Humic Matter in Soil and the Environment: Principles and Controversies - Chapter 1 ppt

Humic Matter in Soil and the Environment Principles and Controversies Kim H. Tan University of Georgia Athens, Georgia, U.S.A. MARCEL MARCEL DEKKER, INC. ~EKKER Library of Congress Cataloging-in-Publication Data A catalog record for this book is available from the Library of Congress ISBN: 0-8247-4272-9 This book is printed on acid-free paper. Headquarters Marcel Dekker, Inc. 270 Madison Avenue, New York, NY 100 16 tel: 212-696-9000; fax: 2 12-685-4540 Eastern Hemisphere Distribution Marcel Dekker AG Hutgasse 4, Postfach 8 12, CH-4001 Basel, Switzerland tel: 41-61-260-6300; fax: 41 -6 1-260-6333 World Wide Web http://www.dekker.com The publisher offers discounts on this book when ordered in bulk quantities. For more infor- mation, write to Special Sales/Professional Marketing at the headquarters address above. Copyright O 2003 by Marcel Dekker, Inc. All Rights Resewed. 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 2003 by Marcel Dekker, Inc. All Rights Reserved. BOOKS IN SOILS, PLANTS, AND THE ENVIRONMENT Agricultural Engineering Animal Science Crops Irrigation and Hydrology Microbiology Plants Soils Editorial Board Robert M. Peart, University of Florida, Gainesville Harold Hafs, Rutgers University, New Bmswick, New Jersey Moharnrnad Pessarakli, University of Arizona, Tucson Donald R. Nielsen, University of California, Davis Jan Dirk van Elsas, Research Institute for P1,ant 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 Miyazaki, 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. Skujiqs Soil Biochemistry, Volume 3, edited by E. A. Paul and A. D. McLaren Soil Biochemistry, Volume 4, edited by E. A. Paul and A. D. McLaren Soil Biochemistry, Volume 5, edited by E. A. Paul and J. N. Ladd Soil Biochemistry, Volume 6, edited by Jean-Marc Bollag and G. Stcltzky Soil Biochemistry, Volume 7, edited by G. Stotzky and Jean-Marc Bollag Soil Biochemistry, Volume 8, edited by Jean-Marc Bollag and G. Sta~tzky Soil Biochemistry, Volume 9, edited by G. Stotzky and Jean-Marc Bollag Soil Biochemistry, Volume 10, edited by Jean-Marc Bollag and G. 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 Procedures, 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 1001 6 TM Copyright n 2003 by Marcel Dekker, Inc. All Rights Reserved. Soil- Water Interactions: Mechanisms and Applications, Shingo lwata and Toshio Tabuchi with Benno P. Warkentin Soil Analysis: Modem 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 Hiatt 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: Modem 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. Wilkinson 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 1001 6 TM Copyright n 2003 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. Frankenberger, 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. Wil- kinson Microbial Pest Control, Sushil K. Khetan MARCEL DEKKER, INC. 270 Madison Avenue, New York, New York 1001 6 TM Copyright n 2003 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 ofArsenic, 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 Oksman- Caldentey and Wolfgang H. Barz Handbook of Postharvest 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 Additional Volumes in Preparation 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 MARCEL DEKKER, INC. 270 Madison Avenue, New York, New York 1001 6 TM Copyright n 2003 by Marcel Dekker, Inc. All Rights Reserved. PREFACE A large amount of information has accumulated on humic acids and related substances, which warrants the creation of an independent science of humic compounds. Two different concepts have emerged from the maze of data, one claiming humic compounds to be operational or fake compounds, produced by the analytical extraction procedures, and the other considering them to be natural compounds occurring in soils, rivers, lakes, oceans and their sediments. Apparently the two opposing opinions have caused considerable confusion among scientists, students, and professionals alike about exactly what humic acid is, or what the difference is between soil organic matter, humus, and humic acid. Several of the books and especially the symposium proceedings on humus and soil organic matter are guilty of making the chaos worse, by using different terms and concepts interchangeably and by only covering "specialty" topics. The need for a book providing comprehensive coverage, on definitions, concepts, genesis, extraction, properties, and the impact of humic matter on agriculture, industry, and environment, is apparent. This book tries to address the problem of complete coverage as highlighted above. In addition to its value as a textbook, it can be used equally well as a reference book by all interested in humic matter. The issues and controversies associated with humic acids are analyzed from the two different viewpoints mentioned above. The advances of the past century, and the prospects for advancing humic acid science in the new millennium, are explored from both viewpoints. The text also carries a message for increasing awareness of the appearance of more and more data, emphasizing the ubiquitous presence of humic compounds in nature and their impact on the environment, soils, and MARCEL DEKKER, INC. 270 Madison Avenue, New York, New York 1001 6 TM Copyright n 2003 by Marcel Dekker, Inc. All Rights Reserved. agriculture. The intensified application of humic substances in industrial and pharmaceutical operations is discussed, underscoring the significance of humic acids as highly important organic substances in nature. The production and use of therapeutic chemicals from humic acids and the manufacture of commercial humates for use in soils, which has grown lately into a multimillion dollar business, are addressed. These are issues of considerable interest to people studying, practicing, and producing medicines and fertilizers, and therefore enlarges the audience for this book beyond the scope of soil, agricultural, and chemical science. The book starts by examining the concepts of humus and humic matter from the two different standpoints. Definitions are given in Chapter 1 to delineate soil organic matter, humus, and humified substances. The term "humic matter" is defined and adopted in this book as the humified fraction of humus, and the controversy ofwhether it is present as an artifact or as a true compound in nature is addressed. Questions are raised on the significance of studying fake compounds, especially in institutions where "publish or perish" prevails. Chapter 2 discusses the nature and distribution of humic matter in soils, wetlands and peat, in aquatic environments, and in geologic deposits. A classification of the different types of humic matter based on origin is provided. The chapter contains a discussion of anthropogenic humic matter, developed from agricultural waste, polluting the environment. The notorious deposits from the so-called CAFOS, confined animal feeding operations, located on top of the recharge zones of aquifers in Texas, are explained as being too close for comfort. The topic of domestic waste, fouling drainage ditches and canals, is included to cover humic matter produced by these rotten pollutants. Extraction, isolation, and fractionation of humic substances are featured in Chapter 3, starting with the search for the 'best' inorganic and organic reagents. Detailed analytical procedures are given according to the International Humic Substances Society, the Soil Science Society of America, and the methods presented by Stevenson and Tan. The extraction of aquatic humic matter is discussed separately and the use ofXAD resins evaluated. A descriptive analysis MARCEL DEKKER, INC. 270 Madison Avenue, New York, New York 1001 6 TM Copyright n 2003 by Marcel Dekker, Inc. All Rights Reserved. is provided at the end on fulvic acids, humic acids, and humin, highlighting their definitions, properties, and significance in soils. Chapter 4 is on the genesis of humic matter. The components from which humic matter is formed are defined here asprecursors, and distinguished into (I) major precursors, e.g., lignin, phenols, quinones, protein, amino acids, and carbohydrates, and (2) miscellaneous humic precursors, e.g., lipids, sterols, and nucleic acids. Growth promoting substances. such as auxin, gibberellin, and vitamins are included in the latter group, and their biotic origin and decomposition are examined in relation to claims that humic acids display hormone-like actions. The section above is then followed by a probing discussion of the processes of formation of humic matter, defined here as humification. The three major theories, ligno-protein, phenol-protein, and sugar-amine condensation theory, are addressed in relation to the biopolyrner degradation andlor polymerization or condensation concept. As a final topic, a detailed analysis is given of the significance of statistical modeling of humification, including the use of stability coefficients, humification indexes, and models. Chapter 5 discusses the chemical composition of humic matter, which is distinguished into an elemental and a group composition. The significance of using weight and atomic percentages is studied, underscoring the importance of C/N ratios, atomic ratios, and functional group contents in the formation of formula composition. Molecular structures of humic acids are created by applying simple basic reactions, and the structural models obtained by the newest advances in computer modeling are a major challenge to the idea that humic substances lack formulas and structures. Chapter 6 is about characterization of hurnic substances by molecular weight and spectroscopic analysis. The types and ranges of molecular weight values are described, and their effect on size and shape of humic molecules is evaluated, including the importance of frictional ratios, E/f,. The usefulness of spectrophotometric color ratios and infrared group frequency and fingerprint regions in the identification of fulvic and humic acids is studied. Characterization by electron spin resonance (ESR), nuclear magnetic resonance (NMR), and electron microscopy is addressed in detail. Characteristic visible light, infrared, ESR, and NMR spectra and electron micrographs are MARCEL DEKKER, INC. 270 Madison Avenue, New York, New York 1001 6 TM Copyright n 2003 by Marcel Dekker, Inc. All Rights Reserved. provided, with detailed descriptions for each of the humic compounds. They are valuable for classroom teaching, and/or for use as standard reference in research and other scientific or industrial analysis; hence they are assets that make this book stand out over any other book published on the subject. Chapter 7 discusses electrochemical properties of humic mat- ter. Negative and positive charges are examined and their magnitude is explained using the Henderson-Hasselbalch equation, pKa, and pK,, values. The issue of COOH and phenolic-OH group contents affecting negative charges and total acidity of humic matter is addressed. Definitions and formulation of surface charge density are studied and the electric double layer theories amended to include a new concept called fused double layer. The proper definitions are given for adsorp- tion, cation exchange, complex, chelation, and bridging reactions, and deviations from the concepts are questioned as aberrations. The importance of these interactions in soils, agriculture, and the environment are addressed, and the role of pK, and stability constants in the reactions evaluated. The agronomic importance of humic matter is featured in Chapter 8, highlighting its effect on soil physical, chemical, and bio- logical properties. The significance of humic matter for terrestrial and aquatic life is explained, and the role of humic matter in the carbon and nitrogen cycles underscored. The action of humic acids as a redox agent is analyzed in the overall soil's redox system. The direct and indirect effect of humic matter on plant growth and crop production are discussed in detail. Chapter 9 covers the environmental and industrial importance of humic matter. The outstanding role humic matter plays in preser- vation of soil organic matter, mobilization and immobilization of elements, and biological detoxification is presented by underscoring the issue of degradation of the soil ecosystem. The use of humic matter in industry is discussed, stressing the production of agrochemicals, e.g., biofertilizers and biopesticides, and the salient features of humic acids considered for use as drilling fluids, paint, ink, tanning, ceramics, and silicones. An assessment is also made of the increased importance of commercial humates, and their production, types, and controversies over their use as fertilizers are addressed. The significance of humic MARCEL DEKKER, INC. 270 Madison Avenue, New York, New York 1001 6 TM Copyright n 2003 by Marcel Dekker, Inc. All Rights Reserved. [...]... New York 10 016 CONTENTS Preface Chapter 1 THE ISSUE OF HUMIC MATTER 1. 1 Concept of Humus 1. 1 .1 The Early Concept of Humus 1. 1.2 Concept of Humus in the Third Millennium 1. 2 Concept of Humic Matter 1. 3 The Issue of Artifacts 1. 4 The Issue of Real Compounds 1. 5 The Issue of Chemical Composition Chapter 2 THE NATURE AND DISTRIBUTION OF HUMIC MATTER 2 .1 Concepts and Historical Background 2 .1. 1 Historical... 2 .1. 2 Concepts in the Early Twentieth Century 2 .1. 3 The Dawn of Modern Concepts 2.2 Distribution of Humic Matter 2.2 .1 Humic Matter in Soils 2.2.2 Humic Matter in Soils of the Wetlands 2.2.3 Humic Matter in Aquatic Environments 2.2.4 Humic Matter in Geologic Deposits TM Copyright n 2003 by Marcel Dekker, Inc All Rights Reserved MARCEL DEKKER, INC 270 Madison Avenue, New York, New York 10 016 2.2.5 Humic. .. Humic Matter in Agricultural, Industrial and Municipal Waste 2.3 Classification of Humic Matter Terrestrial or Terrigenous Humic Matter Aquatic Humic Matter Wetland or Peat Humic Matter Geologic Humic Matter Anthropogenic Humic Matter Chapter 3 EXTRACTION AND FRACTIONATION OF HUMIC SUBSTANCES The Search for Extractants 3 .1. 1 Inorganic Reagents 3 .1. 2 Organic Reagents 3 .1. 3 Reagents for Collecting Aquatic... Precursors of Humic Matter 4.2.1Lignin TM Copyright n 2003 by Marcel Dekker, Inc All Rights Reserved MARCEL DEKKER, INC 270 Madison Avenue New York, New York 10 016 4.2.2 Phenols and Polyphenols 4.2.3 Quinones 4.2.4 Protein and Amino Acids 4.2.5 Carbohydrates 4.2.6 Miscellaneous Humic Precursors 4.3 Theories of Humification 4.3 .1 The Ligno-Protein Theory 4.3.2 The Phenol-Protein Theory 4.3.3 The Sugar-Amine Condensation... DOM scientist (Dutch dom = stupid, dumb) 1. 2 CONCEPT OF HUMIC MATTER The concept of humic matter is very confusing, since many people are using interchangeably the terms soil organic matter (SOM), humic substances, humic material, or the black decomposed organic substances, and the like Since the beginning an exact definition of humic matter has been missing and only lately have efforts been made by... to humic matter was very common in those years, and even now Flaig (19 75) and Haider (19 9 41, both TM Copyright n 2003 by Marcel Dekker, Inc All Rights Reserved MARCEL DEKKER, INC 270 MadisonAvenue, New York, New York 10 016 6 Chapter 1 prominent authorities on the subject, use the term humus and humic matter or humic substances interchangeably Kumada (19 87) adds to the confusion by using in his book the. .. nonhumic matter In contrast, Waksman (19 38) prefers to delete all the terms, and proposes the use of the name humus only for referring to the humic substances Apparently both Waksman's proposal in retaining the name humus and Page's idea of distinguishing nonhumic matter and TM Copyright n 2003 by Marcel Dekker, Inc All Rights Reserved MARCEL DEKKER, INC 270 MadisonAvenue, New York, New York 10 016 4 Chapter. .. equal to, the total organic matter content in soils Considering it synonymous with SOM, defined as the total soil organic matter content (Schnitzer, 2000), will not only bring confusion in the concept of humus, but will also ignore or erase the achievements attained in the development of the many theories on humus By using the term SOM indiscriminately, one wouldn't know whether it is referring to the total... assessing humic substances as real compounds was challenged several times, as discussed in the previous section above, the concept seemed to continue to simmer over the years, especially in Russia and Europe, the birthplace of humus and humic acids It flares up again at the beginning of the twentieth century when new evidence presented by Oden (19 14 ,19 19 )and others provided the right fuel Kononova (19 66),who... below For the reasons discussed above and in view of the increased application of humic substances in other fields, e.g., technology, industry, pharmacy and medicine, Ziechmann questions the merits in defending any further the operational definition In the United States, it is Stevenson (19 94) who views humic substances as distinctive soil components, different from the biopolymers of plants and microorganism, . beyond the scope of soil, agricultural, and chemical science. The book starts by examining the concepts of humus and humic matter from the two different standpoints. Definitions are given in Chapter. Marcel Dekker, Inc. All Rights Reserved. CONTENTS Preface Chapter 1 THE ISSUE OF HUMIC MATTER 1. 1 Concept of Humus 1. 1 .1 The Early Concept of Humus 1. 1.2 Concept of Humus in the Third. 2.2 .1 Humic Matter in Soils 2.2.2 Humic Matter in Soils of the Wetlands 2.2.3 Humic Matter in Aquatic Environments 2.2.4 Humic Matter in Geologic Deposits MARCEL DEKKER, INC. 270 Madison