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Herausgeber: John Wiley & Sons
Kategorie: Wissenschaft und neue Technologien
Sprache: Englisch

Beschreibung

Extraction Techniques for Environmental Analysis Explore the analytical approach to extraction techniques In Extraction Techniques for Environmental Analysis, accomplished environmental scientist and researcher John R. Dean delivers a comprehensive discussion of the extraction techniques used for organic compounds relevant to environmental analysis. In the book, extraction techniques for aqueous, air, and solid environmental matrices are explored and case studies that highlight those techniques are included. Readers will find in-depth treatments of specific extraction techniques suitable for adoption in their own laboratories, as well as reviews of relevant analytical techniques used for the analysis of organic compound extracts (with a focus on chromatographic separation and detection). Extraction Techniques for Environmental Analysis also includes a chapter that extensively covers the requirements for an analytical laboratory, including health and safety standards, as well as: * A thorough introduction to pre-sampling, as well as the extraction of aqueous samples, including the classical approach for aqueous extraction and solid phase extraction * Comprehensive explorations of the extraction of gaseous samples, including air sampling * Practical discussions of the extraction of solid samples, including pressurized fluid extraction and microwave-assisted extraction * In-depth examinations of post-extraction procedures, including pre-concentration using solvent evaporation Extraction Techniques for Environmental Analysis is a must-read resource for undergraduate students of applied chemistry, as well as postgraduates taking analytical chemistry courses or courses in related disciplines, like forensic or environmental science.

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Leseprobe

Cover

Title Page

Dedication Page

Preface

About the Author

Acknowledgements

Section A: Initial Considerations

1 The Analytical Approach

1.1 Introduction

1.2 Environmental Organic Compounds of Concern

1.3 Essentials of Practical Work

1.4 Health and Safety

1.5 Considerations for Data Presentation

1.6 Use and Determination of Significant Figures

1.7 Units

1.8 Calibration and Quantitative Analysis

1.9 Terminology in Quantitative Analysis

1.10 Preparing Solutions for Quantitative Work

1.11 Calibration Graphs

1.12 The Internal Standard

1.13 Limits of Detection/Quantitation

1.14 Dilution or Concentration Factors

1.15 Quality Assurance

1.16 Use of Certified Reference Materials

1.17 Applications

List of Tables

Chapter 1

Table 1.1 Stockholm Convention: The 12 initial persistent organic pollutant...

Table 1.2 Stockholm convention: the additional 16 persistent organic pollut...

Table 1.3 Emerging pollutants in the environment.

Table 1.4 Example template for use electronically or in notebook form: samp...

Table 1.5 Example template for use electronically or in notebook form: samp...

Table 1.6 Example template for use electronically or in notebook form: samp...

Table 1.7 An example of Control of Substances Hazard to Health (COSHH) form...

Table 1.8 Examples of (a) Hazard

and (b) Precautionary

Statements.

Table 1.9 Risk matrix analysis

Table 1.10 Some commonly used base SI Units.

Table 1.11 Some commonly used derived SI units.

Table 1.12 Commonly used prefixes.

Table 1.13 An example of a certificate for a certified reference material

...

Table 1.14 Data for calculation of LOD and LOQ.

Table 1.15 Data for worked example 1.

Table 1.16 Data for worked example 2.

Chapter 2

Table 2.1 The characteristics of natural waters [1].

Table 2.2 Selected examples of preservation techniques

for water samples....

Table 2.3 Critical values, two‐sided, of Students’ t‐statistics at various ...

Chapter 3

Table 3.1 A solvent miscibility table.

Table 3.2 Choice of organic solvent for liquid–liquid extraction.

Table 3.3 Typical K values for some common solvents.

Table 3.4 Analytical data for quantitation of organic compounds.

Table 3.5 Liquid–liquid extraction recoveries of organic pollutants from aq...

Chapter 4

Table 4.1 Some common solid‐phase extraction media.

Table 4.2 Solvent strengths for normal‐ and reversed‐phase sorbents.

Table 4.3 Chromatographic and calibration details (50–100 000 ng l

−1

)...

Table 4.4 Determination of quaternary ammonium compounds in seawater sample...

Table 4.5 Analytical data for the determination of Econea

(4‐bromo‐2‐...

Chapter 5

Table 5.1 Typical solid‐phase microextraction fibre coatings.

Table 5.2 Quantitative data analysis of VOCs using the polyacrylate SPME fi...

Table 5.3 Influence of solution (BHI broth) agitation, and fibre desorption...

Table 5.4 Investigation of fibre type for the determination of volatile org...

Chapter 9

Table 9.1 Some common solvents used for extraction, and their properties.

Table 9.2 GC‐MSD parameters and limits of detection for organic pollutant d...

Table 9.3 Determination of organic pollutants in a certified reference soil...

Chapter 10

Table 10.1 PLE solvent extraction systems (from EPA Method 3545A). Data fro...

Table 10.2

In situ

absorbents for sample clean‐up.

Table 10.3 Analytical data for quantitation of a range of organic pollutant...

Table 10.4 Analysis of BTEX, phenols, pesticides and BNAs in Certified Refe...

Table 10.5 Calibration data for analysis of PAHs by GC‐MS: based on a five‐...

Table 10.6 Determination of PAHs using in situ PLE‐GC‐MS from two certified...

Table 10.7 Analytical figures of merit for analysis of compounds in soil fr...

Table 10.8 Analytical figures of merit for analysis of compounds in soil fr...

Table 10.9 Analytical recovery (pre‐ and post‐PLE) for a soil sample and an...

Table 10.10 Analysis and characterization of soil at a public open space: P...

Table 10.11 Analysis and characterization of soil at a public open space: O...

Chapter 11

Table 11.1 Common organic solvents used in microwave‐assisted extraction.

Table 11.2 A comparison of Soxhlet extraction with microwave extraction for...

Table 11.3 A comparison of Soxhlet extraction with microwave extraction for...

Chapter 12

Table 12.1 Chemical structures of common surfactants.

Table 12.2 Recovery of Lutensol using matrix solid‐phase dispersion extract...

Table 12.3 Recovery of Lutensol using matrix solid‐phase dispersion extract...

Chapter 13

Table 13.1 Critical properties of selected substances.

Table 13.2

In situ

extraction vessel absorbents and their use.

Table 13.3 A comparison of Soxhlet extraction with 20% methanol‐modified su...

Chapter 14

Table 14.1 Typical volatile organic compounds monitored in the atmosphere.

Table 14.2 Examples of safe sampling volumes for thermal desorption‐GC usin...

Table 14.3 Example workplace exposure limits (WELs) for selected VOCs. Data...

Table 14.4 Example biological monitoring guidance values (BMGVs) for select...

Chapter 15

Table 15.1 Investigation of solvent evaporation on the recovery of ten poly...

Chapter 16

Table 16.1 Gas chromatography with flame‐ionization or mass spectrometry de...

Table 16.2 High‐performance liquid chromatography with ultraviolet/visible ...

c17

Table 17.1 Example, analytical figures of merit for the PAHs in soil.

Table 17.2 Analysis of a soil certified reference material (CRM 172).

Table 17.3 Analysis and characterization of soil at public open space.

Table 17.4 PAH incremental lifetime cancer risk for adult and child in soil...

Table 17.5 Category 4 screening levels (mg kg

−1

) based on the risk ma...

Chapter 18

Table 18.1 Historical developments in chromatography and extraction techniq...

Table 18.2 A comparison of the extraction methods for solid matrices.

Table 18.3 A comparison of extraction methods for liquid matrices.

List of Illustrations

Chapter 1

Figure 1.1 Chemical structures of the 12 initial persistent organic pollutan...

Figure 1.2 Calibration graphs. (a) A direct calibration graph and (b) a stan...

Figure 1.3 Quantitative transfer of a known volume of stock solution for pre...

Figure 1.4 A pictorial representation of the term’s accuracy and precision....

Figure 1.5 An investigation of linear dynamic range. (a) Calibration graph, ...

Figure 1.6 An example of a stable isotope‐labelled compound as an internal s...

Figure 1.7 An example of a structural analogue compound as an internal stand...

Figure 1.8 Structure of atropine.

Figure 1.9 Calibration graph for worked example 1, the determination of pent...

Figure 1.10 Calibration graph for worked example 2, the determination of ben...

Chapter 2

Figure 2.1 Potential contaminant distribution across an environmental site. ...

Figure 2.2 Some example approaches for sampling. (a) Random. (b) Systematic....

Figure 2.3 The important crystalline silicate mineral layer structures of (a...

Figure 2.4 An approach to classify soil organic matter.

Figure 2.5 A soil texture diagram as used to classify soils according to the...

Figure 2.6 A typical nomenclature for assessing a soil horizon.

Figure 2.7 An example illustrating the use of the Munsell Soil Colour Chart....

Figure 2.8 A hand‐held auger (with options for three different sampling tool...

Figure 2.9 A phase diagram for water.

Figure 2.10 A schematic diagram of a freeze‐dryer.

Figure 2.11 Grinding and sieving of a soil sample (a) grinding of dried samp...

Figure 2.12 Soil sub‐sampling: coning and quartering. (a) soil sample arrang...

Figure 2.13 Spatial and temporal variation in a flowing stream.

Figure 2.14 Schematic diagram of a spring‐loaded water sampling device.

Figure 2.15 Air sampling using a passive sampler.

Figure 2.16 Air sampling using (a) sorbent tube sampling system and (b) a ty...

Figure 2.17 Sampling operations interrelationships and terminology.

Figure 2.18 Analytical operations interrelationships and terminology.

Figure 2.19 An example of a potential contaminated land site for investigati...

Chapter 3

Figure 3.1 A separating funnel for discontinuous liquid–liquid extraction.

Figure 3.2 Experimental set‐up for continuous liquid–liquid extraction (a) f...

Figure 3.3 Schematic diagram of single drop microextraction procedure.

Figure 3.4 Procedure for dispersive liquid–liquid microextraction (DLLME). A...

Figure 3.5 Schematic diagram of purge and trap extraction system: (a) purge ...

Figure 3.6 Headspace analysis (a) principle of headspace analysis, (b) stati...

Chapter 4

Figure 4.1 Use of solid‐phase extraction for sample clean‐up. Analysis of a ...

Figure 4.2 Solid‐phase extraction cartridges mounted in a vacuum manifold.

Figure 4.3 An adapter to connect solid‐phase extraction cartridges in series...

Figure 4.4 Generic solid‐phase extraction sorbent selection guide (a) for wa...

Figure 4.5 The anatomy of a solid‐phase extraction cartridge.

Figure 4.6 Experimental arrangement for vacuum‐operated, solid‐phase extract...

Figure 4.7 Experimental arrangement for vacuum‐operated, solid‐phase extract...

Figure 4.8 A plunger‐based system for solid‐phase extraction.

Figure 4.9 Experimental arrangement for vacuum‐operated solid‐phase extracti...

Figure 4.10 Experimental arrangement for vacuum‐operated solid‐phase extract...

Figure 4.11 Experimental arrangement for vacuum‐operated solid‐phase extract...

Figure 4.12 Solid‐phase extraction: (a) schematic diagram of the four stages...

Figure 4.13 Example of the influence of pKa on reversed‐phase solid‐phase ex...

Figure 4.14 (a) Reversed‐phase mechanism of sorption (partitioning) of the o...

Figure 4.15 Normal‐phase mechanism of hydrogen bonding for 4‐chlorophenol in...

Figure 4.16 An example of separation of an anionic surfactant (sodium 1‐deca...

Figure 4.17 An example of the retention mechanisms in a mixed‐mode SPE cartr...

Figure 4.18 Online solid‐phase extraction using column switching (a) sample ...

Figure 4.19 Method development: An investigation of compound retention and b...

Figure 4.20 Fragmentation pathway for the formation of the major quantificat...

Scheme 4.1 Hydrolysis of Econea

. Hydrolysis of Econea

(or 4‐brom...

Scheme 4.2 Synthesis of internal standard, the methyl ester of BCCPCA. Compo...

Figure 4.21 Example HPLC‐MS chromatogram of a seawater sample containing 50 ...

Chapter 5

Figure 5.1 Solid‐phase microextraction (a) photograph of a manual holder, an...

Figure 5.2 A typical extraction profile for solid‐phase microextraction: inf...

Figure 5.3 Schematic diagram of solid‐phase microextraction assembly.

Figure 5.4 Headspace solid‐phase microextraction of volatile organic compoun...

Figure 5.5 Influence of extraction time on recovery of an organic compound (...

Figure 5.6 Influence of fibre type on extraction profile for indole using he...

Chapter 6

Figure 6.1 Comparison of (a) solid‐phase microextraction, (b) solid‐phase dy...

Figure 6.2 Microextraction by packed sorbent (MEPS). (a) Complete MEPS syrin...

Figure 6.3 Automated in‐tube extraction (ITEX). (a) Full assembly for mounti...

Figure 6.4 Method of operation of ITEX‐DHS. (a) Sample incubation, (b) adsor...

Figure 6.5 Chemical structure of the four odorants.

Figure 6.6 Influence of ITEX extraction strokes on recovery of organic compo...

Figure 6.7 ITEX‐DHS‐GC‐MS chromatogram for odorants. (a) A standard (5 ng l

−

...

Figure 6.8 Calibration data for odorants in water using ITEX‐DHS‐GC‐MS (0–10...

Chapter 7

Figure 7.1 Schematic diagram of a stir‐bar sorptive extraction device.

Figure 7.2 Modes of operation of stir‐bar sorptive extraction.

Figure 7.3 Chemical structure of pentachlorophenol.

Chapter 8

Figure 8.1 Generic characteristics of a passive sampling device.

Figure 8.2 Variation in concentration of organic pollutant, in natural water...

Figure 8.3 Transport barriers in a passive sampler for polar organic polluta...

Figure 8.4 Typical profile of the uptake of pollutants by a passive sampling...

Figure 8.5 A membrane extraction device for passive sampling of aqueous samp...

Figure 8.6 A membrane extraction device for passive sampling of aqueous samp...

Figure 8.7 A membrane extraction device for passive sampling of aqueous samp...

Figure 8.8 A membrane extraction device for passive sampling of aqueous samp...

Figure 8.9 A membrane extraction device for passive sampling of aqueous samp...

Figure 8.10 A membrane extraction device for passive sampling of aqueous sam...

Figure 8.11 A membrane extraction device for passive sampling of aqueous sam...

Figure 8.12 A membrane extraction device for passive sampling of aqueous sam...

Figure 8.13 Chemical structures of NSAIDs (a) ibuprofen, (b) naproxen and (c...

Figure 8.14 Sampling approach using Chemcatcher® for non‐steroidal anti‐infl...

Chapter 9

Figure 9.1 Extraction from solid matrices.

Figure 9.2 Theory of liquid–solid extraction. Extraction processes: 1. desor...

Figure 9.3 Soxhlet extraction apparatus.

Figure 9.4 Procedure for Soxhlet extraction. (a) Assembled apparatus for Sox...

Figure 9.5 Apparatus and procedure for Soxtec extraction. (a) Stage 1 boilin...

Figure 9.6 Ultrasonic extraction using either (a) sonic probe or (b) an ultr...

Figure 9.7 Apparatus for shake‐flask extraction using a mechanical orbital s...

Chapter 10

Figure 10.1 Theoretical examples of the extraction process in PLE: (a) influ...

Figure 10.2 Schematic diagram of a pressurized liquid extraction system.

Figure 10.3 A photograph of an extraction vessel used for pressurized liquid...

Figure 10.4 Schematic diagram of packing arrangements for the sample in extr...

Figure 10.5 Operation of a pressurized liquid extraction system: (a) system ...

Figure 10.6 Typical procedure for pressurized liquid extraction.

Figure 10.7 In situ packing of extraction vessel in pressurized liquid extra...

Figure 10.8 Separation of the 16 polycyclic aromatic hydrocarbons by gas chr...

Figure 10.9 Mean recoveries of polycyclic aromatic hydrocarbons, from slurry...

Figure 10.10 Mean recoveries of polycyclic aromatic hydrocarbons from soil u...

Figure 10.11 Determination of PAHs from a contaminated land soil using PLE w...

Figure 10.12 Schematic diagram of the public open space with sampling points...

Figure 10.13 GC‐MS chromatograms for a mixture of the target compounds. (a) ...

Chapter 11

Figure 11.1 A microwave heating source: Magnetron.

Figure 11.2 The fundamental basis of conventional heating.

Figure 11.3 The fundamental basis of microwave heating.

Figure 11.4 A comparison of heating methods: a heating profile comparison.

Figure 11.5 Schematic diagram of microwave‐assisted extraction instrument.

Figure 11.6 High‐performance liquid chromatographic analysis of cyclic trime...

Chapter 12

Figure 12.1 Schematic diagram of apparatus for matrix solid‐phase dispersion...

Figure 12.2 Typical procedure for matrix solid‐phase dispersion.

Figure 12.3 Derivatization of alcohol ethoxylates, using phenyl isocyanate f...

Figure 12.4 Derivatization of alcohol ethoxylates (e.g. C12EO1), to increase...

Figure 12.5 Matrix solid‐phase dispersion extraction of fish tissue.

Figure 12.6 Normal‐phase high‐performance liquid chromatogram of fish tissue...

Figure 12.7 Gas chromatogram of (a) Lutensol standard (10 μg ml

−1

), (b...

Chapter 13

Figure 13.1 Schematic diagram of a typical phase diagram for a pure substanc...

Figure 13.2 Schematic diagram of a supercritical fluid extraction system.

Figure 13.3 Operation of a supercritical fluid extraction system: (a) system...

Chapter 14

Figure 14.1 Tedlar bag being sampled by a gas‐tight syringe.

Figure 14.2 Passive sampling using (a) a badge‐type sampler and (b) a tube‐t...

Figure 14.3 Schematic diagram of the thermal desorption process and its oper...

Figure 14.4 High‐volume PM

air sampler.

Figure 14.5 Schematic diagram of scanning electron microscope (SEM) images o...

Chapter 15

Figure 15.1 Needle evaporator with an example needle assembly.

Figure 15.2 Automated evaporator (TurboVap).

Figure 15.3 Rotary film evaporator (or rotovap).

Figure 15.4 Kuderna–Danish evaporative concentrator.

Figure 15.5 Schematic diagram of the automatic evaporative concentration sys...

Figure 15.6 Vortex mixer.

Figure 15.7 Chemical derivatization using (a) aluminium heating block with (...

Chapter 16

Figure 16.1 Schematic diagram of a chromatographic separation: (a) compounds...

Figure 16.2 A chromatogram: A plot of signal (relative abundance) (on the y‐...

Figure 16.3 Selected chromatographic terms.

Figure 16.4 Chromatographic peak shape: (a) peat tailing, (b) Gaussian and (...

Figure 16.5 Approaches for the estimation of the asymmetry factor. (a) Using...

Figure 16.6 An assessment of chromatographic resolution based on the separat...

Figure 16.7 Schematic diagram of a gas chromatograph.

Figure 16.8 Van Deemter plot: Influence of carrier gas on column efficiency ...

Figure 16.9 Sample injector for GC: a split/splitless injector.

Figure 16.10 Sample injector for GC: an on‐column injector.

Figure 16.11 Sample injector for GC: a programmed temperature vapourizer or ...

Figure 16.12 The GC oven with

in situ

column.

Figure 16.13 A schematic diagram of a capillary GC column.

Figure 16.14 Examples of three common GC stationary phases: (a) DB‐1, (b) DB...

Figure 16.15 A flame‐ionization detector for gas chromatography.

Figure 16.16 A quadrupole mass spectrometer (coupled to a GC) detector for g...

Figure 16.17 A schematic diagram of the electron impact ionization method fo...

Figure 16.18 Detectors for mass spectrometry: (a) a discrete dynode electron...

Figure 16.19 Data acquisition in mass spectrometry: (a) full scan (total ion...

Figure 16.20 Common derivatization reagents for low volatility or thermally ...

Figure 16.21 Schematic diagram of a high‐performance liquid chromatograph: (...

Figure 16.22 A schematic diagram of a 6‐port injection valve: (a) sample loa...

Figure 16.23 A schematic diagram of a typical HPLC column.

Figure 16.24 An illustration of an HPLC column stationary phase (i.e. octade...

Figure 16.25 Schematic diagram of ultraviolet – visible spectrometer for HPL...

Figure 16.26 HPLC‐MS methods of ionization: (a) an electrospray ionization s...

Figure 16.27 Typical mass spectrometers for HPLC: (a) a quadrupole MS, (b) a...

Figure 16.28 Examples of portable/handheld analytical instruments.

Figure 16.29 Structure of the sixteen polycyclic aromatic hydrocarbons.

Figure 16.30 GC‐MS chromatograms of the polycyclic aromatic hydrocarbons (a)...

c17

Figure 17.1 Concept of the overall analytical protocol for environmental ana...

Figure 17.2 (a) Present day map of site to be investigated along with histor...

Figure 17.3 A site conceptual model. (a) A description of the site and (b) t...

Figure 17.4 The public open space site with identified sampling points.

Figure 17.5 Example chromatograph of polycyclic aromatic hydrocarbon (PAH) s...

Figure 17.6 A summary of total PAH data across the public open space site.

Figure 17.7 Historical maps of a former, historic contaminated land site kno...

Figure 17.8 Chemical structure of benzo(a)pyrene.

Figure 17.9 A modern map of the St Anthony’s site.

Figure 17.10 Chemical analyses of soil from selected sampling grid areas.

Chapter 18

Figure 18.1 The German agricultural chemist Franz Ritter von Soxhlet (12 Jan...

Figure 18.2 Diagram of the Soxhlet extractor [1].

Figure 18.3 The Russian–Italian botanist Mikhail Semyonovich Tsvet (14 May 1...

Figure 18.4 The original chromatographic apparatus developed by M. Tsvett [2...

Guide

Cover Page

Title Page

Dedication Page

Preface

About the Author

Acknowledgements

Table of Contents

Begin Reading

Appendices

SI Units and Physical Constants

Index

WILEY END USER LICENSE AGREEMENT

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Extraction Techniques for Environmental Analysis

John R. Dean

Northumbria University

Newcastle, UK

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Library of Congress Cataloging‐in‐Publication Data

Names: Dean, John R., author.Title: Extraction techniques for environmental analysis / John R. Dean, Northumbria University, Newcastle, UK.Description: First edition. | Hoboken, NJ, USA : Wiley, 2022. | Includes bibliographical references and index.Identifiers: LCCN 2021050906 (print) | LCCN 2021050907 (ebook) | ISBN 9781119719045 (cloth) | ISBN 9781119719052 (adobe pdf) | ISBN 9781119719038 (epub)Subjects: LCSH: Extraction (Chemistry) | Environmental chemistry.Classification: LCC TP156.E8 D4349 2022 (print) | LCC TP156.E8 (ebook) | DDC 660/.28424–dc23/eng/20211109LC record available at https://lccn.loc.gov/2021050906LC ebook record available at https://lccn.loc.gov/2021050907

This book has been written during the global SARS‐CoV‐2 (COVID‐19) pandemic from 2020 to 2021. So, as well as working from home, with occasional visits to the laboratory on‐campus, most of my time has been sat in front of a PC in the dining room (I suspect like many of you).

Significant changes have also taken place during this time in the Dean family.

My wife Lynne was ordained deacon in the Church of England on Saturday 3 July 2021, so is now known as the Reverend Lynne.

My children, though no longer at home, continue in their respective careers. Naomi, a chemistry teacher in the North Lake District, and Sam, now a part‐time outdoor instructor and full‐time driver for a well‐known manufacturer of shortbread in North‐East Scotland.

And just pre‐pandemic, we welcomed Harris (a border terrier) into our family.

Preface

This book provides a comprehensive overview of the approaches required to obtain relevant and validated data in an environmental context. A comprehensive range of extraction techniques for the recovery of organic compounds from environmental matrices are reviewed in their function and application with illustrated case studies. In addition, other areas within the whole environmental process are included to allow the reader a fuller understanding. Each chapter, as well as being illustrated with tables and figures, also contains example Case Studies that allow a more in‐depth view. The book has been designed to be user‐friendly allowing the reader to investigate one topic at a time or to get an overview. The book is arranged into eight sections (and eighteen chapters) that allow the entire breadth of the environmental context to be highlighted.

Section A (Chapter 1) focuses on the initial considerations necessary to undertake environmental analysis. Specifically, it introduces the most important organic compounds of concern in the environment. The essentials of practical work are considered alongside health and safety. Then, the considerations necessary on data presentation and the importance in understanding the most appropriate units, and the recording of the appropriate number of digits (the use of significant figures). Quantitative analysis is covered in terms of preparation of standards, calibration data, the use of an internal standard, the calculation of limits of detection and quantitation, as well as considerations for sample extracts in terms of dilution and concentration factors. Finally, quality assurance aspects are considered, as well as the role and importance of certified reference materials.

Section B (Chapter 2) considers aspects of sampling and sample storage across the different matrices of aqueous, solid, and gaseous samples. Initial considerations are given to the design of an appropriate sampling strategy, followed by the different types of aqueous and solid matrices that might be encountered in an environmental context. The key physicochemical properties of water and soil matrices are then considered and discussed. A summary of the terminology and inter‐relationships between sampling and analytical operations are outlined. Finally, an overview, and then detailed consideration of the sample storage options and preservation techniques available for liquid, solid, and gaseous samples.

Section C (Chapters 3–8) consider the options available for the extraction of aqueous samples. Each individual chapter, generally, considers the theoretical basis of the selected technique, its method of application and practice, as well as an applications section. The following techniques are covered in this collection of chapters: classical approach for aqueous extraction (Chapter 3), solid‐phase extraction (Chapter 4), solid‐phase microextraction (Chapter 5), in‐tube extraction (Chapter 6), stir‐bar sorptive extraction (Chapter 7) and membrane extraction (Chapter 8).

Section D (Chapters 9–13) consider the options available for the extraction of solid samples. Each individual chapter, generally, considers the theoretical basis of the selected technique, its method of application and practice, as well as an applications section. The following techniques are covered in this collection of chapters: classical approach for extraction of solid samples (Chapter 9), pressurized liquid extraction (Chapter 10), microwave‐assisted extraction (Chapter 11), matrix solid‐phase dispersion (Chapter 12) and supercritical fluid extraction (Chapter 13).

Section E (Chapter 14) considers air sampling with respect to gaseous samples and particulate matter. Consideration is provided of the available techniques, methods of recovery of collected compounds, as well as the legal aspects of workplace exposure limits.

Section F (Chapters 15–16) considers the pre‐concentration, and associated sample extraction procedures necessary for action on sample extracts are considered in Chapter 15. A broad range of solvent evaporation techniques are considered, as well as clean‐up procedures. Finally, the process of chemical derivatization for gas chromatography is outlined. While Chapter 16 provides extensive coverage of the key analytical chromatographic techniques for environmental analysis. From first principles, through the theory of separation and detailed instrumentation for both gas chromatography and high‐performance liquid chromatography. Finally, a brief section on other analytical techniques for organic compound analysis is provided.

Section G (Chapter 17) considers the post‐analysis decision‐making processes by using selected environmental problem‐solving case studies. The first case study considers the initial necessary planning in attempting an environmental problem, the second case study considers the whole concept of environmental analysis and finally, the third case study uses a novel environmental chemistry Escape Room as a problem‐solving tool.

Section H (Chapter 18) considers the historical development of a range of extraction and chromatographic techniques from its earliest stage to the modern day.

Finally, the Appendices provide a useful approach to reframe and consider the key extraction techniques for aqueous and solid samples, as well as the instrumental techniques using crossword puzzles (with available solutions).

John R. DeanSummer 2021

About the Author

John R. Dean

DSc, PhD, DIC, MSc, BSc, FRSC,

CChem, CSci, PFHEA

Since 2004 John R. Dean has been Professor of Analytical and Environmental Sciences at Northumbria University, where he is also currently Head of Subject in Analytical Sciences, which covers all Chemistry and Forensic Science Programmes. His research is both diverse and informed covering such topics as the development of novel methods to investigate the influence and risk of metals and persistent organic compounds in environmental and biological matrices, to development of new chromatographic methods for environmental and biological samples using gas chromatography and ion mobility spectrometry, the development of novel approaches for pathogenic bacterial detection/identification and most recently the use of an unmanned aerial vehicle for precision agriculture applications. Much of the work is directly supported by industry and other external sponsors.

He has published extensively (over 225 papers, book chapters and books) in analytical and environmental science. He has also supervised over 40 PhD students.

John remains an active member of the Royal Society of Chemistry (RSC) and serves on several of its committees, including Committee for Accreditation and Validation of Chemistry Degrees and the Research Mobility Grant committee. His dedication to the society over 40 years was acknowledged in 2021 with the award for Exceptional Service.

After a first degree in Chemistry at the University of Manchester Institute of Science and Technology (UMIST), this was followed by an MSc in Analytical Chemistry and Instrumentation at Loughborough University of Technology, and finally a PhD and DIC in Physical Chemistry at the Imperial College of Science and Technology (University of London). He then spent two years as a postdoctoral research fellow at the Government Food Laboratory in Norwich. In 1988, he was appointed to a lectureship in Inorganic/Analytical Chemistry at Newcastle Polytechnic (now Northumbria University) where he has remained ever since.

John is also active in paddlesport; he holds performance (UKCC level 3) coach awards in open canoe and white water kayak. In 2012, his involvement in a local club was acknowledged by the award of an ‘outstanding contribution’ by the British Canoe Union.

Acknowledgements

Several colleagues and students (undergraduate and postgraduate (past and present) have provided data that has been used in case studies within the chapters. Unless mentioned specifically, all colleagues and students were located at Northumbria University. In addition, I also acknowledge research sponsors who have provided the funding that has allowed the science behind the case studies to have been done. My appreciation is expressed to all of them for their dedication to the science.

Specifically, the following are acknowledged. In Chapter 1, Dr Graeme Turnbull for the original design of the template on the Control of Substances Hazardous to Health (COSHH), and Brooke Duffield and Samantha Bowerbank for the data used in Case Study A. In Chapter 3, Dr Wanda Scott and Edwin Ludkin for the data in Case Study A, as well as the funder: Engineering and Physical Sciences Research Council for the award of an Industrial case award in collaboration with LGC limited, London, with support from the Department of Trade and Industry under the National Measurement System Valid Analytical Measurement (VAM) Programme. In Chapter 4, for the data used in Case Study B, Dr Paul Bassarab, Professor Justin Perry and Edwin Ludkin, as well as the funder: The Royal Commission for the Exhibition of 1851 for the award of an industrial fellowship. For the high‐resolution mass spectra (HRMS), the EPSRC UK National Mass Spectrometry Service Centre, Swansea, UK. For the data used in Case Study C, (the late) Dr Robert Downs, Professor Justin Perry and Edwin Ludkin, as well as the funder: The Engineering and Physical Sciences Research Council (EPSRC) and AkzoNobel Ltd. For the high‐resolution mass spectra (HRMS), the EPSRC UK National Mass Spectrometry Service Centre, Swansea, UK. In Chapter 5, Dr Emma Reed (néeTait), Professor Stephen Stanforth and Professor John Perry (Freeman Hospital, Newcastle), as well as the funder: bioMérieux S.A. In Chapter 6, Samantha Bowerbank along with assistance from Daniela Cavagnino, ThermoFisher, as well as the funder: Northumbria University. In Chapter 9, for the data used in Case Study A, Dr Francesc A.E. Turrillas, University of Valencia, and the funder: V Segles, University of Valencia, and Dr Wanda Scott and Edwin Ludkin, and the funder: Engineering and Physical Sciences Research Council for the award of an Industrial case award, in collaboration with LGC Limited, London, with support from the Department of Trade and Industry under the National Measurement System Valid Analytical Measurement (VAM) Programme. In Chapter 10, for Case Study A, Dr Wanda Scott and Edwin Ludkin, and the funder: Engineering and Physical Sciences Research Council for the award of an Industrial case award, in collaboration with LGC Limited, London, with support from the Department of Trade and Industry under the National Measurement System Valid Analytical Measurement (VAM) Programme. For Case Study B, Dr Damian Lorenzi, and the funder: Northumbria University in collaboration with British Geological Survey, Keyworth. For Case Study C, Joel Sánchez‐Piñero and Samantha Bowerbank, and the funder: Xunta de Galicia and the European Union (European Social Fund ‐ ESF) for a predoctoral grant, as well as Northumbria University. In Chapter 11, Case Study A, Dr Ian Barnabas and Edwin Ludkin, and the funder: Northumbria University and Analytical and Environmental Services Ltd., Northumbria Water plc. For Case Study B, Dr Claire Costley and Edwin Ludkin, and the funder: ICI Research and Technology Centre, Wilton, Middlesbrough and Northumbria University. In Chapter 12, Dr Carolyn Heslop and Edwin Ludkin, and the funder: Unilever, Port Sunlight. In Chapter 13, Dr Ian Barnabas and Edwin Ludkin, and the funder: Northumbria University and Analytical and Environmental Services Ltd., Northumbria Water plc. In Chapter 15, Dr Damien Lorenzi, and the funder: Northumbria University in collaboration with British Geological Survey, Keyworth. In Chapter 16, for Case Study A, Dr Damien Lorenzi, and the funder: Northumbria University in collaboration with British Geological Survey, Keyworth. In Chapter 17, Case Study B, Joel Sánchez‐Piñero and Samantha Bowerbank, and the funder: Xunta de Galicia and the European Union (European Social Fund ‐ ESF) for a predoctoral grant as well as Northumbria University. For Case Study C, the funder: Northumbria University.

Section AInitial Considerations

1 The Analytical Approach

LEARNING OBJECTIVES

After completing this chapter, students should be able to:

Contextualize an environmental problem.

Comprehend the implications of persistent organic pollutants in the environment.

Undertake a COSHH assessment.

Develop a strategy for effective practical work.

1.1 Introduction

Environmental analysis does not start in the laboratory but outside (e.g. in a field, river, lake, urban environment or industrial atmosphere). Therefore, environmental analysis requires more than just knowledge of the analytical technique to be used (e.g. chromatography). It requires a consideration of the vast array of extraction techniques that are available pre‐analysis. The focus of these pre‐analysis extraction techniques (covered in Chapters 3–15) is to recover the organic compounds of interest from a matrix. The matrices can be diverse in their form but generically can be considered as solid, liquid or gas. The purpose of the extraction techniques is to, therefore, recover the organic compounds from the matrices and allow pre‐concentration/matrix clean‐up to take place.

In addition, it is important to place the extraction and subsequent analysis in its context. Important aspects, therefore, are as follows:

Consideration of the appropriate health and safety aspects in the laboratory (and the external environment).

What do you know already about the site to be investigated?

What are the expectations about the results?

What type of sampling regime is planned?

How might the collected samples be stored and preserved?

What type of sample preparation methodologies are appropriate to the sample?

How might the analysis be done?

What are the quality control procedures to be used (including calibration strategies and the use of certified reference materials)?

How will the knowledge of the results and their interpretation, contextualization and subsequent action be considered?

While all of these are covered to some extent in this book, the reader should also consult other resources, e.g. books, scientific journals and the web.

1.2 Environmental Organic Compounds of Concern

The range of potential organic compounds to be identified and quantified is vast. Their sources are equally diverse and varied. The Stockholm Convention is a global initiative, established in 2001 from former international collaborators, by the United Nations Environmental Programme (UNEP) and requires its signatories to take measures to eliminate or reduce the release of persistent organic pollutants (POPs) into the environment to protect human health where exposure is often via the food chain. UNEP identified 12 (initial) POPs that cause adverse effects on humans and the ecosystem (Table 1.1). There chemical structures, molecular formulae and molecular weights are shown in Figure 1.1.

Aldrin:

A pesticide applied to soils to kill termites, grasshoppers, corn rootworm and other insect pests; it can also kill birds, fish and humans. In humans, the fatal dose for an adult male is estimated to be about 5 g. Human exposure is mostly through dairy products and animal meats.

Chlordane:

It is used to control termites and as a broad‐spectrum insecticide on a range of agricultural crops. It can remain in the soil for an extended time and has a reported half‐life of one year. Chlordane may affect the human immune system and is therefore classified as a possible human carcinogen.

Dichlorodiphenyltrichloroethane (DDT):

It was widely used during World War II to protect soldiers and civilians from malaria, typhus and other diseases spread by insects. Subsequently, it has continued to be used to control disease in crops (e.g. cotton) and insects (e.g. mosquitoes). DDT continues to be applied against mosquitoes in developing countries to control malaria. DDT has long‐term soil persistence (10–15 years) after application. It has been used extensively, and so its residues can be found everywhere.

Dieldrin:

It has been used mainly to control termites and textile pests, as well as to control insect‐borne diseases and insects living in agricultural soils. It has a half‐life in soil of approximately five years. Aldrin (see earlier) can rapidly convert to dieldrin, so higher concentrations of dieldrin than expected can be found in the environment. Dieldrin is highly toxic to fish and other aquatic animals (e.g. frogs). Residues of dieldrin can be found in air, water, soil, fish, birds and mammals, including humans.

Endrin:

It is sprayed on the leaves of crops (e.g. cotton and grains) to protect from insects. It can also be used to control rodents (e.g. mice and voles). It has a long half‐life (persisting up to 12 years in soils). In addition, endrin is highly toxic to fish.

Heptachlor:

It is used to kill soil insects and termites, as well as cotton insects, grasshoppers, other crop pests and malaria‐carrying mosquitoes. Heptachlor is classified as a possible human carcinogen.

Hexachlorobenzene (HCB):

It is used to kill fungi that affect food crops (e.g. to control wheat bunt). It is also a byproduct from the manufacture of industrial chemicals and can occur as an impurity in several pesticide formulations. In high doses, HCB is lethal to some animals and, at lower levels, adversely affects their reproductive success.

Mirex:

It is used to control ants and termites. In addition, it has also been used as a fire retardant in plastics, rubber and electrical goods. Direct exposure to Mirex does not appear to cause injury to humans; however, the results of animal studies have led it to be classified as a possible human carcinogen. It has a half‐life in soil of up to 10 years.

Toxaphene:

It is used to protect cotton, cereal grains, fruits, nuts and vegetables from insects. It has also been used to control ticks and mites in livestock. It has a half‐life, in soil, of up to 12 years. It has been listed as a possible human carcinogen due to its effects on laboratory animals.

Polychlorinated biphenyls (PCBs):

These compounds (209 different types of which 13 exhibit a dioxin‐like toxicity) are used in industry as heat exchange fluids, in electric transformers and capacitors, and as additives in paint, carbonless copy paper and plastics. Their persistence in the environment corresponds to the degree of chlorination, and half‐lives can vary from 10 days to 1.5 years.

Polychlorinated dibenzo‐p‐dioxins (PCDDs):

These compounds (75 different types of which 7 are of concern) are produced unintentionally due to incomplete combustion, as well as during the manufacture of pesticides and other chlorinated substances. They are emitted mostly from the burning of hospital waste, municipal waste and hazardous waste, as well as automobile emissions, peat, coal and wood. They can have a half‐life in soil of up to 10–12 years. They are associated with a number of adverse effects in humans, including immune and enzyme disorders and chloracne, and they are classified as possible human carcinogens.

Polychlorinated dibenzofurans (PCDFs):

These compounds (135 different types) are produced unintentionally from many of the same processes that produce dioxins, as well as during the production of PCBs. They have been detected in emissions from waste incinerators and automobiles. Furans are structurally like dioxins and share many of their toxic effects. They are persistent in the environment for long periods and are classified as possible human carcinogens.

Table 1.1 Stockholm Convention: The 12 initial persistent organic pollutants (POPs).