Environmental trace analysis techniques and applications

Dean

Environmental
Trace Analysis
T E C H N I Q U E S A N D A P P L I C AT I O N S

Department of Applied Sciences, Northumbria University, UK
Increasing environmental regulations have resulted in the need for new methods of analysis for
environmental samples. A number of techniques have been developed that reduce or eliminate
the need for toxic organic solvents to be used, and the field of environmental trace analysis
continues to develop and expand both in terms of its application and in the range of analytical
techniques that are applied.
Building upon the knowledge presented in the author’s previous title, Methods for
Environmental Trace Analysis, this book provides new areas of investigation and over 10 years of
developments.
Environmental Trace Analysis: Techniques and Applications covers the essentials of

•
•
•
•
•
•
•

good laboratory housekeeping
making and recording practical results
principles of quantitative analysis
sampling protocols and sample storage
sample preparation for inorganic analysis
sample preparation for organic analysis

the wide range of analytical techniques that are applied to environmental trace elemental
and organic analyses.

Including case studies that highlight the application of the techniques, this book is intended to
provide practical information and a comparison of methods applied to environmental samples.
This text is suitable for students studying environmental science as well as related chemistry
and biology study programmes.
Also available
as an e-book

Tai Lieu Chat Luong

ISBN 978-1-119-96271-7

Environmental Trace Analysis : T E C H N I Q U E S A N D A P P L I C AT I O N S

John R. Dean

Environmental
Trace Analysis
T E C H N I Q U E S A N D A P P L I C AT I O N S
John R. Dean



Environmental Trace Analysis



Environmental

Trace Analysis
Techniques and Applications
John R. Dean
Department of Applied Sciences,
Northumbria University, UK


This edition first published 2014
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Library of Congress Cataloging-in-Publication Data
Dean, John R., author.
Environmental trace analysis : techniques and applications / John R. Dean.
pages cm
Includes bibliographical references and index.
ISBN 978-1-119-96270-0 (hardback) — ISBN 978-1-119-96271-7 (pbk.)
1. Trace analysis—Methodology. 2. Environmental chemistry—Methodology. 3. Sampling.
I. Title.
TD193.D428 2014
2013024965
577.270280 7–dc23
A catalogue record for this book is available from the British Library.
HB ISBN: 978-1-119-96270-0

PB ISBN: 978-1-119-96271-7
Set in 10.5/13pt, Sabon by Thomson Digital, Noida, India.
1

2014


To my wife Lynne
And our children Sam and Naomi



Contents
About the Author

xv

Preface

xvii

Acknowledgements

xix

Acronyms and Abbreviations

xxi

1 Basic Laboratory Procedures

1.1
Introduction
1.2
Health and Safety Issues
1.3
Sample Handling: Solid Samples
1.4
Sample Handling: Liquid Samples
1.5
Sample Handling: Gases/Vapour Samples
1.6
Summary
Further Reading

1
1
2
4
4
5
5
5

2 Investigative Approach for Environmental Analysis
2.1
Introduction
2.2
Recording of Practical Results
2.2.1
Useful Tips on Presenting Data in Tables

2.2.2
Useful Tips on Presenting Data in Graphical
Form
2.2.3
Useful Tips for Templates for Presenting Data
in Your Notebook
2.3
Significant Figures
2.4
Units
2.5
Summary

7
7
7
8
9
9
9
12
13


viii

CONTENTS

Appendix
Example Template A: Sample Collection

Example Template B: Sample Treatment
Example Template C: Sample Preparation for Inorganic
Analysis
Example Template D: Instrumental Analysis
Example Template E: Sample Preparation for Organic Analysis
Example Template F: Instrumental Analysis
Further Reading

14
14
14
15
17
18
20
20

3 Principles of Quantitative Environmental Analysis
3.1
Introduction
3.2
Preparing Solutions for Quantitative Work
3.3
Calibration Graphs
3.4
Limits of Detection/Quantitation
3.5
Calculations: Dilution or Concentration Factors
3.6
Quality Assurance

3.6.1
Certified Reference Materials
3.7
Summary
References
Further Reading

21
21
23
24
27
27
29
30
36
36
36

4 Environmental Sampling
4.1
Introduction
4.2
Sampling Soil (and Sediments)
4.3
Sampling Water
4.4
Sampling Air
4.5
Summary

Further Reading

37
37
39
40
42
44
44

5 Storage of Samples for Analysis
5.1
Introduction
5.2
Choice of Storage Container for Liquid Samples
5.3
Preservation Techniques for Liquid Samples
5.4
Storage and Preservation of Solid Samples
5.5
Storage and Preservation of Gaseous Samples
5.6
Summary
Further Reading

45
45
45
47
48

48
50
50

6 Preparation of Environmental Solid Samples
for Inorganic Analysis
6.1
Introduction
6.2
Decomposition Techniques

51
51
53


CONTENTS

ix

6.3

64
64
67

Selective Extraction Methods
6.3.1
Single Extraction Methods
6.3.2

Sequential Extraction Method
6.3.3
Chemometric Identification of Substrates and
Element Distributions (CISED) Method
6.4
Physiologically-Based Extraction Test or In Vitro
Gastrointestinal Extraction
6.4.1
Procedure for Gastric Extraction
6.4.2
Procedure for Gastric ỵ Intestinal Extraction
6.5
Earthworms
6.5.1
Procedure for Earthworm Bioaccumulation
Studies (Sandoval et al., 2001)
6.6
Summary
Appendix A: Extraction Reagents for Single Extraction
Methods
Appendix B: Extraction Reagents for Sequential Extraction
Method
Appendix C: Extraction Reagents for In Vitro Gastrointestinal
Extraction Using the Unified Bioaccessibility
Method (and the FOREhST Method)
References
Further Reading

69
70

71
72
72
74
75
75
77

77
79
80

7 Preparation of Environmental Liquid Samples
for Inorganic Analysis
7.1
Introduction
7.2
Liquid–Liquid Extraction of Metals
7.2.1
Procedure for APDC Extraction into MIBK
7.3
Ion Exchange
7.3.1
Chelation Ion Exchange
7.3.2
Procedure for Batch Ion Exchange Extraction
7.4
Co-precipitation
7.5
Summary

References
Further Reading

81
81
82
82
83
83
83
84
84
84
84

8 Preparation of Environmental Solid Samples
for Organic Analysis
8.1
Introduction
8.2
Liquid–Solid Extraction
8.2.1
Soxhlet Extraction
8.2.2
Soxtec Extraction

85
85
85
86

87


x

CONTENTS

8.2.3
Shake Flask Extraction
8.2.4
Ultrasonic Extraction
8.3
Pressurised Fluid Extraction
8.3.1
Instrumentation
8.3.2
In Situ Clean-up or Selective PFE
8.3.3
Procedure for Pressurised Fluid Extraction
8.4
Microwave-Assisted Extraction
8.4.1
Instrumentation
8.4.2
Procedure for Microwave-Assisted Extraction
8.5
Supercritical Fluid Extraction
8.5.1
Instrumentation
8.5.2

Procedure for Supercritical Fluid Extraction
8.6
Matrix Solid Phase Dispersion
8.7
Physiologically-Based Extraction Test or In Vitro
Gastrointestinal Extraction
8.7.1
Procedure for Gastric ỵ Intestinal Extraction
8.8
A Comparison of Extraction Techniques
8.9
Summary
Appendix A: Suppliers of Instrumental Techniques
Appendix B: Extraction Reagents for In Vitro Gastrointestinal
Extraction Using the FOREhST Method
(and the Unified Bioaccessibility Method)
Preparation of Simulated Saliva Fluid
Preparation of Simulated Gastric Fluid
Preparation of Simulated Duodenal Fluid
Preparation of Simulated Bile Fluid
References
Further Reading
9 Preparation of Environmental Liquid Samples
for Organic Analysis
9.1
Introduction
9.2
Liquid–Liquid Extraction
9.2.1
Procedure for Discontinuous Extraction

9.2.2
Procedure for Continuous Extraction
9.2.3
An Issue in Liquid–Liquid Extraction
9.3
Solid Phase Extraction
9.3.1
Procedure for Solid Phase Extraction
9.4
Purge and Trap Extraction
9.4.1
Procedure for Purge and Trap Extraction
9.5
Headspace Extraction

89
90
91
91
97
99
100
100
103
103
105
106
107
108
109

109
112
112

112
112
113
113
114
114
114

115
115
116
117
119
119
120
127
127
127
128


CONTENTS

9.5.1
9.5.2

Procedures for Headspace Sampling
Main Issues in Static Headspace (SHS)
Analysis
9.5.3
Main Issues in Dynamic Headspace (DHS)
Analysis
9.6
Solid Phase Microextraction
9.6.1
Procedure for Solid Phase Microextraction
9.6.2
Main Issues in Solid Phase Microextraction
9.7
Stir-Bar Sorptive Extraction
9.7.1
Main Issues in Stir-Bar Sorptive Extraction
9.8
Microextraction in a Packed Syringe
9.8.1
Procedure for Microextraction in a Packed
Syringe
9.8.2
Main Issues in Microextraction in a Packed
Syringe
9.9
Liquid Phase Microextraction
9.9.1
Main Issues in Single Drop Microextraction
9.10 Membrane Extraction
9.10.1 Semi-Permeable Membrane

9.10.2 Polar Organic Chemical Integrative Sampler
9.10.3 Chemcatcher
9.10.4 Ceramic Dosimeter
9.10.5 Membrane Enclosed-Sorptive Coating
9.11 A Comparison of Extraction Techniques
9.12 Summary
References
Further Reading

xi

131
131
132
132
134
135
135
136
137
137
138
139
140
140
140
141
141
143
143

143
143
143
144

10 Preparation of Environmental Air Samples
for Organic Analysis
10.1 Introduction
10.2 Thermal Desorption
10.2.1 Procedure for Thermal Desorption
10.3 Summary
Further Reading

145
145
147
148
148
148

11 Pre-concentration and Clean-up Procedures for Organic
Sample Extracts
11.1 Introduction
11.2 Methods for Solvent Evaporation
11.3 Sample Extract Clean-up Procedures

149
149
149
151

xii

CONTENTS

11.3.1 Column Chromatography
11.3.2 Acid-Alkaline Partition
11.3.3 Acetonitrile-Hexane Partition
11.3.4 Sulfur Clean-up
11.3.5 Alkaline Decomposition
11.4 Summary
Further Reading
12 Instrumental Techniques for Environmental Trace Analysis
12.1 Introduction
12.2 Environmental Inorganic Analysis
12.2.1 Atomic Spectroscopy
12.2.2 Inorganic Mass Spectrometry
12.2.3 X-ray Fluorescence Spectroscopy
12.2.4 Other Techniques for Environmental Inorganic
Analysis
12.3 Environmental Organic Analysis
12.3.1 Gas Chromatography
12.3.2 High Performance Liquid Chromatography
12.4 Other Techniques for Environmental Organic Analysis
12.5 Portable Techniques for Field Measurements
12.6 Summary
Further Reading
Portable Techniques
13 Selected Case Studies

13.1 Introduction
13.2 Total Analysis of Metals from Soils
13.3 Single Extraction of Metals from Soils
13.4 Sequential Extraction of Metals from Soils
13.5 Oral Bioaccessibility Testing of Metals from Soils
13.6 Pressurised Fluid Extraction of Organic Compounds
from Soils
13.7 Solid Phase Extraction of Organic Compounds
from Liquid Samples
13.8 Headspace Solid Phase Microextraction of Organic
Compounds
13.9 Dynamic Headspace Analysis of Organic Compounds
13.10 An Environmental Case Study: From Site to Analysis
to Data Interpretation and Contextualisation
13.10.1 Preliminary Risk Assessment

152
153
154
154
154
154
155
157
157
157
157
168
173
175

176
176
182
188
189
195
195
196
197
197
197
199
201
204
206
210
211
215
217
219


CONTENTS

13.10.2 Generic Quantitative Risk Assessment
(GQRA) (Stanger, 2004)
13.10.3 Detailed Quantitative Risk Assessment
(DQRA)
13.10.4 Remediation
13.11 Summary

References

xiii

225
231
232
232
237

14 Some Numerical Worked Examples
14.1 Introduction

239
239

Index

251



About the Author
John R. Dean D.Sc., Ph.D., D.I.C., M.Sc., B.Sc., FRSC, C.Chem.,
CSci. Cert.Ed.

John R. Dean took his first degree in Chemistry at the University of
Manchester Institute of Science and Technology (UMIST), followed by
an M.Sc. in Analytical Chemistry and Instrumentation at Loughborough
University of Technology and finally a Ph.D. and D.I.C. in Physical

Chemistry at Imperial College of Science and Technology, London. He
then spent two years as a postdoctoral research fellow at the Food Science
Laboratory of the Ministry of Agriculture, Fisheries and Food in
Norwich in conjunction with Polytechnic South West in Plymouth.
This was followed by a temporary lectureship in Inorganic Chemistry
at Huddersfield Polytechnic. In 1988 he was appointed to a lectureship
in Inorganic/Analytical Chemistry at Newcastle Polytechnic (now
Northumbria University). This was followed by promotion to Senior
Lecturer (1990), Reader (1994), Principal Lecturer (1998) and Associate
Dean (Research) (2004). In 2004 he was appointed as Professor of
Analytical and Environmental Science. Since 2008 he has held dual
responsibility as Head of the Graduate School and Research Professor
in the Department of Applied Sciences.
In 1998 he was awarded a D.Sc. (London) in Analytical and Environmental Science and was the recipient of the 23rd SAC Silver Medal in
1995. He has published extensively in analytical and environmental
science. He is an active member of the Royal Society of Chemistry
Analytical Division (RSC/AD) having served as a member of the atomic
spectroscopy group for 15 years (10 as honorary secretary) as well as a
past chairman (1997–99); he has been a member of the North East Region
RSC/AD since 1992 serving as chairman (2001–03; 2013-present) and


xvi

ABOUT THE AUTHOR

Honorary Secretary (2011 onwards). He has served on Analytical Division
Council for four terms as well as being Vice-President (2002–04).
He is an active member of Tyne Valley Canoe Club and can be found
most weekends on a river, lake or the sea. He has achieved BCU personal

performance awards in white water kayaking (4 star leader), sea kayaking (4 star) and open canoe (5 star leader trainee). He holds BCU Level 3
coach status in white water kayaking and sea kayaking and is moderate
water endorsed in open canoe. In addition, he is a UKCC Level 3 coach in
white water kayaking and a UKCC Level 3 open canoe trainee.


Preface
The field of environmental trace analysis continues to develop and
expand both in terms of its application and in the range of analytical
techniques that are applied. While this book is not a direct update of a
previous publication by the author (Methods for Environmental Trace
Analysis, John R. Dean, AnTS, Wiley, 2003: ISBN 0-470-84421-3) it
does build upon the knowledge presented. By taking a different style and
format to the original text, by updating where appropriate and by adding
new areas of investigation that have developed over the intervening 10
years a new text has emerged.
The book is arranged into 14 chapters covering the essentials of good
laboratory housekeeping, making and recording practical results, principles of quantitative analysis, through to sampling protocols and sample
storage. The book is sub-divided to allow the specific techniques that are
used to prepare solid, liquid and, where appropriate, volatile samples for
inorganic and organic analyses to be described. Emphasis is also placed
on the use of pre-concentration techniques and clean-up procedures for
organic samples. Chapter 12 focuses briefly on the wide range of
analytical techniques that are applied to environmental trace elemental
and organic analyses as well as a consideration of portable techniques for
field measurements. Chapter 13 looks at some selected case studies used
to highlight the application of the techniques in environmental trace
analysis.
Finally, a special mention to all the students (past and present) who
have helped to contribute to my interest in the field of environmental

xviii

PREFACE

trace analysis. Our achievements have been many and varied across a
broad area of environmental trace analysis – and mostly enjoyable!
John R. Dean
April 2013


Acknowledgements
Thank you to Lynne Dean for drawing Figures 4.2, 4.3, 4.4, 8.4, 12.11,
12.15(b), 12.16 and 13.8.
Thank you to Naomi Dean for drawing Figure 4.5.
Thank you to Dr Pinpong Kongchana for drawing Figures 8.2 and 8.7
as well as Figures in Box 6.1 illustrating conventional and microwave
heating.
Thank you to Edwin Ludkin for drawing Figures 12.15a and 12.19.
Thank you to Thermo Fisher Scientific for permission to publish
Figure 12.22; to Geotechnical Services for permission to publish Figure
12.23; to Spectral International, Inc. for permission to publish Figure 12.24; to InPhotonics, Inc. for permission to publish Figure 12.25;
to RAE Systems for permission to publish Figure 12.26; and, to Smiths
Detection for permission to publish Figure 12.27.
Thank you to Dr Jane Entwistle for Figure 13.1.
Thank you to Dr Nwabueze Elom for Figure 13.2.
Thank you to Dr Katherine Stapleton for Figures 13.3, 13.4 and 13.5.
Thank you to Dr Michael Deary for Figures 13.6 and 13.7.

Acronyms and Abbreviations
AA
AAS
AES
AFS
APCI
APDC
ASE
BCR
BSA
BSTFA
BTEX
CCD
CI
CID
CISED
CLEA
COSHH
CRM
Da
DAD
DCM
DHS
DTPA
DQRA
EC
ECD
EDTA

acetic acid
atomic absorption spectroscopy
atomic emission spectroscopy
atomic fluorescence spectroscopy
atmospheric pressure chemical ionisation
ammonium pyrrolidine dithiocarbamate
accelerated solvent extraction
Community Bureau of Reference
N, O-bistrimethylsilyl-acetamide
N,O-bis-trimethylsilyl-trifluoroacetamide
benzene, toluene, ethylbenzene and xylene’s
charged coupled device
chemical ionisation
charged injection device
Chemometric Identification of Substrates and Element
Distributions
Contaminated Land Exposure Assessment
Control of Substances Hazardous to Health
certified reference material
dalton (atomic mass unit)
diode array detection
dichloromethane (also known as methylene chloride)
dynamic headspace
diethylenetriaminepentaacetic acid
detailed quantitative risk assessment
end-capped
electron capture detector
ethylenediaminetetraacetic acid

xxii

EDXRF
EI
EMT
ES
EU
FID
FAAS
FOREhST
FTIR
GC
GC-MS
GF
GPC
GQRA
HASAW
HCl
HCL
HDPE
HF
HFBA
HPLC
HPLC-MS
HS
HyAAS
ICP
ICP-AES
ICP-MS

IR
IUPAC
LC
LDPE
LGC
LLE
LOD
LOQ
MAE
MASE
MEPS
MIBK
MS

ACRONYMS AND ABBREVIATIONS

energy-dispersive X-ray fluorescence spectroscopy
electron impact
electron multiplier tube
electrospray (ionisation)
European Union
flame ionisation detector
flame atomic absorption spectroscopy
Fed Organic Estimation human Simulation Test
Fourier-transform infrared (spectroscopy)
gas chromatography
gas chromatography mass spectrometry
graphite furnace (atomic absorption spectroscopy)
gel permeation chromatography
generic quantitative risk assessment

Health and Safety at Work
hydrochloric acid
hollow cathode lamp
high density polyethylene
hydrofluoric acid
heptafluorobutyric acid anhydride
high performance liquid chromatography
high performance liquid chromatography mass spectrometry
headspace
hydride generation atomic absorption spectroscopy
inductively coupled plasma
inductively coupled plasma atomic emission spectroscopy
inductively coupled plasma mass spectrometry
infrared
International Union of Pure and Applied Chemistry
liquid chromatography
low density polyethylene
Laboratory of the Government Chemist
liquid–liquid extraction
limit of detection
limit of quantitation
microwave assisted extraction
microwave assisted solvent extraction
microextraction in a packed syringe
methyl isobutyl ketone (also known as 4-methylpnetan2-one or isobutyl methyl ketone)
mass spectrometry


ACRONYMS AND ABBREVIATIONS

MSD
MSPD
MSTFA
NIST
NMR
NTD
OCP
ODS
PAH
PBET
PC
PCB
PE
PFA
PFE
PFPA
PID
PLE
PMT
POCIS
PP
PTFE
PTV
PVC
REACH
RF
SBSE
SEM
SFC
SFE

SGV
SHS
SPE
SPM
SPMD
SPME
SI (units)
SRM
TD

xxiii

mass selective detector
matrix solid phase dispersion
N-methyl-N-trimethylsilyl-trifluoroacetamide
National Institute of Standards and Technology
nuclear magnetic resonance
needle trap device
organochlorine pesticide
octadecylsilane
polycyclic aromatic hydrocarbon
physiologically-based extraction test
polycarbonate
polychlorinated biphenyl
polyethylene
perfluoroalkoxy (fluorocarbon) polymer
pressurised fluid extraction
pentafluoropropionic acid anhydride
photoionisation detector
pressurised liquid extraction

photomultiplier tube
polar organic chemical integrative sampler
polypropylene
polytetrafluoroethylene
programmed temperature vaporiser (injector)
polyvinyl chloride
Registration, Evaluation, Authorisation and restriction
of CHemicals
radiofrequency
stir-bar sorptive extraction
scanning electron microscopy
supercritical fluid chromatography
supercritical fluid extraction
soil guideline value
static headspace
solid phase extraction
semi-permeable membrane
semi-permeable membrane device
solid phase microextraction
Systeme International (d’Unites) (International System
of Units)
standard reference material
thermal desorption