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Chromatographic Analysis
of the Environment
Mass Spectrometry Based Approaches
FOURTH EDITION
Chromatographic Analysis
of the Environment
Mass Spectrometry Based Approaches
FOURTH EDITION

Edited by
Leo M. L. Nollet
Dimitra A. Lambropoulou
CRC Press
Taylor & Francis Group
6000 Broken Sound Parkway NW, Suite 300
Boca Raton, FL 33487-2742
© 2017 by Taylor & Francis Group, LLC
CRC Press is an imprint of Taylor & Francis Group, an Informa business

No claim to original U.S. Government works

Printed on acid-free paper

Version Date: 20170110

International Standard Book Number-13: 978-1-4665-9756-3 (Hardback)

This book contains information obtained from authentic and highly regarded sources. Reasonable efforts have been
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Library of Congress Cataloging-in-Publication Data

Names: Nollet, Leo M. L., 1948- editor. | Lambropoulou, Dimitra A., editor.
Title: Chromatographic analysis of the environment : mass spectrometry based approaches.
Description: Fourth edition / edited by Leo M. L. Nollet and Dimitra Lambropoulou. |
Boca Raton, FL : CRC Press, [2017]
Identifiers: LCCN 2016028978 | ISBN 9781466597563 | ISBN 9781315316208
Subjects: LCSH: Chromatographic analysis. | Environmental chemistry.
Classification: LCC QD79.C4 C48 2017 | DDC 628.5028/7--dc23
LC record available at https://lccn.loc.gov/2016028978

Visit the Taylor & Francis Web site at

http://www.taylorandfrancis.com
and the CRC Press Web site at
http://www.crcpress.com
 This book is dedicated to all victims of the attacks in
Brussels, Belgium, on March 22, 2016.
We hope it will compensate a very little bit for their
sufferances and the sorrows of their families.
It is also dedicated to the Greek people, who are going
through a very, very long period of uncertainty.

“When the going gets tough, the tough gets going.”

Contents
Preface...............................................................................................................................................xi
Editors ............................................................................................................................................ xiii
Contributors ..................................................................................................................................... xv

Section i Separation

Chapter 1 Gas Chromatography–Mass Spectrometry: Basic Concepts and Instrumentation ...... 3

Basil K. Munjanja

Chapter 2 LC-MS-Based Screening and Targeted Profiling Methods for Environmental

Analysis: Focus on Pharmacologically Active Compounds in the Aqueous
Environment and Critical Evaluation of Analytical Approaches...............................25
Barbara Kasprzyk-Hordern and Bruce Petrie

Chapter 3 High-Resolution Mass Spectrometric Techniques for Structural

Characterization and Determination of Organic Pollutants in the Environment....... 47
Nuria Cortés-Francisco and Josep Caixach

Chapter 4 Application of Thermal Desorption–Mass Spectrometry for the Analysis

of Environmental Pollutants ....................................................................................... 79
Steven Sai Hang Ho, Judith C. Chow, Jian Zhen Yu, John G. Watson,
Jun-Ji Cao, and Yu Huang

Section ii Sample Preparation and Sampling Strategies

Chapter 5 Sample Preparation Methods for Determination of Pollutants in Solid

and Complex Environmental Matrices..................................................................... 111
Carlos Gonçalves, Maria Augusta D. Sousa, Vasilios G. Samaras,
C. Marisa R. Almeida, and M. Clara P. Basto

Chapter 6 Application of Novel Materials in Sample Treatment and Separation:

Cleanup and Chromatographic Improvements......................................................... 199
Núria Fontanals

Chapter 7 Advances in Sample Preparation for Molecular Imprinting in Environmental

Applications.............................................................................................................. 221
George Z. Kyzas, Dimitrios Bikiaris, and Dimitra A. Lambropoulou

vii
viii Contents

Chapter 8 Sample Preparation Methods for Determination of Pollutants in Air Samples ....... 237
Francisco Pena-Pereira and Jacek Namieśnik

Chapter 9 Passive Sampling Strategies for Environmental Monitoring in Air and Aquatic
Environment ............................................................................................................. 265
Anna-Akrivi Thomatou and Ioannis Konstantinou

Section iii Quality Assurance

Chapter 10 Quality Assurance and Validation: General Considerations and Trends ................. 325
Roberta Galarini, Simone Moretti, and Giorgio Saluti

Chapter 11 Proficiency Testing in Environmental Analysis: Achievements and Challenges ..... 371
Charalampos Alexopoulos, Elias Kakoulidis, and Eugenia Lampi

Chapter 12 Reference Methods for the Measurement of Pollutants in Environmental Matrices....409

Leo M. L. Nollet

Section iV Air Pollutants

Chapter 13 Air Pollutants in the Outdoor Environment (NOx, SO2, VOCs, HAPs [CO, O3]).... 427
Carolina Santamaría, David Elustondo, Esther Lasheras,
and Jesús Miguel Santamaría

Section V Residues in Different Matrices

Chapter 14 Pharmaceuticals and Personal Care Products .......................................................... 453

Sergiane Souza Caldas, Ana Laura Venquiaruti Escarrone,
and Ednei Gilberto Primel

Chapter 15 Endocrine-Disrupting Chemicals: Presence in Environmental Matrices ................469

Ramiro Vallejo-Rodríguez, Mario Murillo-Tovar, Leonel Hernández-Mena,
and Alberto López-López

Chapter 16 Analysis of Plasticizers in Food and Environment .................................................. 491

Leo M. L. Nollet
Contents ix

Chapter 17 Instrumental Analysis of Brominated Flame Retardants ........................................ 515

Mohamed Abou-Elwafa Abdallah, Alin C. Dirtu, and Adrian Covaci

Chapter 18 Naphthenic Acids: Environmental Occurrence and Chromatographic Analysis..... 537

Adeola Adenugba, John V. Headley, Kerry Peru, and Dena McMartin

Section Vi transformation Products

Chapter 19 Occurrence of Transformation Products of Pharmaceutical and Personal Care

Products in the Aquatic Environment ...................................................................... 555
Myrsini Papageorgiou, Eleni Evgenidou, and Dimitra A. Lambropoulou

Outlook..........................................................................................................................................605

Index ..............................................................................................................................................609
Preface
Considerable analytical progress in chromatographic analysis has been made over the past decade,
when hyphenated techniques involving highly efficient separation and sensitive detection have
become the techniques of choice. Among them, methods based on chromatographic separation
with mass spectrometric detection have opened new perspectives in terms of identification and are
acknowledged as the major useful and authoritative methods for the determination of pollutants in
the environment.
Since the publication of the third edition of this book in 2005, the focus of chromatographic
research has changed again, and the variety of application fields that have been addressed in the
literature shows that, due to their versatility, chromatographic mass spectrometric techniques have
proven themselves successful in virtually any analytical challenge that makes them robust and
effectively applicable alternatives in pollutant analysis. Obviously, in comparison with different
detection methods, mass spectrometry or tandem mass spectrometry appears to be the technique of
choice in environmental analysis, as it provides reliable results at the subnanogram per liter or per
gram level, while the use of other specific detectors, such as flame-ionization detector, nitrogen–
phosphorus detector, and electron capture detector, has been in gradual decline. Mass spectrometric
analysis has increased exponentially during this time, and important progress has been made in
terms of instrumentation in order to increase the throughput, mass resolving power, mass accuracy,
tandem mass spectrometry capabilities, and resolution for mass spectrometry.
In this context, the main scope of the book is to outline those developments, which are particu-
larly relevant to environmental analysis, especially when using chromatographic mass spectromet-
ric techniques. Accordingly, the fourth edition has been largely changed and updated in comparison
with the previous ones to address these new issues, the new lines of discussions, and new findings.
This edition contains six sections. In Section I, an overview of principles, instrumental aspects,
and conceptual case studies in chromatographic analysis is given. The basic concepts and instru-
mentation of gas chromatography and liquid chromatography combined with mass spectrometry are
discussed. This section includes also a chapter on thermal desorption.
The five chapters in Section II detail sample preparation methods for the determination of pol-
lutants in air, in solid and complex environmental matrices, and in the aquatic environment. The
reader finds much information on novel materials and methods in sample treatment and separation.
Important aspects, such as quality assurance, validation, proficiency testing, and reference meth-
ods, are the elements of the contents of the three chapters of Section III.
Sections IV, V, and VI enumerate chromatographic methods on air pollutants (Section IV), on
environmental residues in different matrices (Section V, five chapters), and on transformation prod-
ucts of pharmaceutical and personal care products (Section VI). The five chapters of Section V
essentially deal with residues with endocrine-disrupting capacities.
Most of the data are compiled in tables and figures to elucidate the text. Presenting important
theoretical and practical aspects from sample collection to laboratory analysis, Chromatographic
Analysis of the Environment, Fourth Edition, is a unique resource of chromatographic techniques,
data, and references that are useful to all scientists involved in the analysis of environmental
compounds.

xi
xii Preface

The redaction of this book was not without obstacles and difficulties. These obstacles were
largely due to severe health issues and other less severe issues of both editors. These health issues
have now been overcome.
We are very thankful to all the contributors for their excellent input and especially for their time
and patience.
I would like to give a kiss to Dimitra for her help, wisdom, and courage.

Leo M. L. Nollet
Dimitra A. Lambropoulou
Editors
Leo M. L. Nollet, PhD, earned an MS (1973) and a PhD degree (1978) in biology from Katholieke
Universiteit Leuven, Leuven, Belgium. He is an editor and associate editor of numerous books. He
edited for Marcel Dekker, New York—now CRC Press of Taylor & Francis—the first, second, and
third editions of Food Analysis by HPLC and Handbook of Food Analysis. The last edition is a
two-volume book. He also edited Handbook of Water Analysis (first, second, and third editions) and
Chromatographic Analysis of the Environment, third edition (CRC Press).
With Fidel Toldrá, he coedited two books published in 2006 and 2007: Advanced Technologies
for Meat Processing (CRC Press) and Advances in Food Diagnostics (Blackwell Publishing—now
Wiley). With Michael Poschl, he coedited the book Radionuclide Concentrations in Foods and the
Environment, also published in 2006 (CRC Press).
Dr. Nollet has also coedited with Y. H. Hui and other colleagues several books: Handbook
of Food Product Manufacturing (Wiley, 2007), Handbook of Food Science, Technology and
Engineering (CRC Press, 2005), Food Biochemistry and Food Processing (first and second edi-
tions; Blackwell Publishing, 2006 and 2012), and Handbook of Fruits and Vegetable Flavors
(Wiley, 2010). In addition, he edited Handbook of Meat, Poultry and Seafood Quality, first and
second editions (Blackwell Publishing, 2007 and 2012).
From 2008 to 2011, he published with Toldrá five books on animal products, namely, Handbook
of Muscle Foods Analysis, Handbook of Processed Meats and Poultry Analysis, Handbook of
Seafood and Seafood Products Analysis, Handbook of Dairy Foods Analysis, and Handbook of
Analysis of Edible Animal By-Products. In 2011, also with Toldrá, he coedited for CRC Press two
books: Safety Analysis of Foods of Animal Origin and Sensory Analysis of Foods of Animal Origin.
In 2012, they both published Handbook of Analysis of Active Compounds in Functional Foods.
Coedited with Hamir Rathore, the book Handbook of Pesticides: Methods of Pesticides Residues
Analysis was marketed in 2009, Pesticides: Evaluation of Environmental Pollution in 2012, and
Biopesticides Handbook in 2015.
Other finished book projects include Food Allergens: Analysis, Instrumentation, and Methods
(with Arjon van Hengel; CRC Press, 2011) and Analysis of Endocrine Compounds in Food (Wiley-
Blackwell, 2011).
Dr. Nollet’s recent projects include Proteomics in Foods with Toldrá (Springer, 2013) and
Transformation Products of Emerging Contaminants in the Environment: Analysis, Processes,
Occurrence, Effects and Risks with Dimitra A. Lambropoulou (Wiley, 2014).
This CRC series, Food Analysis & Properties, was edited by Dr. Nollet with Claudia Ruiz-
Capillas and includes Flow Injection Analysis of Food Additives (CRC Press, 2015) and Marine
Microorganisms: Extraction and Analysis of Bioactive Compounds (CRC Press, 2016).

Dimitra A. Lambropoulou, PhD, is currently assistant professor of environmental chemistry in

the Environmental Pollution Control Laboratory, Department of Chemistry, Aristotle University
of Thessaloniki. She earned her PhD in chemistry from University of Ioannina in 2002. Up till
now, she has published over 75 publications in high-impact international peer-reviewed scientific
journals. With Leo M. L. Nollet, she coedited a book published by John Wiley & Sons, Inc in 2014:
Transformation Products of Emerging Contaminants in the Environment: Analysis, Processes,
Occurrence, Effects and Risks. Her main research interests are the development and application
of novel sample preparation techniques coupled to advanced mass spectrometry approaches in
the field of environmental chemistry, design and application of new materials in analytical and
separation sciences, high resolution mass spectrometry, occurrence, transport, fate and effects of
emerging contaminants in the environment. She is also interested in the development of effective
degradation and purification processes for the mineralization of organic micropollutants.

xiii
Contributors
Mohamed Abou-Elwafa Abdallah Josep Caixach
Division of Environmental Health and Risk Mass Spectrometry Laboratory/Organic
Management Pollutants
School of Geography, Earth and Environmental Institute of Environmental Assessment
Sciences and Water Research
University of Birmingham Spanish Council for Scientific Research
Birmingham, United Kingdom Barcelona, Spain
and
Department of Analytical Chemistry Jun-Ji Cao
Faculty of Pharmacy State Key Lab of Loess and Quaternary Geology
Assiut University Institute of Earth Environment
Assiut, Egypt Chinese Academy of Sciences
Xi’an, People’s Republic of China
Adeola Adenugba
Faculty of Engineering Judith C. Chow
University of Regina Division of Atmospheric Sciences
Regina, Canada Desert Research Institute
Reno, Nevada
Charalampos Alexopoulos
General Chemical State Laboratory Nuria Cortés-Francisco
Chemical Metrology Service Mass Spectrometry Laboratory/Organic
Athens, Greece Pollutants
Institute of Environmental Assessment
C. Marisa R. Almeida and Water Research
Interdisciplinary Centre of Marine and Spanish Council for Scientific Research
Environmental Research and
University of Porto Laboratori de l’Agència de Salut Pública
Porto, Portugal de Barcelona
Barcelona, Spain
M. Clara P. Basto
Interdisciplinary Centre of Marine and Adrian Covaci
Environmental Research Toxicological Center
and Department of Pharmaceutical Sciences
Faculty of Sciences University of Antwerp
University of Porto Antwerp, Belgium
Porto, Portugal
Alin C. Dirtu
Dimitrios Bikiaris Toxicological Center
Laboratory of Polymer Chemistry and Department of Pharmaceutical Sciences
Technology University of Antwerp
Department of Chemistry Antwerp, Belgium
Aristotle University of Thessaloniki and
Thessaloniki, Greece Department of Chemistry
“Al. I. Cuza” University of Iași
Iași, Romania

xv
xvi Contributors

David Elustondo Yu Huang

Integrated Laboratory for Environmental Key Lab of Aerosol Chemistry and Physics
Quality Institute of Earth Environment
Department of Chemistry and Soil Science Chinese Academy of Sciences
School of Sciences Xi’an, People’s Republic of China
University of Navarra
Pamplona, Spain Elias Kakoulidis
General Chemical State Laboratory
Eleni Evgenidou Chemical Metrology Service
Department of Chemistry Athens, Greece
Aristotle University of Thessaloniki
Thessaloniki, Greece Barbara Kasprzyk-Hordern
Department of Chemistry
Núria Fontanals University of Bath
Departament de Química Analítica i Química Bath, United Kingdom
Orgànica
Universitat Rovira i Virgili Ioannis Konstantinou
Tarragona, Spain Department of Chemistry
University of Ioannina
Roberta Galarini Ioannina, Greece
Center for Development and Validation
of Methods George Z. Kyzas
Istituto Zooprofilattico Sperimentale Laboratory of Polymer Chemistry
dell’Umbria e delle Marche and Technology
Perugia, Italy Department of Chemistry
Aristotle University of Thessaloniki
Carlos GonÇalves Thessaloniki, Greece
Interdisciplinary Centre of Marine and
Environmental Research Dimitra A. Lambropoulou
University of Porto Environmental Pollution Control Laboratory
Porto, Portugal Department of Chemistry
Aristotle University of Thessalonikis
John V. Headley Thessaloniki, Greece
Environment and Climate Change Canada
Saskatoon, Canada Eugenia Lampi
General Chemical State Laboratory
Leonel Hernández-Mena Chemical Metrology Service
Centro de Investigación y Asistencia en Athens, Greece
Tecnología y Diseño del Estado de Jalisco
Guadalajara, Mexico Esther Lasheras
Integrated Laboratory for Environmental
Steven Sai Hang Ho Quality
Division of Atmospheric Sciences Department of Chemistry and Soil Science
Desert Research Institute School of Sciences
Reno, Nevada University of Navarra
and Pamplona, Spain
Key Lab of Aerosol Chemistry and Physics
Institute of Earth Environment Alberto López-López
Chinese Academy of Sciences Centro de Investigación y Asistencia en
Xi’an, People’s Republic of China Tecnología y Diseño del Estado de Jalisco
Guadalajara, Mexico
Contributors xvii

Dena McMartin Bruce Petrie

Faculty of Engineering Department of Chemistry
University of Regina University of Bath
Regina, Canada Bath, United Kingdom

Simone Moretti Ednei Gilberto Primel

Center for Development and Validation Escola de Química e Alimentos
of Methods Universidade Federal do Rio Grande
Istituto Zooprofilattico Sperimentale Rio Grande, Brazil
dell’Umbria e delle Marche
Perugia, Italy Giorgio Saluti
Center for Development and Validation
Basil K. Munjanja of Methods
Department of Applied Chemistry Istituto Zooprofilattico Sperimentale
National University of Science and Technology dell’Umbria e delle Marche
Bulawayo, Zimbabwe Perugia, Italy

Mario Murillo-Tovar Vasilios G. Samaras

Centro de Investigación y Asistencia en Water and Air Quality Laboratory
Tecnología y Diseño del Estado de Jalisco Department of Environment
Guadalajara, Mexico University of the Aegean
Mytilene, Greece
Jacek Namieśnik
Department of Analytical Chemistry Carolina Santamaría
Chemical Faculty Integrated Laboratory for Environmental
Gdańsk University of Technology Quality
Gdańsk, Poland Department of Chemistry and Soil Science
School of Sciences
Leo M. L. Nollet University of Navarra
University College Ghent (Retired) Pamplona, Spain
Ghent, Belgium
Jesús Miguel Santamaría
Myrsini Papageorgiou Integrated Laboratory for Environmental
Department of Chemistry Quality
Aristotle University of Thessaloniki Department of Chemistry and Soil Science
Thessaloniki, Greece School of Sciences
University of Navarra
Francisco Pena-Pereira Pamplona, Spain
Analytical and Food Chemistry Department
Faculty of Chemistry Maria Augusta D. Sousa
University of Vigo Faculty of Pharmacy
Vigo, Spain University of Porto
and Porto, Portugal
Department of Analytical Chemistry
Chemical Faculty Sergiane Souza Caldas
Gdańsk University of Technology Escola de Química e Alimentos
Gdańsk, Poland Universidade Federal do Rio Grande
Rio Grande, Brazil
Kerry Peru
Environment and Climate Change Canada
Saskatoon, Canada
xviii Contributors

Anna-Akrivi Thomatou John G. Watson

Department of Chemistry Division of Atmospheric Sciences
University of Ioannina Desert Research Institute
Ioannina, Greece Reno, Nevada

Ramiro Vallejo-Rodríguez Jian Zhen Yu

Centro de Investigación y Asistencia en Department of Chemistry
Tecnología y Diseño del Estado de Jalisco Hong Kong University of Science
Guadalajara, Mexico and Technology
Kowloon, Hong Kong
Ana Laura Venquiaruti Escarrone
Instituto de Ciências Biológicas
Universidade Federal do Rio Grande
Rio Grande, Brazil
Section I
Separation
 1 Gas Chromatography–Mass
Spectrometry
Basic Concepts
and Instrumentation
Basil K. Munjanja

CONTENTS
1.1 Introduction ..............................................................................................................................3
1.2 Sample Introduction..................................................................................................................4
1.3 Separation .................................................................................................................................5
1.3.1 Fast Gas Chromatography ............................................................................................6
1.3.2 Comprehensive Two-Dimensional Gas Chromatography ............................................ 8
1.3.3 Low-Pressure Gas Chromatography.............................................................................9
1.4 Ionization Techniques ...............................................................................................................9
1.4.1 Electron Impact Ionization ...........................................................................................9
1.4.2 Chemical Ionization.................................................................................................... 10
1.4.3 Atmospheric Pressure Ionization ................................................................................ 10
1.5 Mass Analyzers....................................................................................................................... 13
1.5.1 Single Quadrupole Mass Analyzer (GC-MS) ............................................................. 13
1.5.2 Ion Trap Mass Analyzer ............................................................................................. 15
1.5.3 Triple Quadrupole Mass Analyzer ............................................................................. 16
1.5.4 Time-of-Flight Mass Analyzer ................................................................................... 17
1.6 Future Trends and Conclusion ................................................................................................ 17
References ........................................................................................................................................ 18

1.1 INTRODUCTION
Gas chromatography–mass spectrometry (GC-MS) continues to play a pivotal role in environmental
analysis of pollutants despite the increasing use of liquid chromatography–MS by most research
groups. This is because of the high separation efficiency of GC and the wide range of mass analyz-
ers that it can be coupled to simplify analysis of pollutants in complex environmental matrices.
Examples of pollutants include nonpolar and thermally labile analytes such as polyaromatic hydro-
carbons (PAHs), pesticides, polychlorinated biphenyls (PCBs), water disinfection by-products, poly-
chlorinated dibenzo-p-dioxins and furans (PCDD/F), and endocrine disruptors, some of which are
shown in Figure 1.1. In addition, GC-MS can also be applied in the analysis of polar substances such
as pharmaceuticals and personal care products, only after derivatization (Subedi et al., 2011). To
date the use of this technique in environmental analysis is on an upward trend because of the very
high separation efficiency of GC coupled to the high sensitivity offered by MS. In view of this, it is
critical that we discuss the basic concepts of GC-MS and all the essential aspects of instrumentation
in this chapter. Moreover, we discuss recent advancements in sample introduction, chromatographic
separation, mass analyzers, and the different applications of GC-MS in environmental analysis.

3
4 Chromatographic Analysis of the Environment

CI

CI CI

CI CI
Benzo[a]pyrene

Br Br Br Br

Br O Br N

Br Br Br Br O NH2

Decabromopiphenylether (BDE209) Carbamazepine

O CH3

Cl
N CH3

Propachlor

FIGURE 1.1 Chemical structures of some GC-MS-amenable organic compounds.

1.2 SAMPLE INTRODUCTION

The first stage in GC-MS is sample introduction. It is important to note that a good injection tech-
nique should not compromise the separation efficiency and should not induce a change in the sample
composition. Hence, depending on the physical properties of the analyte such as physical state,
chemical stability, and thermal degradation, one can choose between thermal desorption (TD) and
large volume injection (LVI) techniques (Hird, 2008). TD techniques involve the removal of volatile
(Ribes et al., 2007) or semivolatile analytes (Falkovich and Rudich, 2001) from solid matrices by
heated gas flow and their subsequent extraction into a stream of inert gas and their transfer to the
gas chromatograph in a small volume of concentrated vapor. TD techniques come in various forms,
and their advantages are low costs and reduced labor requirements. However, their major drawback
is the reduced sensitivity as the number of samples increases (Ho et al., 2011). Furthermore, other
forms of TD suffer from the drawback of needing to modify the injector port and an additional
transfer line. For this reason, in-injector port TD is the most common form used in environmental
analysis, offering an additional advantage of high transfer efficiency because of the elimination of
transfer lines between the sample and the analytical instrument. Thus, it has been widely used in
the analysis of volatile organic compounds, explosives, and aerosol organics (Ho and Yu, 2004).
The use of unusually high injection volumes greater than 2 μm in LVI is an important feature
that improves the sensitivity of the technique and simplifies the sample preparation step. In addition,
LVI can serve as an interface for the automation of sample preparation steps such as solid-phase
Gas Chromatography–Mass Spectrometry 5

extraction (SPE) with GC (Hoh and Mastovska, 2008). The traditional LVI techniques such as on-
column, programmed temperature vaporization (PTV) in solvent split mode had serious drawbacks
with volatile analytes and high-molecular weight analytes (Li et al., 2009). However, newer modes
of LVI, including direct sample introduction, splitless overflow, at-column and through-oven trans-
fer adsorption–desorption overcome these drawbacks.
Some compounds may degrade in the injection port because either they lack thermal lability or
they have relatively high polarity (Lambropolou and Hela, 2015). For such, an additional step of
derivatization is done by silylation, acylation, or alkylation (Yang and Shin, 2013). For instance, in
the analysis of seven pharmaceuticals and personal care products (PPCPs) in biosolids, after opti-
mization of derivatization conditions, N,O-bis(trimethylsilyl)-trifluoroacetamide and 1% trimeth-
ylchlorosilane was used because it allowed effective detection of all polar compounds (Rice and
Mitra, 2007). However, a major drawback of derivatization is that it is time consuming and some of
the derivatization agents may damage the column.

1.3 SEPARATION
The column is the heart of the GC because separation takes place there. Earlier on, packed columns
were used, but their use has since been discontinued because of their lower resolution when applied
to the analysis of many compounds. They have since been replaced by the capillary column, which
provides better resolution and increases the speed of analysis when coupled to a mass spectrometer.
GC analysis can be one dimensional (1D), where one column is used, or two dimensional (2D),
where two columns are used. In both cases, separation takes place based on the partition of the ana-
lyte between the mobile phase and the stationary phase. The mobile phase is usually nitrogen gas
or helium, but the stationary phase can be polar (made from polyethylene glycol) or apolar (dimeth-
ylsiloxane, etc.). Thus, the selection of the stationary phase depends on the nature of the analytes.
For instance, in the analysis of fatty acids such as methyl esters, polar stationary phases coated with
polyethylene glycol (DB-WAX) or with bis(cyanopropyl) siloxane (e.g., BPX70) are used because
they allow the differentiation of fatty acids with different carbon numbers, unsaturations, locations,
and geometries of double bonds (Gu et al., 2011).
However, nowadays, a recent development is the use of ionic liquids as a new class of stationary
films in capillary films with remarkable properties and benefits for GC-MS such as low volatility,
high thermal stability, and selectivity toward certain chemical (Ballesteros-Gomez and Rubio, 2011).
Initially, molten salts were first used as GC stationary phases. However, imidazolium-based ionic liq-
uids that have higher viscosity, broader liquid range, and higher thermal stability have since replaced
these. Other types of ionic liquids that are now used include dicationic ionic liquids, functionalized
ionic liquids, and polymerized ionic liquids (Yao and Anderson, 2009). Ionic liquids were tested in
1D-MS and 2D-MS in the analysis of fatty acid methyl esters from algae. The ionic liquid stationary
phases showed comparable resolution but lower column bleeding, with MS detection resulting in
better sensitivity as compared to polyethylene glycol- and cyanopropyl-substituted polar stationary
phases (Gu et al., 2011). It is worth noting that despite the unique selectivity that ionic liquids offer,
they have not achieved the separation efficiency of polysiloxanes (Dorman et al., 2010). For this
reason, different authors have proposed methods of combining polysiloxanes and ionic liquids based
on their merits. For instance, Sun et al. (2010) synthesized an ionic liquid-bonded polysiloxane as a
stationary phase, and it was used to construct an 8 m capillary column. The stationary phase showed
good film-forming ability and high durability. In addition, it had stronger dispersive forces than the
neat ionic liquid due to the presence of the polysiloxane skeleton. This accounted for its good selec-
tivity and high separation efficiency for a wide range of analytes (Sun et al., 2010).
In addition to ionic liquids, other types of stationary phases such as graphene (Fan et al., 2015),
graphene oxide (Feng et al., 2015), cyclotriveratrylene (CTV; Lv et al., 2015), and cyclodextrins (Shi et
al., 2001; Grisales et al., 2009) are still being tried out by various research groups in a bid to increase
the separation efficiency of GC. In most of these studies, high separation efficiency is being obtained
6 Chromatographic Analysis of the Environment

1,4-Dichlorobenzene

1,2,4-Trichlorobenzene
1,3-Dichlorobenzene

1,3,5-Dichlorobenzene

1,2,3-Trichlorobenzene
n-Propylbenzene
Isopropylbenzene

scc-Butylbenzene

1,2-Dichlorobenzene
n-Butylbenzene
1.2 1.4 1.6 rar-Butylbenzene
1.5 2.0 3 4 5 1.2 1.5
Time (min) Time (min) Time (min) Time (min)
1,2,4-Trimethylbenzene

trans-1,3-Dichloropropene

1,1,12-Tetrachlorocthane
1,3,5-Trimethylbenzene

cis-1,3-Dichloropropene
1,2,3-Trimethylbenzene

1,1,2,2-Tetrachlorocthane
1.5 1.8 1.1 1.2 1.2 1.5
Time (min) Time (min) Time (min)

FIGURE 1.2 Chromatograms for GC separations of isomers on CTV capillary column. (Reproduced from
Journal of Chromatography A, 1404, Lv, Q., Q. Zhang, M. Qi, H. Bai, Q. Ma et al., Cyclotriveratrylene as
a new-type stationary phase for gas chromatographic separations of halogenated compounds and isomers,
89–94, Copyright (2015), with permission from Elsevier.)

for most organic compounds that compares very well with those of the conventional columns. Feng
et al. (2015) explored the separation performance of grapheme oxide nanosheets as a stationary phase
for the hydrogen bonding analytes such as alcohols and amines. Better separation compared to con-
ventional columns was obtained, because the stationary phase interacts with the analytes by either
hydrogen bonding, dipole–dipole, or dispersive interactions (Feng et al., 2015). In different studies,
moreover, a remarkable feature of the new-generation stationary phases is their enhanced ability to
resolve isomers of many organic compounds. For instance, Lv et al. (2015) investigated the potential
of CTV as a stationary phase for GC separations. An important feature of the stationary phase was
the excellent selectivity for halogenated compounds and positional and geometrical isomers (Lv et
al., 2015), as shown in Figure 1.2. In a different study, Shi et al. (2001) found cyclodextrin phenyl
carbamate to have good separation ability when it comes to disubstituted benzene isomers. Concisely,
these developments in stationary phase will improve GC separations in the future, although their
application in the environmental analysis of organic pollutants now is still scarce.

1.3.1 Fast Gas ChromatoGraphy

A major challenge for analytical chemists has always been to increase the sample throughput and
minimize time wasted during analysis. Conventional capillary columns are as long as 30 m, thus
increasing the analysis time. Thus, fast GC seeks to maintain the efficient separation of the GC pro-
cess by altering the analysis time. Most of these changes have been done on the column itself. Fast
GC utilizes a number of approaches outlined as follows:
Gas Chromatography–Mass Spectrometry 7

• Reduced column length and narrow internal diameter: Most fast GC columns do not exceed
20 m in length, and their internal diameters vary from 0.10 to 0.18. The narrow internal diam-
eters increase the separation efficiency by providing a higher signal-to-noise ratio, leading
to higher sensitivity. Furthermore, less band broadening occurs in the narrow 1D columns
because the analytes are diluted in a small volume of carrier gas (Banerjee and Utture, 2015).
• Fast temperature programming: This can be achieved using conventional ovens, resistive
heating, or microwave ovens. To ensure that fast GC is achieved, the rate of temperature
programming must be fast and so must the cooldown and equilibration times. This is
where conventional ovens have a limitation because they can achieve rates of only 1–2°C
s−1, which is very slow (Mastovska and Lehotay, 2003). Resistive heating can achieve tem-
perature programming rates of up to 20°C s−1 through the heating of a metal that encases
the column and then determining the temperature by resistance measurements (Mastovska
et al., 2001). Compared to the conventional oven, it offers rapid cooldown rates that result
in higher sample throughput and very good repeatability of retention time is obtained.
Furthermore, it also offers improved peak capacity and peak width compared to an iso-
thermal separation (Reid et al., 2007). However, faster temperature programming leads to
higher compound elution temperature, decreased separation efficiency, and greater ther-
mal breakdown of susceptible analytes. For this reason, it is often combined with other
techniques such as using a microbore column and a thin film of stationary phase in order
to reduce the analysis time (Xu et al., 2008).
• Altered stationary phase: The use of a thin film of stationary phase ensures the rapid parti-
tioning of analytes back into the carrier gas stream. This avoids band broadening. A column
with a narrow internal diameter with a thin film of stationary phase has limited sample
capacity compared to a conventional column. For this reason a smaller amount of sample is
injected onto the column to avoid distorted peak shapes (Banerjee and Utture, 2015).
• Higher flow rate of carrier gas: A faster carrier gas flow rate causes the analytes to travel
quickly through the column, leading to reduced analysis times. However, the carrier gas
velocity should be optimized, as deviations might lead to reduced separation efficiency. Flow
rates above the optimum value result in a reduced signal-to-noise ratio. On the other hand,
lower velocities result in poor peak shapes and longer run times (Banerjee and Utture, 2015).
• Microbore columns: The specifications of the column are outlined in Table 1.1. Fast GC
with microbore columns provides improved separation efficiency at reduced analysis times
compared to conventional capillary columns (Húsková et al., 2009). However, their draw-
back is low sample capacity, which may cause band broadening, tailing, and ghost peaks
(Kirchner et al., 2005).

TABLE 1.1
Classification of Capillary Columns
Column Diameter Standard Commercial Max. Flow Rate
Category Range (mm) Column Diameters (mm) (mL min−1)
Megabore ≥0.5 0.53 ≥660
Wide bore ≥0.3 to <0.5 0.32, 0.45 ≥85 to <660
Narrow bore ≥0.2 to <0.3 0.20, 0.25, 0.28 ≥17 to <86
Microbore ≥0.1 to <0.2 0.10, 0.15, 0.18 ≥1 to <17
Sub-microbore <0.1 Various <1

Source: Reproduced from Journal of Chromatography A, 1000, Mastovska, K., and

Lehotay, S.J., Practical approaches to fast-gas chromatography, 153–180,
Copyright (2003), with permission from Elsevier.
8 Chromatographic Analysis of the Environment

1.3.2 Comprehensive two-Dimensional Gas ChromatoGraphy

The use of multidimensional gas chromatography (MDGC) coupled to MS is on the increase.
MDGC, also known as 2D-GC, is a separation technique that relies on two columns for enhanced
resolving power. The main approaches use the same hardware, but operate differently, viz., heart-
cutting 2D-GC and comprehensive two-dimensional gas chromatography (GC×GC). Of these
two techniques, many reviews have been published on the latter, covering areas such as principles
and developments in instrumentation (Adahchour et al., 2005; Mondello et al., 2008), detection
techniques (Adahchour et al., 2006a), and applications (Adahchour et al., 2006b,c; Mitrevski et al.,
2011). This shows that the applications of the latter are more than those of the former. This is partly
because GC×GC allows solute band concentration, which consequently enables detection of trace
volatile substances with minimum interference from matrix components (Mondello et al., 2008).
Heart-cutting 2D-GC is famous for performing genius separations using the so-called heart-
cutting technique, which is the passing of only a small fraction of the eluate from the primary
column to the secondary column with the aid of an interface that switches on and off periodically.
It follows that the technique offers high resolving power to a limited number of analytes (Seeley
and Seeley, 2013). However, major drawbacks of this technique stem from the partial analysis of
the sample in the two different dimensions and to the increased analysis time, thus not improving
on the limitations of 1D-GC. Furthermore, the instrumentation is very complex and requires great
skill to operate.
Liu and Philips (1991) overcame these limitations by producing a high-frequency heart-cutting
separation of the entire sample and introduced GC×GC or 2D-GC. Compared to heart-cutting
2D-GC, where a fraction of the analyte from the primary column is separated in the secondary
column, in GC×GC, the entire effluent of the primary column can pass to the secondary column,
where it is also separated. The combination of the nonpolar primary column and the polar second-
ary column through the thermal modulator provides adequate separation efficiency for complex
mixtures with a large number of compounds in a single analytical run (Seeley and Seeley, 2013).
The high separation efficiency lies in the fact that the compounds are analyzed twice—that is, in
both the primary and secondary columns. Moreover, the nonpolar primary column separates com-
pounds by dispersive forces and not intermolecular forces, thus increasing the separation efficiency
(Gorecki et al., 2006). The modulator transfers part of the effluent from the primary column in the
form of a pulse. The time between the transfers is called the modulation period. Modulation results
in cryofocusing of the narrow bands of each compound, leading to very narrow signals eluting from
the secondary column (Banerjee and Utture, 2015). For this reason, 2D-GC is coupled to very fast
detectors such as the time-of-flight (TOF) mass analyzers that were dominant in previous years.
However, because of the high cost of TOF analyzers, many authors have recently made efforts to
couple 2D-GC to quadrupole (Purcaro et al., 2010) and triple quadrupole (QqQ) mass analyzers
(Tranchida et al., 2013). They have been successful because the mass analyzers are now capable
of operating at high scan speeds that are comparable to those of the TOF ones. Most recently,
Mitrevski and Marriot (2014) discovered that 2D-DC and a quadrupole time-of-flight (QTOF) mass
analyzer complement each other in the analysis of isobaric compounds. For simple cases where
QTOF mass spectrometry fails to differentiate isobaric compounds, 2D-GC is able to do so. In addi-
tion, where 2D-GC fails in separation, a QTOF mass analyzer makes use of mass filtering, and in
the case of coeluting isobaric compounds, a QTOF mass analyzer can be used in tandem with mass
analysis (tandem mass spectrometry [MS/MS] mode) (Mitrevski and Marriot, 2014).
A distinct advantage of 2D-GC over 1D-GC is the ease with which analyte identification can
be carried out, as each peak is described by two retention times as compared to one in the latter.
In addition, chemometric tools can also assist in peak identification, especially when chromato-
graphic conditions such as oven temperature may change from run to run (Gorecki et al., 2006). A
comprehensive review published by Pierce and Mohler describes the chemometrics used in terms
of unsupervised, supervised, preprocessing, resolution, and image analysis algorithms (Pierce and
Gas Chromatography–Mass Spectrometry 9

Mohler, 2012). In addition, they also discussed the factors that affect the conversion of data into
useful information.
Many authors have reported the use of 2D-GC coupled to MS in environmental analysis of
organic pollutants. Megson et al. used 2D GC coupled to time-of-flight mass spectrometry (TOFMS)
to fingerprint PCBs in environmental samples (Megson et al., 2013). In a different study, chlorinated
and brominated PAHs were analyzed in environmental samples such as soil by using 2D-GC cou-
pled to high-resolution time-of-flight mass spectrometry (HR-TOFMS) with very high selectivity
(Ieda et al., 2011). Another method was reported for ultratrace analysis of organochlorine pesticides
in water by using 2D-GC coupled to HR-TOFMS (Ochiai et al., 2011). A review was published on
the application of 2D-GC in the analysis of illicit drugs (Mitrevski et al., 2011). Another review was
published to summarize some of the applications of 2D-GC/MS in the analysis of polybrominated
diphenyl ethers (PBDEs) (Król and Namie, 2012). Lima Gomes et al. (2013) analyzed for steroids,
caffeine, and methylparaben in water samples by using automated solid-phase microextraction
(SPME) with 2D-GC–TOF-MS.

1.3.3 low-pressure Gas ChromatoGraphy

Low-pressure GC uses a short microbore column at the injector side, connected to a zero dead vol-
ume connector to a short megabore column (10 m × 0.53 mm) to be used with higher gas velocities.
Injection is carried out at atmospheric pressure while the column is operated at lower pressures that
are compatible with different mass analyzers (Ravindra et al., 2008). Consequently, the helium car-
rier gas becomes more viscous and behaves more like hydrogen, thereby shifting the optimal flow
velocity from the Van Deemter equation, which increases the flow rates (Koesukwiwat et al., 2010).
The increased flow rates result in reduced interaction with the active sites in the inlet (Banerjee and
Utture, 2015). The advantages of low-pressure GC compared to those of conventional GC include
shorter run times, enhanced sensitivity, reduced peak tailing, and increased ruggedness (due to
wider column and thicker film) (Koesukwiwat et al., 2011). In addition, they also offer reduced
degradation of thermally labile analytes and high sample loadability (Dirtu et al., 2008). However,
the major drawback is that the high flow rates used may increase the pressure in the ion source to an
intolerable limit, which may result in damage of the filament, especially when chemical ionization
(CI) is used (Ravindra et al., 2008). Low-pressure GC has been applied in environmental analysis
by using different mass analyzers such as single quadrupole (Hájková et al., 2007), ion trap (IT)
(Joos et al., 2003; Ravindra et al., 2006), GC-QqQ (Gonzalez-Rodriguez et al., 2002; Fernandes et
al., 2014), and TOF mass analyzers (Cajka et al., 2008; Lehotay et al., 2011).

1.4 IONIZATION TECHNIQUES

1.4.1 eleCtron impaCt ionization
In electron impact ionization (EI), the gaseous analyte is bombarded by a beam of electrons at
70 eV. Consequent ionization of molecules takes place by the loss of one electron. The use of 70 eV
electrons results in transfer of sufficient energy, which results in structurally informative fragmenta-
tion and the generation of reproducible mass spectra. Consequently, because of this benefit, exten-
sive libraries such as those of National Institute of Standards and Technology (NIST) and Wiley are
compiled for 70 eV EI spectra (Banerjee and Utture, 2015). Thus, electron ionization is preferred
for identifying unknowns, determining molecular structure, and confirming target the compound’s
identity through consistent ion abundance ratios (Banerjee and Utture, 2015). In EI, the ion source
temperature is an important parameter that influences the extent of analyte ionization and fragmen-
tation. It is usually set at a high value of approximately 220–240°C in order to increase ionization
efficiency (Gómez et al., 2009; Prieto et al., 2010). However, it is important to note that the optimum
value of ion source temperature varies with the instrument vendor.
10 Chromatographic Analysis of the Environment

1.4.2 ChemiCal ionization

The extensive fragmentation of EI can also be a disadvantage, as it leaves no trace of the molec-
ular ion, making it difficult to determine the molecular weight (Hajslova and Cajka, 2007). For
this reason, CI, which is a soft ionization technique and does not produce extensive fragmenta-
tion, is used as an alternative. CI operates in two modes—namely, positive chemical ionization
(PCI) and negative chemical ionization (NCI). In PCI, the ion source is filled with a reagent gas,
such as methane, at a relatively high pressure—that is, ionized using EI to produce reagent ions.
The sample molecules are ionized by the reagent gas, producing pseudomolecular ions that have
less internal energy and are less prone to fragmentation than the molecular ions generated by EI.
Thus, because of the reduced fragmentation in PCI, intense and more specific molecular ions are
obtained and, consequently, unambiguous identification can be obtained. Furthermore, lower detec-
tion limits and increased sensitivity are obtained due to the reduction in background noise (Banerjee
and Utture, 2015).
The principle of NCI is the same as that of electron capture detection, whereby a low-energy
electron is captured by an electronegative sample molecule, forming a molecular anion that may
undergo fragmentation, depending on its structure, thus generating a mass spectrum. For effi-
cient ionization to be obtained, optimization of essential parameters (ionizing gas and its pres-
sure, source temperature, electron energy, and emission current intensity of the beam) needs to be
done (Amendola et al., 2002). It is worth noting that a relatively high pressure of the reagent gas is
important in ensuring a sufficiently high number of ion–molecule collisions during the dwell time
of the reactants in the ion source. On the other hand, extremely low electron energy and emission
current decrease the ionization efficiency (Zhao et al., 2007). Furthermore, methane is commonly
used as a reagent gas because it does not produce any negative ions, thus ensuring a low background
signal (Worton et al., 2008). It follows that the advantages of NCI over CI and EI include improved
sensitivity and high selectivity for analytes containing a halogen atom, a nitro group, or an extended
aromatic ring. These include PAHs (Kamiya et al., 2015), PBDEs (Li et al., 2011), alkyl nitrates, and
halocarbons (Worton et al., 2008). However, despite its great selectivity, a major disadvantage is that
NCI is limited to a few chemical classes of compounds such as those listed earlier. In addition, it
suffers from lack of commercial spectral libraries (Lambropolou and Hela, 2015). For this reason,
another soft ionization technique, atmospheric pressure ionization (API), can also be used.

1.4.3 atmospheriC pressure ionization

Having been introduced by Horning et al. in 1977, this technique has been modified by several
research groups to be what it is nowadays (Horning et al., 1977). For instance, McEwen and McKay
(2005) and Schiewek et al. (2008) finally produced source designs that led to commercially avail-
able atmospheric pressure gas chromatography–mass spectrometry (AP-GC-MS) instruments.
Ionization in the gas phase is generated using a corona needle by charge transfer or protonation
using a reagent gas such as nitrogen, and, consequently, molecular and quasimolecular ions are gen-
erated. Charge transfer is carried out under dry conditions in the absence of a modifier, and it results
in increased fragmentation. It is suitable for nonpolar compounds such as PCBs and chlorinated
pesticides. On the contrary, proton transfer is carried out under wet conditions, in the presence of a
modifier such as water, leading to better retention of the molecular ion. Likewise, it is excellent for
compounds of moderate polarity such as organophosphates.
Portoles et al. (2010) investigated the ionization behavior of 100 GC-amenable pesticides in
food by using AP-GC-QTOF-MS regarding the formation of either the molecular ion or the pro-
tonated molecule under charge transfer or protonated transfer. Thus, the presence of the molecular
ion/protonated molecule allowed the rapid application of a screening method in a posttarget way,
easily generating a list of compounds to be monitored by making use of their molecular for-
mula. The presence of a QTOF mass analyzer made it possible to perform additional tandem mass
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