform serious analysis of huge datasets.
Chemometrics, the science related to the systematic optimization of methods and to the analysis
of the gathered data, is at the fingertips of every chromatographer and is not an alien discipline,
made by specialists for highly experienced users. It is a great practical and it helps in chromato-
graphic experimenting, from a proper design of the research projects (reducing the effort and the
costs) to the extraction of hidden information in large datasets collected from modern equipment
with hyphenated detectors.
The proper use of chemometrics requires the understanding of how these methods work. However,
there is no need to dig deeply into the mathematical background, as contemporary chromatographer
do not need to write their own software routines. Compare the situation with using a calculator—
computing a square root does not require the knowledge of how the calculator computes the value,
but one must understand what the square root is and how to use the obtained value in the context of
a given problem. In an analogous way, the researcher cannot treat chemometrics as a “black box”
approach (because this often leads to misuse and errors), but the algorithmic details of the software
can be neglected if the cognitive value of the results is known.
It can be honestly stated that many chromatographers still have some fear about chemometrics
and cannot come to terms with the fact that it became the de facto standard in modern analytical
chemistry. Although several great textbooks on the topic exist, they may be quite huge, they focus on
other domains of application, and they often terrify potential users, who have to read about several
methods (including those applied rarely in chromatography) to make potential connections between
pure theory and chromatographic practice.
These facts were the main impulse to start this book project. Our main goal was to create a book
dedicated to chromatographers, covering the most important chemometric methods that are now also
important from a chromatographer’s point of view, explained in strict connection with chromato-
graphic practice. Although this book is written by specialists, effort was made to explain chemometrics
from the basics, as chromatographers are generally not trained chemometricians.
We hope that the text will be useful for readers that like to use chemometrics in chromatographic
analysis. The book may also be interesting for scientists with some chemometric experience who
want to reread about known methods, but now occasionally seen from a different point of view.
The theory of chemometric methods is explained in relation to chromatography, but the knowledge
gathered after reading this book may be applied in other disciplines of analytical chemistry, as well
as in other applications. Depending on the context, it can be considered as a manual, a reference
book, or a teaching source.
We thank Barbara Knott, Senior Editor—Chemistry, CRC Press/Taylor & Francis Group, for her
support of our book proposal and S. Valantina Jessie, Project Manager, for her help in all aspects
of our subsequent editorial work. We also thank the chapter authors for great cooperation and their
exceptionally valuable contributions.

xv
xvi Preface

MATLAB® is a registered trademark of The MathWorks, Inc. For product information, please
contact:

The MathWorks, Inc.


3 Apple Hill Drive
Natick, MA, 01760-2098 USA
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Web: www.mathworks.com
8 Chemometrics in Chromatography

Factor 2

Factor 1

Factor 3

FIGURE 1.1 Three-dimensional representation of a 2(3−1) fractional factorial design. From eight full factorial
experiments, represented as the vertices of a cube, half of them are chosen in a way to be viewed as a square
when projected onto two dimensions. To fulfill this requirement, the remaining points must be arranged as a
tetrahedron.

interactions. Resolution V uncovers main effects, two-factor interaction effects, and also gives
possibility of computing three-factor interaction effects, but these confound with two-factor inter-
actions (and vice versa).
There is no easy rule to remember what efficiency can be obtained with a particular number of
experiments and factors, but the (most often used) combinations can be summarized in the follow-
ing way:

1. Four experiments give full resolution for 2 factors.


2. Eight experiments give full resolution for 3 factors, IV for 4 factors, and III for 5–7 factors.
3. Sixteen experiments give full resolution for 4 factors, V for 5 factors, IV for 6–8 factors,
and III for 9–15 factors.
4. Thirty-two experiments give full resolution for 5 factors, VI for 6 factors, and IV for 7–15
factors.

Table 1.1 contains fractional designs for 8, 16, and 32 experiments. In each case, the three or four
smallest numbers of possible factors are shown.

1.4.1 Plackett–Burman Designs
An alternative for the fractional factorial designs are the Plackett–Burman designs [20,35–37]. It
can be constructed for a number of experiments n, which is a multiple of four (starting from eight,
the most useful example, i.e., with 12 experiments is shown in Table 1.2), and it can estimate up to
n − 1 main effects (the resolution is always III). To be more precise, this design always estimates
n − 1 factor effects, but when the real factor number is smaller, the remaining factors are treated
as dummy variables (nothing changes when such factor is either at low or high level; their effects
should be insignificant and are used to estimate the experimental error).
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CONTENTS

OF

THE THIRD VOLUME.

CHAPTER I.

Prince Pückler Muskau—His letter to Lady Hester


Stanhope—Story of the Serpent’s Cave—Letter from
Lady Hester to the Prince—Ride from Jôon to Sayda—
Cadi’s Justice—Madame Conti—Syrian surgeons 1

CHAPTER II.

Mehemet Ali’s hospitality to travellers—Prince


Pückler Muskau’s appreciation of it—His reception of
the Author—Reflections on passports—Lady Hester’s
pecuniary difficulties—Her reluctance to reduce her
establishment—Her restlessness—Presents in Eastern
countries—Severity necessary with Eastern servants—
Letter from Lady Hester to Lord Ebrington—Outrage
committed on old Pierre—Defection of the Ottoman
fleet—Khalyl Aga 29

CHAPTER III.

Lady Hester’s mode of life—Boghoz Bey—The 50


insurrection of the Druzes—Character of the Emir
Beshýr—Ibrahim Pasha—Lady Charlotte Bury—
Preparations for the reception of Prince Pückler
Muskau

CHAPTER IV.

Prince Pückler Muskau’s arrival at Jôon—His


costume—Physiognomical doctrines—The Prince’s
remarks on Lady Hester—Dr. Bowring—Lady Hester’s
remarks on the Prince—Race of Abyssinian women—
Remarks on public grants, &c.—The polytheistic
school of Germany—Remarks on pensions, on
Abyssinian slaves, &c.—Story of Sultan Abdallah, the
negro—Excursion on horseback—Horse-jockeys in
Syria—Servants’ vails—Lord M. and Captain G.—
Talismanic charm about Lady Hester—Her visions of
greatness 73

CHAPTER V.

Prince Pückler Muskau’s style of writing—Talking


beneficial to health—Young men of Lady Hester’s time
—Lady Hester’s superstitious belief in good and bad
days—Hamâady, the executioner—His importance—
Folly of education, according to Lady Hester—Lord
Hood, Lord Bridport, Payne, the smuggler’s son—the
O****s—The Prince’s self-invitations to dine out—B.—
Prince Pückler and old Pierre—The American
Commodore—Lady Hester’s cats—Mahomet Ali’s
secret devices 107

CHAPTER VI.

Author’s dilemma—Apprehensions of poisoning— 128


Mr. Cooper’s dray-boy—Memoirs of a Peeress—Lady
B. and the Duchess of——Novel scheme for making
maids obedient—English servants—Lady J.—Lord C.
—Mr. Pitt, and the disturbed state of England—Peers
made by Mr. Pitt—Footmen’s nosegays—Mr. Pitt’s last
words, as related by Gifford—Melancholy reflections—
Mr. Pitt’s signature—Mr. Pitt a Statesman inferior to
Lord Chatham—Mr. Fox—Sir Walter Scott—Shaykh
Mohammed Nasýb—Turkish dervises—Anecdote of
Sir William Pynsent—Sir John Dyke—High and low
descent exemplified in Captain—and Count Rewisky—
Lady Charlotte Bury—The Empress Josephine—
Buonaparte—Mr. Pitt’s physiognomy—Advantageous
offers refused by Lady Hester—Her house in
Montague Square—The Cheshire Squire—Ingratitude
of the world—Trust not in man, but in God

CHAPTER VII.

Journey to Beyrout—Death of Mrs. K—- —Mr.


George Robinson and M. Guys—The River Damoor—
Khaldy—Letter from Lady Hester to Mr. K.—Lord
Prudhoe—Mrs. Moore—Lady Hester’s dislike to be the
subject of occasional poetry—Striking a Turk—Lady
Hester’s opinion of Lord Byron—Arrival of Maximilian
Duke of Bavaria—Letter to the Baron de Busech—
Letter to H.R H. the Duke Maximilian—Adventures of
the Duke—Illness of the Duke’s negro, Wellington—
Vexation of His Royal Highness—Letter to Mr. K.,
merchant at Beyrout—Letter to Lord Brougham—
Professional visit to Sulyman Pasha’s child—League
between the maids and receivers of stolen goods—
Black doses for the Prince’s suite—Letter from Lady
Hester to the Duke of Bavaria on his intended visit—
The Duke leaves Syria 171

CHAPTER VIII.

Petty annoyances in hot countries—Lady Hester 225


refuses Duke Maximilian’s portrait—She insists on the
Author’s leaving her—Continuation of the negro
Wellington’s case—Progress of the Druze insurrection
—Destruction of locusts—Mysterious visit at the Dar—
Reasons why Lady Hester kept daring fellows in her
service—Russian spies—Dr. Lœve’s visit—Dangerous
state of the country—Lady Hester’s dream—Her
resolution to immure herself—Visit from Mr. M.—Visit
from Colonel Hazeta and Dr. Mill—Letter from Lord
Palmerston to Lady Hester—Her answer—
Inexpediency of having consular agents, not natives of
the country they represent—Successes of the Druzes
—Lady Hester’s belief in fortune-telling—Letter from
Sir Francis Burdett—Colonel Needham’s property—
Lord Coutts—Subscribers to pay Mr. Pitt’s debts—
Fright from a serpent—Battle of Yanta—Sir N. Wraxall
a peer—Discourse upon heads—A spy—Letter to the
Duke Maximilian of Bavaria

CHAPTER IX.

Vessel hired for the Author’s departure—Lady 271


Hester’s intention of writing her Memoirs—Letter from
Lady Hester to Sir Francis Burdett—From Lady Hester
to Count Wilsensheim—Events of the Druze
insurrection—Inexpediency of M. Guys’s removal from
Beyrout—Letter from the Author to Count Wilsensheim
—Letter from Lady Hester Stanhope to the Baron de
Busech—Lady Hester immured—Principal reason of
the Author’s return to Europe—His adieux—Passage
to Cyprus—Reception by Signor Baldassare Mattei—
Provisions in Cyprus—Mademoiselle Longchamps—
Letter from Lady Hester to the Author—Commissions
—Second Letter from Lady Hester to the Author—
Third Letter from Lady Hester to the Author—Advice—
Obligations—Violence of temper—Mr. U.—General
Loustaunau—Logmagi and the muleteer—Fourth
Letter from Lady Hester to the Author—
Correspondence of the first Lord Chatham—Lady
Hester’s death—Conclusion
MEMOIRS

OF

LADY HESTER STANHOPE.


chapter i.
Prince Pückler Muskau—His letter to Lady Hester Stanhope—Story of the
Serpent’s Cave—Letter from Lady Hester to the Prince—Ride from Jôon to Sayda
—Cadi’s Justice—Madame Conti—Syrian surgeons.

March 20.—Lady Hester rose about three in the afternoon, and


went into her garden: I joined her about five o’clock. Spring had
already begun to display its verdant livery. The weather was
exceedingly fine, and every bush and tree seemed to have swollen
with sap, buds, and leaves, so that the eye could perceive a palpable
difference even from the preceding day. The birds were singing on
every branch (for nobody dared to molest them in this sacred spot),
and the bulbuls sat warbling a low but gentle music, which, now and
then, was broken in upon by their clear whistle, falling in cadences
on the ear like sweet concords. It was one of those hours which a
man, who feels himself in the decline of life, or gradually sinking
under disease, would most regret, in thinking that the harmony of
nature must soon close on him for ever.
Lady Hester had placed herself in a small white alcove, which
closed the vista at the bottom of a walk. A sofa, covered with
marone-coloured cloth, with flowered chintz cushions, ran across the
back of the alcove. On this she was leaning; and, being dressed in
her white abah with its large folds, she looked exactly like an antique
statue of a Roman matron. Half way up the avenue stood an
attendant in a handsome white Nizàm dress, which is exceedingly
becoming to youth, waiting her call. As I advanced towards her,
between two hedges—the one of double jessamine in full bud, and
the other of the bright green pervenche, or periwinkle-plant, with its
blue flowers, forming an azure band from one end to the other, I was
struck with the magical illusion which she ever contrived to throw
around herself in the commonest circumstances of life.
As I approached, she addressed me with more cheerfulness than
usual. “Do you know, doctor, that Prince Pückler Muskau is come to
Sayda, and has written me a very agreeable, and what appears to
be a very sincere, letter. Read it, and say what you think of it.”
Translated, it was as follows:

Prince Pückler Muskau to Lady Hester Stanhope.


March 20th, 1838.
My Lady,
As I am aware that you are but little fond of strangers’
visits, from having often found they proceeded from idle
curiosity, and sometimes even from more illiberal motives, I
freely confess, madam, it is not without some degree of
apprehension that, in my turn, I solicit permission to pay my
respects to you. Permit me, nevertheless, to assure you that,
for many years past, I have anticipated in fancy the pleasure
of knowing you, and that it would be a downright act of cruelty
on your part, if now, when the long wished-for moment is at
last arrived, you should refuse me the happiness of paying my
homage to the queen of Palmyra and the niece of the great
Pitt.
Besides, madam, I have the presumption to add that, from
what I have heard of you, there must exist some affinity of
character between us: for, like you, my lady, I look for our
future salvation from the East, where nations still nearer to
God and to nature can alone, some one day, purify the rotten
civilization of decrepit Europe, in which everything is artificial,
and where we are menaced, in a short time, with a new kind
of barbarism—not that with which states begin, but with which
they end. Like you, madam, I believe that astrology is not an
empty science, but a lost one. Like you, madam, I am an
aristocrat by birth and in principle; because I find a marked
aristocracy in nature everywhere. In a word, madam, like you,
I love to sleep by day and be stirring by night. There I stop;
for, in mind, energy of character, and in the mode of life, so
singular and so dignified, which you lead, not every one that
would can resemble Lady Hester Stanhope.
I close this letter, which already must appear too long to
you, in earnestly entreating you not to set down as mere
expressions the dictates of a heart artless and ingenuous,
though old. I am neither a Frenchman nor an Englishman: I
am but an honest and simple German, who perhaps lies open
to the charge of too much enthusiasm, but never to that of
flattery or insincerity.
[Signed] Prince of Puckler Muskau.
PS. Should you consent to my coming, might I presume to
beg of you still farther to allow me to bring Count Tattenbach,
a young man in my employ, who would be so much hurt to
see me set off without him that I am induced to risk the
request! Although severely wounded from a pistol-shot, he
would not remain at Acre, for fear of losing the opportunity of
paying his homage to you: nevertheless, your will, my lady,
and not mine, be done in everything.
When I had finished reading the letter, Lady Hester resumed:
“Now, doctor, you must go and see the prince at Sayda, for I can’t
see him myself. The fatigue is too great for the present; but I will
engage him to return again when I am better. I could wish you to say
many things to him; for I can see that he and I shall do very well
together: besides, I must be very civil to him; for he has got such a
tongue and such a pen! I think I shall invite him to come and see the
garden and the horses; but you must tell him the mare’s back is not
only like a natural saddle, but that there are two back bones for a
spine; that is the most curious part.—But no! if he comes it will fill my
house with people, and I shall be worried to death; it will only make
me ill: so I’ll write to him after dinner.
“What I would wish you to talk to him about is principally the
serpent’s cave. You must tell him that, at ten or twelve hours’
distance from Tarsûs, there is a grotto, where once lived an
enormous serpent with a human head, such as he may have seen in
paintings representing the temptation of Eve. This serpent was
possessed of all the skill in demonology and magic known on earth.
There was an ancient sage who was desirous of acquiring this
serpent’s wisdom, which he knew could be come at by destroying
the serpent: he therefore induced the king of the country in which the
grotto is situate to enter into his views, and, by the king’s orders, the
neighbouring peasantry were assembled for that purpose. The sage,
who had given instructions that, in killing the serpent, they were to
proceed in a particular manner, and that the head was to be
reserved for him, stationed himself not far off: and when the
peasants went as usual to carry his food, intending to seize a proper
moment for effecting the destruction of so formidable a reptile, the
serpent, being gifted with the power of speech, said, ‘I know what
you are come for; you are come to take my life. I am aware that I am
fated to die now, and I shall not oppose it: but, in killing me, beware
how you follow the instructions which the wicked man who sent you
gave—do exactly the reverse.’ The peasants obeyed the serpent;
and, doing precisely the reverse of what the sage had enjoined them
to do, the king too died, and thus met the reward of his treacherous
conduct. Since that time no other serpent has appeared with a
human head, but several are living in the same grotto, and they still
are fed by the neighbouring villages, which send the food at stated
times, and the people have opportunities of seeing them with their
own eyes.
“You must tell the prince that this story is perfectly authentic, and
that, since the time of Sultan Mûrad down to the present day, certain
villages are exempted from taxes in consideration of providing
sustenance for the serpents. As he naturally must wish to inquire into
and see so remarkable a phenomenon, you may tell him that, if he
puts himself into a boat, he can land at Tarsûs or Swadéya, and
thence find his way a few hours’ distance farther, where the grotto
is.”
I hung my head during the whole of this story, reflecting what a
pretty errand I was going upon—to tell with a serious air a story so
devoid of probability, and so likely to strengthen the supposition,
common in England and elsewhere, that Lady Hester was crazy. She
observed my ill-concealed incredulity, and bawled out rather than
said, “Do you understand what I have been telling you? I suppose
you’ll tell me I am mad. Do you believe these things or not? why
don’t you answer?” As I remained mute, she said, “Well, will you
repeat them to the prince as I have related them?” I answered, “Yes,
I would do that.”—“But there,” said she, “go to dinner now, and come
again in the evening: I suppose you are thinking more of your soup
getting cold than of anything else.”
It was now sunset, and I found my family waiting dinner for me:
but that was a very common occurrence, and excited no surprise.
Having dined, I returned to Lady Hester. She was in the drawing-
room, and she immediately renewed the subject of the grotto.
“The king’s name,” said she, “was Tarsenus—he gave the name
to Tarsûs, or took his from it, I don’t know which. You must not forget
to speak to the prince likewise of the dervises’ monastery, called
Sultan Ibrahim, which is near Tripoli. He has only to present himself
there, and use my name; they are all like my brothers; they have
many learned men amongst them: if he wants a letter to them, I’ll
give him one. As for the Ansaréas, the Ishmäelites, the Kelbëas, and
all the sects on the mountains between Tripoli and Latakia, he will
get nothing out of them; so it is of no use his trying. If he returns to
Jerusalem, beg him not to extend his excursions towards the back of
the Dead Sea, or beyond the Jordan; for, as he is known to be a
friend of Mahomet Ali’s, some Arab behind a rock may pick him off,
just out of spite to Ibrahim Pasha.”
Lady Hester went on. “Did you perfectly understand what I said
before dinner about the serpents?” “Not altogether,” I replied.
“Perhaps,” she observed, “you don’t like to go down to the prince?” I
replied, anxious to seize any excuse for getting rid of the serpent
story, “I can’t say I have any particular wish to go.”—“Why,” said
Lady Hester, “you have done nothing but talk about him for these last
five months; what was that for, if you don’t want to see him?”—“I
talked about him,” answered I, “because I thought, from what I had
read of his works, you would be pleased to see him, if he came this
way?”
Lady Hester paused a little while, and then proceeded:—“Well,
doctor, look here—you will talk a great deal about the serpents, and,
when you can see a proper opportunity, and that nobody is likely to
hear you, you will say to the prince in a low voice, ‘Lady Hester
recommends you to make some inquiries about the serpents’ cave[1]
when you are at Beyrout; for near to Tarsûs is Kolôok Bogàz, where
Ibrahim Pasha’s army is encamped: you will probably like to see it,
and this will be a good excuse, as everybody then will fancy you had
no political motive for going there.’”
The mystery was out; for two or three months Lady Hester had
been introducing the story of the human-headed serpent into her
conversations; for two or three months she had known of Prince
Pückler Muskau’s coming; for the same period I had entertained
apprehensions that her reason was impaired: M. Guys had been
primed in the same way, and formed the same conclusions; and all
turned out to be one of those long-laid plots, for which she was so
famous, to save the prince from being considered as a spy in the
dangerous neighbourhood of two hostile armies.
It had happened some years before, when the prince’s letters on
England were first translated, I, being in London, had noticed the
work in a letter to her, and had copied out a few observations on
herself made to the prince by a Hanoverian gentleman.
Subsequently, when with her, I had spoken of the prince’s increasing
reputation as a literary man, and mentioned such particulars of him
as had come to my knowledge. All this, and his alliance with the
family of Prince Hardenberg, with whom Lady Hester had been
acquainted, increased her desire to see him: but how to accomplish
it now was the difficulty. The few hours she spent with M. Guys had
done her a great deal of harm; for, being obliged to exert herself, and
not being able to treat a guest as unceremoniously as she could me,
the exertion proved too much for her strength. “Englishmen,” she
said, “are fond of turning everything into ridicule, and of saying
spiteful things of me; with the French and foreigners in general, it is
not so: and with a man of the world, like the prince, I have nothing to
fear on that score; but then how am I to lodge him and accommodate
his people and his dinners, with a wretched cook and nothing of any

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