Environmental Analytical Chemistry

by Fifield, F. W.; Haines, P. J.

• ISBN13: 9780632053834
• ISBN10: 0632053836
• Edition: 2nd
• Format: Paperback
• Copyright: 2000-05-18
• Publisher: Wiley-Blackwell

Summary

The first edition of this book established a niche as the only volume with a wide ranging review of analytical chemistry having a focus specific to environmental science.This new edition has been thoroughly revised to take full account of the rapid changes and development in the field over the past five years. Separation science, atomic spectroscopy and speciation determinations are areas in which significant developments have been made, and these are reflected in the new edition. The importance of the assessment of the effects of pollutants on real systems has been recognised by the restructuring of the chapter on biological testing and incorporation of a new one on environmental toxicology. Self-assessment questions have been added.Environmental science was one of the key concerns of the latter part of the twentieth century and will continue to be into the twenty-first. Concerns for environmental protection and public health worldwide have led to extensive legislation. The investigation and modelling of environmental systems, together with the implementation of laws and regulations, has led to a demand for a large number of environmental measurements, many of which are made by techniques falling within the broad range of analytical chemistry. Many professionals make regular use of data obtained by techniques of analytical chemistry. Thus, although not primarily analytical chemists or even chemists, they need sufficient knowledge of the background of analytical chemistry to judge the quality and limitations of the environmental data obtained. Very much the same situation arises in the academic world, where students are involved in environmental science studies or projects in which they need appropriate analytical chemistry information.Both analytical chemistry and environmental science have an extensive literature at varying levels of sophistication. However, there have been few attempts to link the two. This book sets out the background to analytical chemistry and covers the principles of its most important techniques. This is done in a way that enables a user to grasp the strengths and weaknesses of a technique, together with its principles of operation, without becoming enmeshed in the chemical small print. Links to environmental uses are indicated in broad terms and then exemplified in more detail by accounts of specific and important environmental problems.Written for students of chemistry, environmental science and related disciplines, the book is also an essential reference source for those who use environmental information and need to be aware of the factors affecting its quality and reliability. This is still the only book to focus exclusively on the analytical chemistry methods relevant to environmental studies. As useful to chemists as it is to non-specialists who require an understanding of the techniques employed to collect data in their disciplines (e.g. environmental researchers, ecotoxicologists, etc).

Author Biography

F.W. Fifield is a former Principal Lecturer in Analytical Chemistry in the School of Applied Chemistry at Kingston University, UK, and now works in association with The Centre for Earth and Environmental Science Research at Kingston. His current research interests concern mainly the environmental problems of the former Soviet Union including Belarus and especially the Irkutsk/Baikal Region of Eastern Siberia.

P.J. Haines taught physical and analytical chemistry at Kingston University for thirty years. His research interests include the uses of thermal analysis and spectroscopic methods especially in the area of fire- retardant polymers. He now works as an analytical chemistry consultant.

Table of Contents

Contributors	v
Preface to First Edition	xvii
Preface to Second Edition	xix
Part I General principles and techniques	1	(306)
Introduction	3	(10)
F.W. Fifield
P.J. Haines
Environmental science and analytical chemistry	3	(1)
Analytical chemistry	4	(2)
Overall analytical processes	6	(7)
Defining the aims of an analytical programme	7	(1)
Selection of an analytical method	7	(1)
Sampling, sample handling and pretreatment	7	(3)
Analytical measurements	10	(1)
Method validation and quality assurance	10	(1)
Data assessment and interpretation	11	(1)
Safety	11	(2)
Analytical environmental data: assessment and interpretation	13	(23)
F.W. Fifield
Introduction	13	(1)
Basic concepts and definitions	13	(5)
True result	13	(1)
Population	14	(1)
Statistical sample	14	(1)
Error	14	(1)
Accuracy	14	(1)
Precision	15	(1)
The range, or spread of data	15	(1)
Distribution curves	16	(1)
The mean	16	(1)
The mode	16	(1)
The median	16	(1)
Degrees of freedom	17	(1)
Standard deviation	17	(1)
The variance	18	(1)
Confidence levels and confidence limits	18	(1)
The nature and origin of errors	18	(3)
Types of errors	19	(2)
Frequency distributions	21	(2)
Normal and Student t distributions	22	(1)
Other distributions	23	(1)
Assessment and interpretation of analytical results	23	(13)
Introduction	23	(1)
Data reliability	23	(2)
Precision comparisons	25	(2)
The assessment and comparison of means	27	(2)
Graphical methods	29	(5)
Detection limits	34	(1)
Further reading	35	(1)
Self-study exercises	35	(1)
Answers	35	(1)
Chemical principles	36	(40)
P.J. Haines
Introduction	36	(7)
Periodicity	38	(1)
Atomic spectra	39	(1)
Nature of the electron	40	(3)
Population of energy levels	43	(1)
Atomic orbitals and chemical bonds	43	(14)
Ionic bonds	43	(2)
Covalent molecules	45	(2)
Polyatomic molecules	47	(3)
Metal compounds and complexes	50	(3)
Chains, rings and networks	53	(4)
Molecular energy levels	57	(2)
Energy of assemblies of molecules	58	(1)
Enthalpies of formation and reaction	59	(1)
Entropy and free energy	60	(1)
Free energy and equilibrium	61	(2)
The effects of temperature	63	(1)
Application to equilibria	63	(7)
Phase equilibria	63	(1)
Ions in solution	64	(1)
Solubility	64	(2)
Acid-base equilibria	66	(1)
Oxidation-reduction equilibria	67	(1)
Electrochemical reactions	67	(2)
Complexation	69	(1)
Reaction kinetics	70	(1)
Examples of reaction kinetics	71	(2)
Radioactive reactions	71	(1)
Ionic reactions	72	(1)
Solid-state reactions	72	(1)
Photochemical reactions	72	(1)
Summary	73	(3)
Further reading	73	(1)
Self-study exercises	74	(1)
Answers	74	(2)
Titrimetry and gravimetry	76	(15)
F.W. Fifield
Introduction	76	(1)
Titrimetry	76	(12)
Introduction	76	(2)
Acid-base titrations	78	(3)
Complexometric titrations	81	(5)
Redox titrations	86	(2)
Gravimetry	88	(3)
Principles	88	(1)
Gravimetric procedures	88	(2)
Further reading	90	(1)
Separation techniques	91	(27)
F.W. Fifield
Introduction	91	(1)
Solvent extraction	91	(5)
Introduction	91	(1)
Solvent extraction of analytes from environmental samples	91	(1)
Separation of mixtures by solvent extraction	92	(4)
Chromatography	96	(16)
Introduction	96	(1)
Characteristics of chromatograms	97	(3)
High-performance liquid chromatography	100	(3)
Ion-exchange chromatography	103	(3)
Thin-layer and paper chromatography	106	(2)
Gas chromatography	108	(4)
Electrophoresis	112	(3)
Introduction	112	(1)
Capillary electrophoresis (CE)	112	(3)
Other separation techniques	115	(3)
Supercritical fluid chromatography (SFC)	115	(1)
Gel permeation chromatography (GPC)	115	(1)
Distillation and volatilisation	115	(1)
Precipitation	116	(1)
Further reading	116	(1)
Self-study exercises	116	(1)
Answers	117	(1)
General principles of spectrometry	118	(16)
P.J. Haines
Introduction	118	(1)
Energy levels	118	(1)
Types of transition	118	(3)
Lasers	119	(2)
Molecular dissociation	121	(1)
Electromagnetic radiation	122	(2)
The electromagnetic spectrum	124	(1)
Interaction of species with electromagnetic radiation	124	(4)
Absorption laws	128	(1)
Spectrometric instrumentation	129	(5)
Single-beam spectrometer	130	(1)
Double-beam spectrometer	131	(1)
Fourier-transform instruments	132	(1)
Further reading	133	(1)
Atomic spectrometry	134	(27)
F.W. Fifield
Introduction	134	(1)
Flame emission spectrometry	135	(3)
The chemical flame	135	(3)
Plasma emission spectrometry	138	(4)
Introduction	138	(1)
Inductively coupled plasma-atomic emission spectrometry (ICP-AES)	138	(4)
Inorganic mass spectrometry	142	(1)
Introduction	142	(1)
Inductively coupled plasma-mass spectrometry (ICP-MS)	142	(1)
X-ray emission techniques	143	(8)
Introduction	143	(4)
Electron probe microanalysis	147	(1)
X-ray fluorescence spectrometry	148	(3)
Atomic absorption spectrometry	151	(5)
Introduction	151	(1)
Sharp-line radiation	151	(1)
AAS measurements	152	(1)
Flame AAS	153	(1)
Electrothermal AAS	154	(2)
Atomic fluorescence spectrometry	156	(1)
Use of atomic spectrometry	157	(4)
Further reading	159	(1)
Self-study exercises	159	(1)
Answers	160	(1)
Molecular spectrometry	161	(42)
P.J. Haines
Introduction	161	(1)
Ultraviolet and visible spectrophotometry	161	(7)
Instrumentation	161	(1)
Band spectra	162	(1)
Polyatomic organic molecules	163	(1)
Solvent effects	164	(1)
Metal complexes	165	(1)
Applications	165	(1)
UV fluorescence methods	166	(2)
Combined separation and UV techniques	168	(1)
Infrared spectrometry	168	(9)
Sampling	169	(1)
Infrared absorption	170	(2)
Polyatomic molecules	172	(3)
Combinations of infrared and separation techniques	175	(1)
Applications of infrared spectrometry in environmental analysis	175	(2)
Nuclear magnetic resonance spectrometry (NMR)	177	(10)
Instrumentation	178	(1)
Solvents for NMR work	179	(1)
The chemical shift	179	(3)
The peak area	182	(1)
Spin--spin coupling	182	(4)
Applications of NMR	186	(1)
Mass spectrometry (MS)	187	(7)
Instrumentation	187	(3)
Isotopic composition and accurate masses	190	(1)
Nitrogen rule	190	(1)
Fragmentation	191	(1)
Applications of mass spectrometry	192	(2)
Structure elucidation	194	(9)
Further reading	201	(1)
Self-study exercises	201	(1)
Answers	202	(1)
Measurement of ionising radiations and radionuclides	203	(17)
F.W. Fifield
Introduction	203	(1)
Ionising radiations and radioactivity	203	(7)
Alpha radiation (α)	204	(1)
Beta radiation (β- or β+)	204	(1)
Gamma radiation (γ)	205	(1)
Internal conversion (ic)	206	(1)
Radioactive decay	207	(2)
Units of radioactivity and radiation measurement	209	(1)
The detection and measurement of radiation	210	(10)
Gas ionisation detectors	211	(1)
Semiconductor detectors	212	(1)
Sodium iodide detectors	213	(2)
Organic scintillators	215	(1)
Liquid scintillation counting	215	(2)
Detection by films	217	(2)
The importance of autoradiographic techniques in environmental analysis	219	(1)
Concentration and separation of radionuclides	219	(1)
Further reading	219	(1)
Electroanalytical techniques	220	(33)
E. Buckley-Dhoot
Introduction	220	(1)
Electrochemical principles	220	(2)
Potentiometric techniques	222	(12)
Introduction and theory	222	(2)
Practical considerations and applications	224	(9)
Potentiometric titrations	233	(1)
Current developments	234	(1)
Voltammetric and controlled potential techniques	234	(12)
Introduction	234	(1)
Theory	235	(1)
Practical considerations and applications	236	(4)
Techniques	240	(6)
Electrochemical detection in flowing streams	246	(3)
Introduction	246	(1)
Potentiometric measurements in flowing streams	247	(1)
Voltammetric measurement in flowing streams	247	(2)
Other electroanalytical techniques	249	(4)
Introduction	249	(1)
Conductometry	249	(1)
Coulometry	250	(1)
Electrogravimetry	250	(1)
Further reading	251	(1)
Self-study exercises	251	(1)
Answers	252	(1)
Thermal methods of analysis	253	(27)
P.J. Haines
Introduction	253	(1)
Definitions	253	(1)
General apparatus	254	(1)
Factors affecting thermal analysis results	255	(2)
The sample	256	(1)
The crucible	256	(1)
The rate of heating (dT/dt)	256	(1)
The atmosphere	256	(1)
The mass of the sample	257	(1)
Thermogravimetry	257	(5)
Apparatus	257	(2)
Applications of thermogravimetry	259	(3)
Differential thermal analysis (DTA) and differential scanning calorimetry (DSC)	262	(6)
Differential thermal analysis (DTA)	262	(1)
Differential scanning calorimetry (DSC)	262	(1)
Apparatus	263	(1)
Applications	264	(4)
Thermomechanical analysis (TMA) and dynamic mechanical analysis (DMA)	268	(3)
Apparatus	268	(1)
Applications	269	(2)
Simultaneous techniques and product analysis	271	(4)
Apparatus	271	(1)
Evolved gas analysis (EGA)	272	(1)
Analysis of products and reactions	273	(1)
Recent advances in thermal analysis techniques	274	(1)
Environmental applications of thermal methods	275	(3)
Geological materials	275	(1)
Recycling	276	(1)
Residues	277	(1)
Vaporisation studies	277	(1)
Flue gas treatment	277	(1)
Purity	278	(1)
Summary	278	(2)
Further reading	278	(1)
Self-study exercises	278	(1)
Answers	279	(1)
Biological indicators	280	(27)
R. Manly
Introduction	280	(3)
Monitoring community structure	283	(3)
Diversity indices	283	(1)
Similarity indices	284	(1)
Species abundance patterns	284	(1)
Multivariate analyses	285	(1)
Bioindicator methods	286	(13)
Biotic indices	287	(3)
Pollutant mapping	290	(2)
Biochemical indicators	292	(4)
Morphological and histological indicators	296	(2)
Detector and sentinel organisms	298	(1)
Comparative methods	298	(1)
Microbiological monitoring	299	(2)
Intrusive microorganisms and faecal contamination	299	(2)
Bioaccumulators	301	(5)
Bioassays	306	(1)
Further reading	306	(1)
Part II Specific applications	307	(164)
Speciation	309	(17)
G.L. Christie
The importance of speciation	309	(1)
Definition of speciation	309	(1)
The determination of trace metal speciation	309	(15)
Computer modelling	309	(5)
Experimental determination of speciation	314	(10)
Concluding remarks	324	(2)
Further reading	325	(1)
The analysis of atmospheric samples	326	(34)
C.K. Laird
Introduction	326	(1)
Atmospheric analyses	327	(1)
Measurements of atmospheric composition	327	(1)
Emission measurements	327	(1)
Indoor and workplace atmospheres	328	(1)
Techniques for gas analysis	328	(11)
Gas chromatography	328	(1)
Spectrometric methods	328	(8)
Electrochemical sensors	336	(1)
Chemical methods and detector tubes	336	(1)
Diffusion tubes and diffusion denuder tubes	337	(2)
Sampling	339	(2)
Ambient air	339	(1)
Emissions	340	(1)
Calibration of gas analysers	341	(2)
Determination of the main air pollutants and oxygen	343	(8)
Carbon monoxide	343	(1)
Nitrogen oxides	344	(1)
Ozone	345	(1)
Sulphur dioxide	346	(1)
Volatile organic compounds	347	(1)
Oxygen	348	(3)
Determination of some other air pollutants	351	(2)
Methane	351	(1)
Chlorofluorocarbons	351	(1)
Organic nitrates	351	(1)
Nitrous oxide	352	(1)
Toxic organic micropollutants	352	(1)
Hydroxyl and hydroperoxyl radical	353	(1)
Combustible gases	353	(1)
Sampling and analysis of particles and aerosols	353	(7)
Sampling particles and aerosols	354	(5)
Particle and aerosol composition	359	(1)
Further reading	359	(1)
References	359	(1)
Trace elements	360	(33)
N.I. Ward
Trace elements in the environment	360	(2)
Natural levels and chemical forms	362	(6)
Trace element contamination and pollution	368	(7)
Air particulates	368	(2)
Natural waters	370	(1)
Soils and sediments	371	(2)
Plants	373	(1)
Animals and humans	374	(1)
Sampling and sample preparation	375	(9)
Atmospheric samples	377	(1)
Water samples	378	(1)
Soils and sediments	379	(2)
Plants	381	(1)
Biological tissues and fluids	382	(1)
Sample digestion methods	383	(1)
Methods of analysis	384	(4)
Selected important examples	388	(5)
Lead	388	(2)
Aluminium	390	(2)
Further reading	392	(1)
Environmental radiation and radioactivity	393	(18)
F.W. Fifield
Introduction	393	(1)
The hazards of ionising radiations and their assessment	394	(1)
Natural sources of radiation	395	(7)
Radionuclides of geological origin	395	(6)
Radionuclides resulting from cosmic rays	401	(1)
Artificial sources of radiation	402	(5)
Radiation and radioactivity in research and medicine	402	(1)
Nuclear power	402	(5)
Radiogenic dating	407	(4)
Geological dating	408	(1)
Carbon dating	408	(1)
Tritium dating	409	(1)
Lead-210 dating	409	(1)
Thermoluminescence and electron spin resonance dating	410	(1)
Further reading	410	(1)
Contaminated landsites	411	(8)
F.W. Fifield
Introduction	411	(1)
The nature of contaminated sites	412	(2)
Origins of contamination	412	(1)
Physical characteristics of landsites	412	(2)
Assessments	414	(5)
Investigational plan	415	(3)
Further reading	418	(1)
The analysis of water	419	(10)
F.W. Fifield
Introduction	419	(2)
pH, acidity and alkalinity	421	(1)
Dissolved oxygen and oxygen demand	422	(2)
Total organic carbon	424	(1)
Metals	424	(1)
Dissolved salts	425	(1)
Trace organics	426	(1)
Radioactivity and radionuclides in water	427	(1)
Water surveys and sampling	427	(2)
Further reading	428	(1)
The determination of trace amounts of organic compounds	429	(23)
C.J. Welch
Introduction	429	(2)
Sample preparation	431	(6)
Maceration, dissolution and extraction	432	(1)
Partition	433	(3)
Concentration of the analyte	436	(1)
Chromatography	437	(3)
Gas chromatography	438	(1)
High-performance liquid chromatography	439	(1)
Capillary (zone) electrophoresis	439	(1)
Quantitation	439	(1)
Screening analysis	440	(1)
GC applications: pesticide analysis	441	(2)
HPLC: trace analysis	443	(2)
HPLC applications	445	(1)
Aromatic hydrocarbons	445	(1)
GC/HPLC applications	446	(6)
Trace organic analysis in water	446	(3)
Analysis of organic materials in soil and sediments	449	(1)
Analysis of amines	449	(1)
Further reading	450	(2)
Ecotoxicology	452	(19)
R. Manley
Introduction	452	(1)
Toxicant behaviour in living organisms	452	(2)
Dose-response relationships of toxicants	454	(6)
Toxicants and the environment	460	(1)
Toxicity testing	461	(7)
Bioassays	463	(5)
Ecological risk assessment	468	(3)
Further reading	470	(1)
Glossary	471	(9)
Index	480