Soil and Environmental Analysis Modern Instrumental Techniques Third Edition edited by Keith A. Smith The University of Edinburgh Edinburgh, Scotland Malcolm S. Cresser The University of York York, England MARCEL MARCEL DEKKER, INC. DEKKER TM Copyright n 2004 by Marcel Dekker, Inc. All Rights Reserved. The previous edition was Soil Analysis: Modern Instrumental Techniques, Second Edition, K. A. Smith, ed. (Marcel Dekker, Inc., 1991). Although great care has been taken to provide accurate and current information, neither the author(s) nor the publisher, nor anyone else associated with this publication, shall be liable for any loss, damage, or liability directly or indirectly caused or alleged to be caused by this book. The material contained herein is not intended to provide specific advice or recommendations for any specific situation. 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For more information, write to Special Sales/Professional Marketing at the headquarters address above. Copyright ß 2004 by Marcel Dekker, Inc. All Rights Reserved. Neither this book nor any part may be reproduced or transmitted in any form or by any means, electronic or mechanical, including photocopying, microfilming, and recording, or by any information storage and retrieval system, without permission in writing from the publisher. Current printing (last digit): 10987654321 PRINTED IN THE UNITED STATES OF AMERICA TM Copyright n 2004 by Marcel Dekker, Inc. All Rights Reserved. BOOKS IN SOILS, PLANTS, AND THE ENVIRONMENT Agricultural Engineering Animal Science Crops Irrigation and Hydrology Micro biology Plants Soils Editorial Board Robert M. Peart, University of Florida, Gainesville Harold Hafs, Rutgers University, New :Brunswick, New Jersey Moharnmad Pessarakli, University of Axizona, Tucson Donald R. Nielsen, University of Califcmia, Davis Jan Dirk van Elsas, Research Institute for Plant Protection, Wageningen, The Netherlands L. David Kuykendall, U.S. Department of Agriculture, Beltsville, Maryland Kenneth B. Marcum, Texas A&M University, El Paso, Texas Jean-Marc Bollag, Pennsylvania State University, University Park, Pennsylvania Tsuyoshi Miyazalu, University of Tokyo Soil Biochemistry, Volume I, edited by A. D. McLaren and G. H. Peterson Soil Biochemistry, Volume 2, edited by A. D. McLaren and J. SkujinS Soil Biochemistry, Volume 3, edited by E. A. Paul and A. D. Mcl-aren Soil Biochemistry, Volume 4, edited by E. A. Paul and A. D. Mcl-aren Soil Biochemistry, Volume 5, edited by E. A. Paul and J. N. Ladld Soil Biochemistry, Volume 6, edited by Jean-Marc Bollag and G. Stotzky Soil Biochemistry, Volume 7, edited by G. Stotzky and Jean-Ma~rc Bollag Soil Biochemistry, Volume 8, edited by Jean-Marc Bollag and G. Stotzky Soil Biochemistry, Volume 9, edited by G. Stotzky and Jean-Ma1.c Bollag Soil Biochemistry, Volume 10, edited by Jean-Marc Bollag and (2. Stotzky Organic Chemicals in the Soil Environment, Volumes 1 and 2, edited by C. A. I. Goring and J. W. Hamaker Humic Substances in the Environment, M. Schnitzer and S. U. Khan Microbial Life in the Soil: An Introduction, T. Hattori Principles of Soil Chemistry, Kim H. Tan Soil Analysis: Instrumental Techniques and Related Procedufies, edited by Keith A. Smith Soil Reclamation Processes: Microbiological Analyses and Applications, edited by Robert L. Tate Ill and Donald A. Klein Symbiotic Nitrogen Fixation Technology, edited by Gerald H. Elkan MARCEL DEKKER, INC. 270 Madison Avenue, New York, New York 10016 TM Copyright n 2004 by Marcel Dekker, Inc. All Rights Reserved. TM Copyright n 2004 by Marcel Dekker, Inc. All Rights Reserved. Soil-Water Interactions: Mechanisms and Applications, Shingo lwata and Toshio Tabuchi with Benno P. Warkentin Soil Analysis: Modern Instrumental Techniques, Second Edition, edited by Keith A. Smith Soil Analysis: Physical Methods, edited by Keith A. Smith and Chris E. Mullins Growth and Mineral Nutrition of Field Crops, N. K. Fageria, V. C. Baligar, and Charles Allan Jones Semiarid Lands and Deserts: Soil Resource and Reclamation, edited by J. SkujinS Plant Roots: The Hidden Half, edited by Yoav Waisel, Amram Eshel, and Uzi Kafkafi Plant Biochemical Regulators, edited by Harold W. Gausman Maximizing Crop Yields, N. K. Fageria Transgenic Plants: Fundamentals and Applications, edited by Andrew H iatt Soil Microbial Ecology: Applications in Agricultural and Environmental Management, edited by F. Blaine Metting, Jr. Principles of Soil Chemistry: Second Edition, Kim H. Tan Water Flow in Soils, edited by Tsuyoshi Miyazaki Handbook of Plant and Crop Stress, edited by Mohammad Pessarakli Genetic Improvement of Field Crops, edited by Gustavo A. Slafer Agricultural Field Experiments: Design and Analysis, Roger G. Petersen Environmental Soil Science, Kim H. Tan Mechanisms of Plant Growth and Improved Productivity: Modern Ap- proaches, edited by Amarjit S. Basra Selenium in the Environment, edited by W. T. Frankenberger, Jr., and Sally Benson Plant-Environment Interactions, edited by Robert E. W il kinson Handbook of Plant and Crop Physiology, edited by Mohammad Pessarakli Handbook of Phytoalexin Metabolism and Action, edited by M. Daniel and R. P. Purkayastha Soil- Water Interactions: Mechanisms and Applications, Second Edition, Re- vised and Expanded, Shingo Iwata, Toshio Tabuchi, and Benno P. Warkentin Stored-Grain Ecosystems, edited by Digvir S. Jayas, Noel D. G. White, and William E. Muir Agrochemicals from Natural Products, edited by C. R. A. Godfrey Seed Development and Germination, edited by Jaime Kigel and Gad Galili Nitrogen Fertilization in the Environment, edited by Peter Edward Bacon Phytohormones in Soils: Microbial Production and Function, William T. Frankenberger, Jr., and Muhammad Arshad Handbook of Weed Management Systems, edited by Albert E. Smith Soil Sampling, Preparation, and Analysis, Kim H . Tan Soil Erosion, Conservation, and Rehabilitation, edited by Menachem Agassi Plant Roots: The Hidden Half, Second Edition, Revised and Expanded, edited by Yoav Waisel, Amram Eshel, and Uzi Kafkafi Photoassimilate Distribution in Plants and Crops: Source-Sink Relation- ships, edited by Eli Zamski and Arthur A. Schaffer MARCEL DEKKER, INC. 270 Madison Avenue, New York, New York 10016 TM Copyright n 2004 by Marcel Dekker, Inc. All Rights Reserved. TM Copyright n 2004 by Marcel Dekker, Inc. All Rights Reserved. Mass Spectrometry of Soils, edited by Thomas W. Boutton and Shinichi Yamasaki Handbook of Photosynthesis, edited by Mohammad Pessarakli Chemical and Isotopic Groundwater Hydrology: The Applied Approach, Second Edition, Revised and Expanded, Emanuel Mazor Fauna in Soil Ecosystems: Recycling Processes, Nutrient Fluxes, and Agri- cultural Production, edited by Gero Benckiser Soil and Plant Analysis in Sustainable Agriculture and Environment, edited by Teresa Hood and J. Benton Jones, Jr. Seeds Handbook: Biology, Production, Processing, and Storage, B. B. Desai, P. M. Kotecha, and D. K. Salunkhe Modern Soil Microbiology, edited by J. D. van Elsas, J. T. Trevors, and E. M. H. Wellington Growth and Mineral Nutrition of Field Crops: Second Edition, N. K. Fageria, V. C. Baligar, and Charles Allan Jones Fungal Pathogenesis in Plants and Crops: Molecular Biology and Host Defense Mechanisms, P. Vidhyasekaran Plant Pathogen Detection and Disease Diagnosis, P. Narayanasamy Agricultural Systems Modeling and Simulation, edited by Robert M. Peart and R. Bruce Curry Agricultural Biotechnology, edited by Arie Altman Plant-Microbe Interactions and Biological Control, edited by Greg J. Boland and L. David Kuykendall Handbook of Soil Conditioners: Substances That Enhance the Physical Properties of Soil, edited by Arthur Wallace and Richard E. Terry Environmental Chemistry of Selenium, edited by William T. Fran ken berger, Jr., and Richard A. Engberg Principles of Soil Chemistry: Third Edition, Revised and Expanded, Kim H. Tan Sulfur in the Environment, edited by Douglas G. Maynard Soil-Machine Interactions: A Finite Element Perspective, edited by Jie Shen and Radhey Lal Kushwaha Mycotoxins in Agriculture and Food Safety, edited by Kaushal K. Sinha and Deepak Bhatnagar Plant Amino Acids: Biochemistry and Biotechnology, edited by Bijay K. Singh Handbook of Functional Plant Ecology, edited by Francisco I. Pugnaire and Fernando Valladares Handbook of Plant and Crop Stress: Second Edition, Revised and Ex- panded, edited by Mohammad Pessarakli Plant Responses to Environmental Stresses: From Phytohormones to Ge- nome Reorganization, edited by H. R. Lerner Handbook of Pest Management, edited by John R. Ruberson Environmental Soil Science: Second Edition, Revised and Expanded, Kim H. Tan Microbial Endophytes, edited by Charles W. Bacon and James F. White, Jr. Plant-Environment Interactions: Second Edition, edited by Robert E. W il- kinson Microbial Pest Control, Sushi1 K. Khetan MARCEL DEKKER, INC. 270 Madison Avenue, New York, New York 10016 TM Copyright n 2004 by Marcel Dekker, Inc. All Rights Reserved. TM Copyright n 2004 by Marcel Dekker, Inc. All Rights Reserved. Soil and Environmental Analysis: Physical Methods, Second Edition, Re- vised and Expanded, edited by Keith A. Smith and Chris E. Mullins The Rhizosphere: Biochemistry and Organic Substances at the Soil-Plant Interface, Roberto Pinton, Zeno Varanini, and Paolo Nannipieri Woody Plants and Woody Plant Management: Ecology, Safety, and Envi- ronmental Impact, Rodney W. Bovey Metals in the Environment: Analysis by Biodiversity, M. N. V. Prasad Plant Pathogen Detection and Disease Diagnosis: Second Edition, Revised and Expanded, P. Narayanasamy Handbook of Plant and Crop Physiology: Second Edition, Revised and Expanded, edited by Mohammad Pessarakli Environmental Chemistry of Arsenic, edited by William T. Frankenberger, Jr. Enzymes in the Environment: Activity, Ecology, and Applications, edited by Richard G. Burns and Richard P. Dick Plant Roots: The Hidden Half, Third Edition, Revised and Expanded, edited by Yoav Waisel, Amram Eshel, and Uzi Kafkafi Handbook of Plant Growth: pH as the Master Variable, edited by Zdenko Rengel Biological Control of Crop Diseases, edited by Samuel S. Gnanamanickam Pesticides in Agriculture and the Environment, edited by Willis B. Wheeler Mathematical Models of Crop Growth and Yield, Allen R. Overman and Richard V. Scholtz Ill Plant Biotechnology and Transgenic Plants, edited by Kirsi-Marja Oksrnan- Caldentey and Wolfgang H. Barz Handbook of Posthatvest Technology: Cereals, Fruits, Vegetables, Tea, and Spices, edited by Amalendu Chakraverty, Arun S. Mujumdar, G. S. Vijaya Raghavan, and Hosahalli S. Ramaswamy Handbook of Soil Acidity, edited by Zdenko Rengel Humic Matter in Soil and the Environment: Principles and Controversies, Kim H. Tan Molecular Host Resistance to Pests, S. Sadasivam and B. Thayumanavan Soil and Environmental Analysis: Modern Instrumental Techniques, Third Edition, edited by Keith A. Smith and Malcolm S. Cresser Chemical and Isotopic Groundwater Hydrology: Third Edition, Ema~nuel Mazor Additional Volumes in Preparation Agricultural Systems Management: Optimizing Efficiency and Performance, Robert M. Peart and Dean W. David Shoup Seeds Handbook: Biology, Production, Processing, and Storage, Second Edition, Revised and Expanded, Babasaheb B. Desai Physiology and Biotechnology Integration for Plant Breeding, edited by Henry T. Nguyen and Abraham Blum MARCEL DEKKER, INC. 270 Madison Avenue, New York, New York 10016 TM Copyright n 2004 by Marcel Dekker, Inc. All Rights Reserved. TM Copyright n 2004 by Marcel Dekker, Inc. All Rights Reserved. Preface This third edition retains the range of analytical techniques and the structure of individual chapters of the second edition. However, there are some significant changes, with the introduction of new topics and some deletions, to take into account the changing priorities in environmental analysis. The chapters on atomic absorption and flame emission spectrometry, inductively coupled plasma spectrometry, continuous-flow and flow- injection analysis, ion chromatography, combustion analyzers for carbon, nitrogen and sulfur, an d x-ray fluorescence spectrometry have new or additional authors and their applications sections cover a wider range of environmental materials than before. This latter feature is one that generally applies to this edition, so that although the most important application is still the analysis of soils, much more attention is given to other materials. Thus, for example, the chapter on CNS analyzers has been extended to cover the important topic of the measurement of dissolved C and N in waters, which involves the use of different instruments from those used for soil analysis. The coverage of ion-selective electrodes in the second edition has been included in an extended chapter on electroanalytical methods. Similarly, the previous chapter on isotope-ratio mass spectrometry has been extended to cover isotopes of hydrogen, carbon, and sulfur, as well as those of nitrogen, because of the importance of isotopic studies in current research into environmental and biospheric processes involving these elements. The previous chapters on nuclear and radiochemical analys is and instrumental neutron activation analysis have been replaced by a new chapter on the measurement of radioisotopes and ionizing radiation. The chapter on the measurement of gases in the soil atmosphere has been replaced by two chapters dealing with the measurement of gas fluxes between the land surface and the atmosphere, reflecting the current concentration of research effort on global warming. This expansion into a new interdisciplinary field, taken together with other changes already mentioned, means that the scientific coverage of the book extends to most of the techniques involved in TM Copyright n 2004 by Marcel Dekker, Inc. All Rights Reserved. studies of the biogeochemical cycles of carbon, nitrogen, and sulfur, in the context of improving our understanding of global change. Contamination of soils, waters, and sediments with heavy metals continues to present problems of a more localized nature, and several chapters provide appropriate analytical techniques for investigating them. The concern over organic pollutants has changed over the last few years from a strong focus on persistent pesticides to worries about other categories of organic compounds, such as PCBs and aromatic hydrocarbons. The book reflects this change in that the chapter on pesticide analysis has been replaced by one concentrating on these other contaminants. This third edition is aimed at researchers working in soil science, environmental chemistry, or ecological science, as well as scientists operating analytical service laboratories with substantial throughputs of soil, water, and other environmental samples. It provides information that should help in method selection by those who need to undertake a new determination as their projects develop. It will also guide those who are considering replacing outdated or worn out equipment used for a particular routine analytical task, either with a later model with new features (and probably more ‘‘bells and whistles’’), or alternatively, with a new method of instrumental analysis. In regard to selection of a new method, the book should help in evaluating the techniques available, so that the optimal choice, in terms of speed, cost, or sensitivity, may be selected. It will also be useful to teachers and students of postgraduate courses in soil chemistry, environmental chemistry, and soil and environmental analysis. We wish to thank the contributors for their efforts, Mary Lightbody for preparing the index, and Ann Pulido at Marcel Dekker, Inc., for managing the editing process. We acknowledge the tolerance of colleagues, families, and students who may have found us somewhat distracted from other tasks from time to time, as this volume passed through its various stages. Keith A. Smith Malcolm S. Cresser TM Copyright n 2004 by Marcel Dekker, Inc. All Rights Reserved. Contents Preface Contributors 1.AtomicAbsorptionandFlameEmissionSpectrometry Malcolm S. Cresser 2.InductivelyCoupledPlasmaSpectrometry Stephen J. Hill, Andrew Fisher, and Mark Cave 3. Electroanalytical Methods in Environmental Chemical Analysis Iain L. Marr 4.Continuous-Flow,Flow-Injection,andDiscreteAnalysis Anthony C. Edwards, Malcolm S. Cresser, Keith A. Smith, and Albert Scott 5.IonChromatography M. Ali Tabatabai, Nicholas T. Basta, and Shreekant V. Karmarkar 6. Automated Instruments for the Determination of Total Carbon,Hydrogen,Nitrogen,Sulfur,andOxygen Keith A. Smith and M. Ali Tabatabai 7.X-RayFluorescenceAnalysis Philip J. Potts 8.MeasurementofRadioisotopesandIonizingRadiation Olivia J. Marsden and Francis R. Livens 9.StableIsotopeAnalysisandApplications Charles M. Scrimgeour and David Robinson TM Copyright n 2004 by Marcel Dekker, Inc. All Rights Reserved. 10. Measurement of Trace Gases, I: Gas Analysis, Chamber Methods,andRelatedProcedures Keith A. Smith and Franz Conen 11. Measurement of Trace Gases, II: Micrometeor ological MethodsatthePlot-to-LandscapeScale John B. Moncrieff 12.AnalysisofOrganicPollutantsinEnvironmentalSamples Julian J. C. Dawson, Helena Maciel, Graeme I. Paton, and Kirk T. Semple TM Copyright n 2004 by Marcel Dekker, Inc. All Rights Reserved. [...]... Scotland Andrew Fisher Advanced Environmental Diagnostics, The University of Plymouth, Plymouth, England Stephen J Hill Advanced Environmental Diagnostics, The University of Plymouth, Plymouth, England Shreekant V Karmarkar U.S.A Lachat Instruments, Milwaukee, Wisconsin, Francis R Livens Department of Chemistry, The University of Manchester, Manchester, England Helena Maciel Department of Plant and Soil. .. Plant and Soil Sciences, Oklahoma State University, Stillwater, Oklahoma, U.S.A Mark Cave British Geological Survey, Nottingham, England Franz Conen School of GeoSciences, The University of Edinburgh, Edinburgh, Scotland Malcolm S Cresser York, England Environment Department, The University of York, Julian J C Dawson Department of Plant and Soil Science, The University of Aberdeen, Aberdeen, Scotland... of Aberdeen, Aberdeen, Scotland Philip J Potts Department of Earth Sciences, The Open University, Milton Keynes, England David Robinson Department of Plant and Soil Science, The University of Aberdeen, Aberdeen, Scotland Albert Scott Scottish Agricultural College, Edinburgh, Scotland Charles M Scrimgeour Scotland The Scottish Crop Research Institute, Dundee, Kirk T Semple Environmental Science Division,... solution to the flame In the late 19 60s, this prompted a number of distinguished researchers such as L’vov, West, Massmann, and others to look for alternative atomization systems that did not depend upon generation and transport of aerosol to flames (Potts, 19 87; Slavin, 19 91; Lajunen, 19 92) Early systems used small discrete portions of sample solution (ca 50 mL) injected by hand onto the center of a resistively... additions technique as well to a selection of samples For bismuth, cadmium, lead, silver, and thallium, detection limits by AAS are a few ng mL 1 or better (Kirkbright and Sargent, 19 74) For arsenic, selenium, and tellurium they tend to lie in the range 10 –30 ng mL 1, depending upon the source used (Cresser, 19 94) Small tungsten filaments (often extracted carefully from small lightbulbs) have also attracted... upon the surface tension, density, and viscosity of the sample solution An empirical equation relating aerosol size distribution to these parameters and to nebulizer gas and solution flow rates was first worked out by Nukiyama and Tanasawa in 19 39 (Cresser, 19 94) Careful matrix matching is therefore essential not just for matching aspiration rates of samples and standards but also for matching the size... Flame Emission Spectrometry 3 be positive and proportional to concentration Thus absorbance is the parameter that should be measured if linear calibration plots are required in AAS Note that if 90% of the light is absorbed, It/I0 is equal to 10 /10 0 or 0 .1, and A is equal to 1 Similarly 99% absorption corresponds to an absorbance of 2, 99.9% to an absorbance of 3, and so on Precisely measuring values of... simplicity, the water-cooled electrical connectors, lenses, and gas sheathing systems are not shown TM Copyright n 2004 by Marcel Dekker, Inc All Rights Reserved Atomic Absorption and Flame Emission Spectrometry 13 sample could first be dried by evaporating the solvent and then ashed at a few hundred degrees Celsius to remove any organic matrix, and finally atomized at a high temperature A fourth and even hotter... functions both as a pump for the sample solution and to break the sample up into a fine aerosol (Lopez-Garcia et al., 19 87) The aerosol is then immediately and intimately mixed with the fuel and oxidant and then transported through a spray chamber to the base of the burner head Figure 6 shows a typical pneumatic nebulizer The oxidant doubles as the nebulizing gas, and issues at high velocity from a narrow... hydride, the adsorption of hydrogen, and the disturbance of hydride transfer to the gas phase (Cresser, 19 94) Techniques to eliminate interference include separation by solvent extraction, coprecipitation or ion exchange, and use of masking reagents A helpful summary of these procedures can be found in a review of hydride generation techniques by Nakahara (19 90) Table 1 Volatile Hydride Compounds of Groups . 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