Developments in Soil Science SOIL ORGANIC MATTER Further Titles in this Series I VALETON BAUXITES I.A H.R FUNDAMENTALS OF TRANSPORI' PHENOMENA IN POROUS MEDIA F.E A L L ISON SOIL ORGANIC MATTER AND ITS ROLE IN CROP PRODUCTION R W SIMONSON (Editor) NON-AGRICULTURAL APPLICATIONS O F SOIL SURVEYS G.H BOLT (Editor) SOIL CHEMISTRY ( t w o volumes) H.E DREGNE SOILS O F ARID REGIONS H AUBERT and M PINTA TRACE ELEMENTS IN SOILS Developments in Soil Science SOIL ORGANIC MATTER Edited by M SCHNITZER Soil Research Institute Agr ic u t u re Canada Ottawa, Ont., Canada and S.U KHAN Chemistry and Biology Research Institute Agriculture Canada Ottawa, Ont., Canada ELSEVIER SCIENTIFIC PUBLISHING COMPANY Amsterdam Oxford New York 1978 ELSEVIER SCIENCE PUBLISHERS B.V Sara Burgerhartstraat 25 P.O Box 1, 1000 AE Amsterdam, The Netherlands Distributors for the United States and Canada: ELSEVIER SCIENCE PUBLISHING COMPANY INC 655, Avenue of the Americas New York, NY 10010, U.S.A First edition 1978 Second impression 1983 Third impression 1985 Fourth impression 1989 ISBN 0-444-4 16 10-2 (Vol 8) ISBN 0-444-40882-7 (Series) Elsevier Science Publishers B.V., 1978 All rights reserved No part of this publication may be reproduced, stored in a retrieval system or transmitted in any form or by any means, electronic, mechanical, photocopying, recording or otherwise, without the prior written permission of the publisher, Elsevier Science Publishers B.V./ Physical Sciences & Engineering Division, P.O Box 330, lo00 AH Amsterdam, The Netherlands - Special regulations for readers in the USA This publication has been registered with the Copyright Clearance Center Inc (CCC), Salem, Massachusetts Information can be obtained from the CCC about conditions under which photocopies of parts of this publication may be made in the USA All other copyright questions, including photocopying outside of the USA, should be referred t o the publisher No responsibility is assumed by the Publisher for any injury and/or damage to persons or property as a matter of products liability, negligence or otherwise, or from any use or operation of any methods, products, instructions or ideas contained in the material herein Printed in The Netherlands List of Contributors V.O BIEDERBECK Research Station, Agriculture Canada Swift Current, Sask., Canada C.A CAMPBELL Research Station, Agriculture Canada Swift Current, Sask., Canada S.U KHAN Chemistry and Biology Research Institute Agriculture Canada Ottawa, Ont., Canada C.G KOWALENKO Soil Research Institute, Agriculture Canada Central Experimental Farm Ottawa, Ont., Canada L.E LOWE The University of British Columbia Department of Soil Science Vancouver, B.C., Canada M SCHNITZER Soil Research Institute, Agriculture Canada Central Experimental Farm Ottawa, Ont., Canada This Page Intentionally Left Blank PREFACE Soil organic matter, a key component of soils, affects many reactions that occur in these systems In spite of this, soil organic matter remains a neglected field in soil science and receives but scant attention in soil science courses One of the purposes of this book is t o remedy this situation and t o provide researchers, teachers and students with an up-to-date account of the current state of knowledge in this field The first three chapters of the book deal with the principal components of soil organic matter, that is, humic substances, carbohydrates and organic nitrogen-, phosphorus- and sulfur-containing compounds In Chapter reactions between soil organic matter and pesticides are discussed, whereas Chapters and are concerned with the more practical aspects of soil organic matter The author of each chapter is an active researcher in the field about which he is writing We were hoping that the direct involvement that each author has with his subject would result in a more adequate and relevant book Hopefully, the book will be of interest not only to soil scientists and agronomists but also to oceanographers, water scientists, geochemists, environmentalists, biologists and chemists who are concerned with the role of organic matter in terrestrial and aquatic systems Ottawa, April 1977 M Schnitzer S.U Khan This Page Intentionally Left Blank CONTENTS Preface Chapter Humic Substances: Chemistry and Reactions M SCHNITZER Introduction Synthesis of humic substances Extraction of humic substances Fractionation and purification The characterization of humic materials Elementary analysis Oxygen-containing functional groups Distribution of N in humic materials The analysis of humic substances - non-degradative methods Spectrophotometry in the UV and visible region Infrared spectrophotometry Nuclear magnetic resonance spectrometry Electron spin resonance spectrometry X-ray analysis Electron microscopy and electron diffraction Viscosity measurements Surface tension measurements Molecular weight measurements Vapor pressure osmometry The ultracentrifuge Gel filtration Othermethods Electrometric titrations Degradative methods Oxidative degradations Major degradation products Major types of products resulting from the oxidation of HA’s and FA’S extracted from soils formed under widely differing climatic environments Products resulting from the alkaline CuO oxidation of HA’s and FA’S Maximum yields of principal products Hypohalite oxidation Reductive degradation Na-amalgam reduction Hydrogenation and hydrogenolysis VIJ 1 7 10 11 11 13 14 14 17 18 21 22 23 24 24 24 25 25 26 27 28 31 33 34 34 35 37 306 SOIL ORGANIC SULFUR A N D FERTILITY tants (Williams and Steinbergs, 1964) Bicarbonate was also found t o extract preferentially the recently immobilized organic S which consists mainly of 131-reducible S (Freney e t al., 1971) However, in a recent study of available and isotopically exchangeable S in several Australian soils Probert (1976) found that the bicarbonate extractant measured a much larger pool of soil S than that which is available t o plants He concluded that this fraction does not represent the potentially mineralizable S since it was not sufficiently correlated with the “L” values of the soils examined ( d ) Reducible S This method measures the HI-reducible S in soils and as mentioned earlier (see the section on p 275) it accounts for 1/3 t o 2/3 of the total organic S in most mineral soils Although this fraction is generally thought t o be more labile or degradable than the C-bonded and the residual fraction of soil organic S (see the section on p 285), it is much too large a fraction t o provide a suitable index of plant available S Nevertheless, Spencer and Freney (1960) found that reducible S was significantly correlated with both S uptake and yield on several Australian soils In an earlier study Williams and Steinbergs (1959) showed very close correlations between reducible S and total S, organic S and NaOH-soluble S, but reducible S was not significantly correlated with plant uptake ( e ) Reserve S Bardsley and Lancaster (1960) suggested that a fraction designated as “reserve S” could be used as an indicator of the soil S status This method involves the ignition of a soil-sodium bicarbonate mixture followed by the extraction of sulfates Although this fraction contains essentially the total organic soil S and some inorganic S it was found t o be reasonably well correlated with S uptake by clover ( r = 0.79) Incubation techniques Incubation procedures of the type commonly used for assessing the availability of N in soils (Chapter ) appear to offer little promise for estimating the S availability status of soils This is because only a few ppm of sulfate S are normally released during laboratory incubation of soils, particularly in the absence of plants (Nicolson, 1970) Some success was reported by Harward et al (1962); the correlation of S released on incubation plus extractable S versus percentage yield was r = 0.75 However, this correlation was considerably weaker than that obtained for “A” values or 5% S in the plants Microbial assays Aspergillus niger has been used by several workers as a test organism for available soil S (Ensminger and Freney, 1966) This fungus can obtain similar amounts of S from soils as can be extracted with phosphate solutions Spencer and Freney (1960) found that the growth of Aspergillus on several Australian soils was closely correlated with S uptake by plants ( r = 0.83) In assessing the aforementioned tests it becomes apparent that some degree of correlation with plant uptake has been found for every method CONCLUSIONS 307 suggested However, these correlations with S tests, particularly with those which include some measure of labile soil organic S, have been largely restricted to pot experiments In such tests the extractability and availability of soil S can be markedly influenced by the pretreatment of the soil; consequently this artifact will contribute significantly to the observed correlations More emphasis should therefore be placed on field testing of these availability indexes A real need still exists for a quick and simple laboratory procedure which will adequately estimate the S supplying power of soils To develop such a soil test it is necessary t o identify those fractions of the soil organic S that decompose during the growing season and provide plant available S It will be difficult to attain this goal with existing fractionation procedures, because Freney et al (1975) have established that all of the major soil organic S fractions contribute available S for plant uptake and that no single fraction is likely to be of much value for assessing S availability Until fractionation techniques yielding biologically more meaningful fractions can be developed it might be useful to reexamine, modify and improve some of the more promising soil tests for labile S (e.g., heat-soluble and bicarbonate extractable s) CONCLUSIONS In this chapter we have discussed the nature, distribution and transformations of soil organic S, its relationship to other soil organic constituents, the factors that affect its turnover, and its function as a reserve for the supply of S to crops During the last two decades steady progress has been made toward a better understanding of S dynamics in the soil-plant system Thus S can no longer be viewed as the “neglected nutrient” or the “step child of soil fertility research”, a concern frequently expressed during the early 1950’s The fractionation techniques developed by Australian and Canadian workers have provided a useful basis for further partitioning and characterization of soil organic S Future progress in attempts to identify the source, nature and dynamics of the most labile components of organic S will depend largely on the partitioning into fractions of greater biological significance This information is without doubt of great agronomic importance because it provides the means for assessing more accurately the availability of S in soils The research to date has indicated that, contrary t o earlier assumptions, there are marked differences between the dynamics of S and N as exemplified by the dissimilar mineralization pattern in response t o plant growth, fertilization and changes in environmental conditions Consequently, experimental techniques and approaches that have been used successfully to characterize the N turnover are not necessarily applicable to the study of S dynamics However, it should be possible t o delineate more clearly the differences and similarities between the cycling of these two nutrients by simultaneous labelling 308 SOIL ORGANIC SULFUR AND FERTILITY of soil organic matter with 35Sand "N and subsequent tracing of their concomitant transformations In the area of S immobilization and mineralization, the imaginative and comprehensive tracer studies conducted by Freney e t al (1971, 1975) represent a significant advance by providing some insight into the quantitative transfer of S into and out of major soil organic fractions It is hoped that their results will stimulate further efforts t o elucidate the complex dynamics of soil organic S From an agronomic standpoint more accurate information is required on the long-term effects of cultivation and different cropping systems on the quantity and nature of the organic S reserve in soils We need to learn more about the factors that govern the release of plant available S from this reserve such as the role of arylsulfatase and other S-hydrolysing soil enzymes, the rhizosphere effect, and the effects of freeze thaw cycles and other drastic environmental changes It is essential that the theories developed on the basis of trends observed in laboratory and greenhouse experiments be taken t o the field and tested under more realistic conditions The development of sound models for the turnover of S requires a more effective use of tracers in well co-ordinated multifactored laboratory and field experiments which are designed to quantify the various biological interconversions of S within the complex soil-plant system REFERENCES Alexander, M., 1961 Introduction t o Soil Microbiology Wiley, New York, N.Y 472 pp Allison, F.E., 1973 Soil Organic Matter and its Role in Crop Production Developments in Soil Science, Elsevier, Amsterdam, 637 pp Anderson, G., 1975 In: J.E Gieseking (Editor), Soil Components, Organic Components Springer, New York, N.Y., pp 333-341 Aulakh, M.S., Dev, G and Arora, B.R., 1976 Plant Soil, 45: 75-80 Banwart, W.L and Bremner, J.M., 1975 Soil Biol Biochem., : 359-364 Banwart, W.L and Bremner, J.M., 1976 Soil Biol Biochem., : 19-22 Bardsley, C.E and Lancaster, J.D., 1960 Soil Sci SOC Am Proc., 24: 265-268 Barrow, N.J., 1960 Aust J Agric Res., 1 : 960-969 Barrow, N.J., 1961 Aust J Agric Res., : 306-319 Barrow, N.J., 1969 Soil Sci., : 193-201 Beaton, J.D., Burns, G.R and Platou, J., 1968 Sulphur Inst Tech Bull : 1-56 Bettany, J.R., Stewart, J.W.B and Halstead, E.H., 1973 Soil Sci SOC.Am Proc., 37: 91 5-918 Bettany, J.R., Stewart, J.W.B and Halstead, E.H., 1974 Can J Soil Sci., : 309-315 Biederbeck, V.O., 1969 Microbial Degradation and Chemical Characterization of Soil Humic Nitrogen Ph.D Thesis, Dept Soil Sci., Univ of Sask., Saskatoon, Sask Biederbeck, V.O and Paul, E.A., 1973 Soil Sci., 1 : 357-366 Birch, H.F., 1959 Plant Soil, 11: 262-286 Birch, H.F., 1960 Plant Soil, : 81-96 Bremner, J.M and Banwart, W.L., 1976 Soil Biol Biochem., : 79-83 Bremner, J.M and Bundy, L.G., 1974 Soil Biol Biochem., : 161-165 Campbell, C.A., Paul., E.A and McGill, W.B., 1976 Canada Nitrogen Symp., Calgary, Alta, pp 9-101 REFERENCES 309 Chandra, P and Bollen, W.B., 1960.Appl Microbiol., 8:31-38 Clark, F.E and Paul, E.A., 1970.Advan Agron., 22: 375-435 Coleman, R., 1966.Soil Sci., 101: 230-239 Cooper, P.J.M., 1972 Soil Biol Biochem., 4: 333-337 Cowling, D.W and Jones, L.H.P., 1970.Soil Sci., 110:346-354 Dijkshoorn, W and Van Wijk, A.L., 1967.Plant Soil, 26: 129-157 Donald, C.M and Williams, C.H., 1954.Aust J Agric Res., 5: 664-687 Ensminger, L.E and Freney, J.R., 1966.Soil Sci., 101: 283-290 Evans, C.A and Rost, C.O., 1945.Soil Sci., 59: 125-137 Fox, R.L., Olson, R.A and Rhoades, H.F., 1964.Soil Sci SOC Am Proc., 28: 243-246 Frederick, L.R., Starkey, R.L and Segal, W., 1957 Soil Sci SOC Am Proc., 21: 287292 Freney, J.R., 1958.Soil Sci., 86: 241-244 Freney, J.R., 1961.Aust J Agric Res., 12:424-432 Freney, J.R., 1967 In: A.D McLaren and G.H Peterson (Editors), Soil Biochemistry, Dekker, New York, N.Y., pp 229-259 Freney, J.R and Spencer, K., 1960.Aust J Agric Res., 11: 339-345 Freney, J.R and Stevenson, F.J., 1966.Soil Sci., 101: 307-316 Freney, J.R., Barrow, N.J and Spencer, K., 1962.Plant Soil, 27: 295-308 Freney, J.R., Melville, G.E and Williams, C.H., 1970.Soil Sci., 109:310-318 Freney, J.R., Melville, G.E and Williams, C.H., 1971.Soil Biol Biochem., 3: 133-141 Freney, J.R., Stevenson, F.J and Beavers, A.H., 1972.Soil Sci., 114: 468-476 Freney, J.R., Melville, G.E and Williams, C.H., 1975.Soil Biol Biochem., 7: 217-221 Hamm, J.M., Bettany, J.R and Halstead, E.H., 1973 Comm Soil Sci Plant Anal., 4: 219-231 Haque, I and Walmsley, D., 1972.Plant Soil, 37: 255-264 Haque, I and Walmsley, D., 1974.Plant Soil, 40: 145-152 Harward, M.E., Cha0,T.T and Fang, S.C., 1962.Agron J., 54: 101-106 Hesse, P.R., 1957.Plant Soil, 9:86-96 Hoeft, R.G., Walsh, L.M and Keeney, D.R., 1973 Soil Sci SOC Am Proc., 37: 401404 Houghton, C and Rose, F.A., 1976.Appl Environ Microbiol., 31: 969-976 Jenkinson, D.S., 1966.J Soil Sci., 17: 280-302 Jenny, H., 1930.Missouri Agr Exp Sta Res Bul., 152: 1-66 Johnson, C.M and Nishita, H., 1952.Anal Chem., 24: 736-742 Jones, L.H.P., Cowling, D.W and Lockyer, D.R., 1972.Soil Sci., 114: 104-114 Jones, M.B., Williams, W.A and Martin, W.E., 1971 Soil Sci SOC Am Proc., 35: 542546 Jordan, H.V and Ensminger, L.E., 1958.Advan Agron., 10: 407-434 Jordan, J.V and Baker, G.O., 1959.Soil Sci., 88: 1-6 Kilmer, V.J and Nearpass, D.C., 1960.Soil Sci SOC Am Proc., 24: 337-340 Kowalenko, C.G and Lowe, L.E., 1975a.Can J Soil Sci., 55: 1-8 Kowalenko, C.G and Lowe, L.E., 197513.Can J Soil Sci., 55: 9-14 Larson, W.E., Clapp, C.E., Pierre, W.H and Morachan, Y.B., 1972 Agron J., 64: 204208 Levesque, M., 1974.Can J Soil Sci., 54: 333-335 Lewis, J.A and Papavizas, G.C., 1970.Soil Biol Biochem., 2: 239-246 Lowe, L.E., 1964.Can J Soil Sci., 44: 176-179 Lowe, L.E., 1965.Can J Soil Sci., 45: 297-303 Lowe, L.E., 1969a.Can J Soil Sci., 49: 129-141 Lowe, L.E., 1969b.Can J Soil Sci., 49: 375-381 Lowe, L.E and DeLong, W.A., 1963.Can J Soil Sci., 43: 151-155 310 SOIL ORGANIC SULFUR AND FERTILITY MacKenzie, A.F., DeLong, W.A and Ghanem, I.S., 1967 Plant Soil, 27: 408-414 Mann, H.H., 1955 J Soil Sci., 6: 241-247 Martin, W.E and Walker, T.W., 1966 Soil Sci., 01: 248-257 Mathur, S.P., 1971 Soil Sci., 111: 147-157 McClung, A.C., DeFreitas, L.M.M and Lott, W.L., 1959 Soil Sci Soc Am Proc., 23: 2 1-224 McLachlan, K.D., In: K.D McLachlan (Editor), Sulphur in Australasian Agriculture Sidney Univ Press, Sidney, pp 58-67 Mehring, A.L and Bennett, G.A., 1950 Soil Sci., 70: 73-81 Nelson, L.E., 1964 Soil Sci., : 300-306 Nelson, L.E., 1973 Soil Sci., 115: 447-454 Neptune, A.M.L., Tabatabai, M.A and Hanway, J.J., 1975 Soil Sci Soc Am Proc., 39: 51-55 Nicolson, A.J., 1970 Soil Sci., : 345-350 Nyborg, M., 1968 Can J Soil Sci., : 37-41 Olson, R.A., 1957 Soil Sci., : 107-111 Paul, E.A., Recent Advan Phytochem., : 59-104 Paul, E.A and Schmidt, E.L., 1961 Soil Sci Soc Am Proc., 25: 359-362 Probert, M.E., 1976 Plant Soil, 45: 461-475 Rehm, G.W and Caldwell, A.C., 1968 Soil Sci., : 355-361 Roberts, S and Koehler, F.E., 1968 Soil Sci., : 53-59 Scharpenseel, H.W and Krausse, R., 1963 Z Pfl Ernahr Dung Bodenk., 101: 11-23 Scott, N.M., J Sci F o o d Agric., : 367-372 Scott, N.M and Anderson, G., 1976 J Sci F o o d Agric., 27: 358-366 Seim, E.C., Caldwell, A.C and Rehm, G.W., 1969 Agron J., : 368-371 Simon-Sylvestre, G., 1965 C.R Hebd Seances Acad Agric Fr., 51: 426-431 Spencer, K and Freney, J.R., Aust J Agric Res., 11: 948 959 Starkey, R.L., 1950 Soil Sci., : 55-65 Starkey, R.L., 1966 Soil Sci., 101: 297-306 Stewart, B.A and Porter, L.K., 9 Agron J., 1: 267-271 Stewart, B.A., Porter, L.K and Viets Jr., F.G., 1966a Soil Sci Soc Am Proc., 30: 355-358 Stewart, B.A., Porter, L.K and Viets Jr., F.G., 1966b Soil Sci Soc Am Proc., 30: 453-456 Stotsky, G and Norman, A.G., 1961 Arch Mikrobiol., : 370-382 Swaby, R.J and Fedel, R., 1973 Soil Biol Biochem., 5: 773-781 Tabatabai, M.A and Bremner, J.M., 1970a Soil Sci Soc Am Proc., 34: 225-229 Tabatabai, M.A and Bremner, J.M., 1970b Soil Sci Soc Am Proc., 34: 427-429 Tabatabai, M.A and Bremner, J.M., 1972a Agron J., 64: 40-44 Tabatabai, M.A and Bremner, J.M., 1972b Soil Sci., 114: 380-386 Till, A.R., 1975 I n : K.D McLachlan (Editor), Sulphur in Australasian Agriculture Sidney Univ Press, Sidney, pp 68-75 Ulrich, A., Tabatabai, M.A., Ohki, K and Johnson, C.M., 1967 Plant Soil, 26: 235252 Van Praag, H.J., , Plant Soil, : 61-69 Walker, D.R and Doornenbal, G., Can J Soil Sci., 52: 261-266 Walker,T.W., 1957 J Brit Grassl Soc., : 10-18 White, J.G., 1959 New Zealand, J Agr Res., : 255-258 Whitehead, D.C., 1964 Soils Fert., 27: 1-8 Williams, C.H., 1967 Plant Soil, : 205-223 Williams, C.H and Donald, C.M., 1957 Aust J Agric Res., 8: 179-189 Williams, C.H and Lipsett, J., 1961 Aust J Agric Res., : 612-629 Williams, C.H and Steinbergs, A., 1959 Aust J Agric Res., ; 340 352 Williams, C.H and Steinbergs, A., 1962 Plant Soil, : 279-294 Williams, C.H and Steinbergs, A., Plant Soil, : 50-62 SUBJECT INDEX Actinolite, 52 -, dissolution by HA, 52 adenine, 107 adsorption of huniic substance, 52-53 -, in clay interlayers, 53 -, on external surfaces, 53 adsorption isotherms, 148-152 -, classification, 149 -, Freundlich, 149 -, Langmuir, 150 -, mass action, 152 -, Rothmund-Kornfeld, 152 adsorption of pesticides, 137 -, acidic, 155 -, basic, 154 -, cationic, 152 -, effect of cations, 159 -, effect of pH, 141,146,147,155 -, effect of solubility, 141 -, mechanisms, 162 -, non-ionic, 157 -, on charcoal, 154,155,157-160 -,on humic acid, 150,151,154-162 -, on lignin, 154,161 -, on lipid, 158 -, on marine sediments, 157 -, on muck, 155,156,160 -, o n nylon, 155 -, on organic matter-clay complex, 161-162 -, on straw, 155 -, techniques, 162 aggregation, 86-87 aldrin, 157, 158, 164 alkaline CuO oxidation of HA’s and FA’S, 27,31-34 alkaline KMn04 oxidation of HA’s and FA’S, 27, 29,31,33-34 alkaline nitrobenzene oxidation of humic substances, 27 alkanes, 42-44 -, isolation from humic substances, 42-43 allantoin, 105 aluminum -, stability constants of AI-FA complexes, 50 aminoacids, 95,99,105, 106,111, 112, 113, 114, 115, 116, 117, 123, 126, 127 amino sugar, 117,127 amitrole, 164 ammonium -, fixed (non exchangeable), 100,102, 127 ammonification, see mineralization analysis of humic substances by nondegradative methods, 11-26 -, electrometric titrations, 25-26 -, electron microscopy and electron diffraction, 18-21 -, electron spin resonance spectrometry, 14-17 -, infrared spectrophotometry, 13 -, gel filtration, 24 -, molecular weight measurements, 23-25 -, nuclear magnetic resonance spectrometry, 14 -, spectrophotometry in the UV and‘ visible regions, 11-33 -, surface tension measurements, 22-23 -, ultracentrifuge, 24 -, vapor pressure osmometry, 23-24 -, viscosity measurements, 21-22 -, X-ray analysis, 17 animal wastes (feces, urine, excretions), 95-96.105 atrazine, 143,151, 155, 164, 165 A-value (nitrogen), 216,222 Barium, 48 -, complexes with humic substances, 48 basalt, 52 -, dissolution by HA, 52 benefin, 159 benzenecarboxylic acids, 28, 30,31,32, 33 312 biological degradation of HA’s and FA’S, 42 biomass, 202,204, 214,216, 243,248 -, calculation of, 243 biotin, 110 biotite, 52 -, dissolution by HA, 52 bromacil, 157 burning plant residues, 196-199, 264 butralin, ‘‘C-glucose, 83 cacodylic acid, 157 cadmium, -, complexes with humic substances, calcium, 48, 50 -, stability constants of Ca2+-FA complexes, 50 carbaryl, carbohydrates, 65-80 -, composition, 74-80 -, distribution in soil, 67-70 -, fractions in soil, 70-74 -, nomenclature, - carbon, , 177, 196 -, in atmospheric C02, -, in biomass, -, in coal, -, in deep sea, -, in fresh water, -, in humic materials, -, in marine C, -, in marine detritus, -, in petroleum, -, in sediments, -, in soil organic matter, carbon burning, 197 -, effect of long term cropping on, 185-1 88 -, effect of tillage on, 199 -,losses of, 185-188,191,199, 230 -, mineralization of, 217, 218 -, profile distribution of, 177, 180 -, turnover of, see organic matter, turnover carbon dating soils, 205, 228, 245-247 -, bomb carbon effect, 246 -, De Vries effect, 246 -, Suess effect, 246 C-bonded S,1 2 , , , , C/N ratios, 177-180, 196, 199, 209, 212,213, 244 -, effect of cultivation on, 186 SUBJECT INDEX -, profile distribution of, 177-180 cellulose, 71, 78, characterization of humic substances, 7-3 -, by elementary analysis, - -, by degradative methods, 26-45 -, by non-degradative methods, 11-26 charcoal, adsorption on, 72 charge transfer, chemical structure of humic substances, 45-47,57 chitin, 99 chlordane, 158 chlorite, 52 -, dissolution by FA, 52 chlorpropham, 160 choline, 108 chromatography, 113, 120, 121, 130 clay-organic complexes, 127 cobalt, 48, 50 -, stability constants of Co2*-FA complexes, 50 complex formation of fulvic acids, -, with organics, -, with toxic metals, complex formation of humic substances, -, with clay minerals, -, with hydrous oxides, -, with metal ions, -, with organic compounds, copper, 48-50 -, stability constants of CuZ+-FA complexes, 50 correlations, 102 creatinine, 1 crop residues, 191, 193, 195-196, 206, 214 -, burning, 196-199 -, decomposition rate of, 195, 213 -, nitrogen composition of, 195 -, yield depression by, 196, 197, 199, 214 crop rotations, 185-191, 194 cycle, see also nitrogen -, “continuous internal”, see organic matter, turnover -, Krebs, 206 -, melting and drying, 224 cytosine, 107 2,4-D, 156, 161, DDT, , , , , , SUBJECT INDEX 313 decomposition, see also organic matter epidote, 52 -, aerobic, 203-206 -, anaerobic, 206-207 -, dissolution by HA, 52 - carbohydrate, 206, 209, 211 -, lignin, 209 -, protein, 206 degradation of humic substances, 26-45 -, alkaline CuO oxidation, 27, 31-34 -, alkaline KMnO, oxidation, 27, 29, 31, 33-34 -, biological degradation, 42 -, high-energy irradiation, -, hydrogenation and hydrogenolysis, 37 -, hydrolysis with acid, 38 -, hydrolysis with base, 38-39 -, hydrolysis with water, 37-38 -, hypohalite oxidation, 34 -, major degradation products, 28-32 -, oxidation, 27-34 -, pyrolysis-gas chromatography, 39-41 -, reduction, 34-37 -, sodium-amalgam reduction, 35-37 -, thermal methods, 39-41 -, yields of products, 33-34 -, zinc dust distillation and fusion, 3435 dialysis of humic substances, diazinon, 158 dicamba, 156 dichlobenil, 161 3,4-dichloroaniline, 160 dieldrin, 157, 158 dimefox, 159 dinoseb, diphenamide, 160 diquat, 144, 145, 163, 164 diuron, 159 DSMA, 157 Dumas, 102 E4/E6 ratios of HA’s and FA’s, 11-12 electrometric titrations of humic substances, 24-25 electron diffraction, 20-21 electron microscopy of HA’s and FA’s, 18-20 electron spin resonance spectrometry of HA’s and FA’S, 14-17 endrin, 158, enstatite, 52 -, dissolution by HA, 52 enzymes, , erosion, see nitrogen, losses of ethanolamine, 108 extraction of humic substances by, 3-5 -, cation exchange resins, -, NaOH solution, , -, Na-pyrophosphate solution, 4, -, organic solvents, -, sequential reagents, -, ultrasonic dispersion, Fatty acids, 42-45, 108-109 -, isolation from humic substances, 42-45 -, phenol-fatty acid esters, feldspar, 52 -, dissolution by HA, 52 fluorescence of HA’s and FA’s, 12-13 fonofos, 150, 158 forest humus, 72, fractionation of humic substances by, 5-7 -, acidification, -, activated charcoal, -, addition of electrolyte, -, addition of metal ions, -, Alz03,6 -, electrophoresis, -, freezing, -, gel filtration, -, methylation and chromatographic methods, -, mixtures of organic solvents and , water, -, salting out, -, varying pH and ionic strength, free sugars, 76 fulvic acid, 2, 7-8, 8-10, 11-54, 111, 116,117,124,126 -, analysis by chemical methods, 26-45 -, analysis by physical methods, 11-26 -, chemical structure, - -, definition, -, elementary analysis, 7-8 -, oxygencontaining functional groups, 8-1 -, physiological effects, 55-56 -, reactions with metals and minerals, 47-54 -, reactions with organic compounds, 54-56 314 furans, 28 Galactosamine, 114 gas chromatography-mass spectrometry computer, 27, 28 -, separation and identification of HA and FA degradation products, 27-28 gel filtration of humic substances, 24-25 gibbsite, -, dissolution by FA, 52 glucosamine, 114 glycerophosphate, 109 goethite, 52 -, dissolution by FA, 52 -, green manure, see manures guanine, 107 Hematite, 52 -, dissolution by HA, 52 hemicellulose, heptachlor, 158, 164 heptachlor expoxide, 158 hexosamine, 74, 76, 79, 112, 113 HI-reducible S, 122, 123, 124, 125, 126, 127 high-energy irradiation of HA’s and FA’S, 41 human wastes, humic acid, 2, 7-8, 8-10, 11-54, 72, 73,111,116,117,124-126 -, analysis by chemical methods, 26-45 -, analysis by physical methods, 11-26 -, chemical structure, 45-47 -, definition, -, elementary analysis, 7-8 -, oxygen-containing functional groups, 8-1 -, physiological effects, 55-56 -, reactions with metals and minerals, 47-54 -, reactions with organic compounds, 54-56 humic substances, 1-7, 10,41-42 -, definition, -, distribution of N in, -, extraction, 3-5 -, fractionation, 5-7 -, purification, -, radiocarbon dating, 1-42 -, synthesis, 1-3 humification, 113 humin, 2,116-117 -, definition, SUBJECT INDEX humoprotein, 117 humus, 105, 107, 111, 117, 193, 196, 202, 203, 204 -, humification of, 204 -, mean residence time of, 205, 246 -,stability of, 205, 206, 211, 220, 228, 246 hydrogen-bonding, 18, 19, 46, 47, 53, ‘ 143 hydrogen peroxide oxidation of humic substances, 27 hydrogenation and hydrogenolysis of HA’s, 37 hydrolysis, 37-39 -, with acid, 38 -,with base, 38-39 -, with water, 37-38 hydrophobic bonding, 142 hydroxamic acid, 1 hymatomelanic acid, hypohalite oxidation of HA’s, 34 Illite, 100 immobilization, 97 infrared spectrophotometry of humic substances, 13 inositol PO4, 102, 107, 117, 119, 120, 127 ion exchange, iron, 49, 50 -, stability constants of Fe3+-FAcomplexes, 50 -, reactions with HA and FA, 52-53 isocil, 157 isotope, 111, 128, isotopic discrimination, 246 isotopic exchange, 214 Kjeldahl, Lead, 48, 50 -, stability constants of Pb2+-FA complexes, 50 ligand exchange, 148 light fraction, 71, 73, 76, 77, 79 lindane, 157, 158, 164 linuron, lipids, 108, 122 Magnesium, 48, 50 -, stability constants of Mg2+-FA complexes, 50 manganese, 48, 50, 52 31 SUBJECT INDEX -, stability constants of Mn*+-FA complexes, 50, 52 manganese oxides, 52 -, dissolution by HA, 52 manures, 191-195 -, benefits of, 193 -, compost, -, effect on soil aggregation, 257-258 -, farmyard, 191, 194, 231 -, green, 191, 193-195, 203, 214, 215 -, N-P-K content of, 191 -, nutrient losses from, -, pollution potential of, 193 mean residence time, see organic matter metals, reactions of humic substances with, 47-52 -, copper, 49 -, ferric iron, -, manganese, 51-52 -, metal ions, 48-52 -, stability constants, 49-50 mica, 52 -, dissolution by FA, 52 mineralization of N, 173, 196, 202, 204, 294-295, 298, 299, 300, 301, see also turnover -, effect of burning on, 197-198 -, effect of chemical tillage on, 200 -, effect of environmental factors on, 220-228 -, effect of fertilizers on, see priming effect -, effect of freezing and thawing on, 225-228 -, effect of moisture on, 221 -, effect of ploughing on, 199 -, effect of salts on, see priming effect -, effect of temperature on, 221-223 -, effect of trees on, 191 -, effect of melting and drying on, 223-225 -, flush of, 220,221, 224, 225-228 -, potential of soil, 254-256 -, remineralization, 202, 210, 211, 212 -, of organic sulfur, see turnover of organic sulfur -, amino acids, 290-291 -, effect of drying on, 299-301 -, effect of environmental factors on, 297-3 01 -, effect of melting and drying on, 301 -, effect of moisture on, 297-298 -, effect of temperature on, 298-299 minerals, 52-53 -, adsorption of humic substances in clay interlayers, -, adsorption of humic substances on external surfaces, -, dissolution by humic substances, 53 molecular weights of HA's and FA'S, 25 monosaccharides, 74, 75, 77 monuron, mulching, 200-201 -, effect on microbial activity see microflora -, to control erosion, 201 Nickel, 48, 50 -, stability constants of Ni2+-FA complexes, 50 nitric acid oxidation of humic substances, 27 nitrogen, 175, 196, 199 -, amount in USA soils, 177 -, amount on Canadian prairies, 177 -, amount on earth, 175-177 -, available, 248-256 -, crop requirement of, -, cycle, 201-203, 285 -, effect of burning on, 197 -, effect of crop rotations on, 197 -, effect of long term cropping on, 185-188 -, effect of manures on, -, effect of mulching on, 200, 201 -, effect of temperature on, 180-184, 210 -, effect of water supply on, 181-184 -, equilibrium level of, 185, 188, 209, 229-232,244, 245 -,hydrolysis, 112, 116 -, immobilization, 195, 196, 202, 203, 205-213 -, leaching of, 192, 198, 200 -, losses of, 185-188.191, 194, 198, 202,230,263 -,organic, 95-102, 104-118, 121, 125-130 -, plant tissue, 97 -, root excretion of, 190 -, roots, 96 -, sources of, nitrogen availability indexes, 249-256 -, aerobic incubation, 250 SUBJECT INDEX 316 -, anaerobic incubation, 250 -, boiling water, 250 -, transformation dynamics, see -, Jenkinson’s Ba(OH)2, 251 -, nitrate-N, 250 -, turnover, 207-213, 237-243 -, under forests, 234 N0~,99,100,101,102 -, under pastures, 231-232, 235 -, using carbon dating, 245-247 -, Cornfields’, 251 non-humic substances, -, amino acids, -, carbohydrates, -, fats, -, low-molecular weight organic acids, -, peptides, -, proteins, -, waxes, nuclear magnetic resonance spectrometry of HA’s and FA’S, 14 nucleic acid, 95,99,107,108,117,119 nucleoprotein, 107 Organic complexes, 184-205, 206, 261- 262 -, metal-clay, 184,205 -, organa-etal, see chelation, soil colloidal properties organic compounds, reactions with humic substances, 54-55 organic fertilizers, 248 organic matter, active fraction of, 190, 193,199,204,208,211 -, amino acids in, 204,205,211, 212, 224 -, amino sugars in, 204, 205,211, 212 -, decomposition of, 173, 193,199,200, 202-207,209, 214 -, distribution in profile, 177-180 -, effect of management practices on, 185-201 -, effect of soil farming factors on, 177 -, effect on soil acidity, 262 -, effect on soil drainage, 263 -, effect on soil moisture relationships, 262 -, effect on soil physico-chemical -, properties, 173,256-263 fractionsof, 204, 210, 230,246, 248, 264 -, light fraction of, 190,204 -,losses of, 185-188, 194,198,199, 263 -, mean residence time of, 205,246 -, mineralization of, see mineralization -, optimum level of, 184-185 dynamics, organic matter dynamics, 228-247 -, using long term cropping data, 229237 -, using Morrow plot data, 237 -, using Rothamsted data, 230-231 -, using Sanborn plot data, 237 -, using Waite Institute data, 232 organic matter-metal-phosphate complex, 127 organic sulfur, decomposition and stabilization of, 286-293 -, effect of cropping on, 281-283 -, effect of liming on, 284-285 -, effect of management on, 281-285 -, effect of manures and residues on, 283-284 -, effect of soil farming factors on, 279-281 -, enzyme breakdown of, 287-288, 292-293 -, forms of, 276-278,287 -, in biomass, 288 -, in humus, 286,288-290 -, mineralization-immobilization of, see turnover of organic sulfur -, nature and distribution of, 275-276, 278-2 79 -, stability of, 288-289 -, turnover of, 290-297 oryzalin, 160 oxidation degradation of humic substances with, 27-28 -, alkaline CuO, 27 -, alkaline CuO + KMn04, 27 -, alkaline CuO + KMn04 + H z O z , 27 -, alkaline KMn04, 27 -, alkaline nitrobenzene, 27 -, hydrogen peroxide, 27 -, nitric acid, 27 -, peracetic acid, 27 Paraquat, 143-145, 162, 163 parathion, 142, 158,161 PCP, 156 pastures, 190,191,231-232, 235 -, legume-based, 190 SUBJECT INDEX -, leys, 190 peptides, 106,112, 116, 117 peracetic acid oxidation of humic substances, 27 pesticides, 138,139 -, bound residues, 165 -, chemical alteration, 164 -, common names, 138,139 -, nature, 140, 141 -9 PK,, 146,147,156 -, protonation, 145-147 phanacridane chloride, 154 phenolic acids, 28,30,32,33,35,44 phorate, 158,164 phosphon, 154 phospholipids, 95,108,109, 117, 119 phosphoprotein, 99 phosphorus, biomass, 104 -, hydrolysis, 102 -, organic, 95-105, 107-112, 117-122, 125-130 -, plant tissue, 97 -, roots, 95 physiological effects of humic substances, 55-56 -, direct effects, 55-56 -,hydrogen acceptors, 55 -, indirect effects, 55-56 -, interactions with growth regulators, 56 -, on absorption ofmetal ions, 56 -, on carbohydrate metabolism, 56 -, on cell elongation, 56 -, on invertase development in beets, 56 -, on protein synthesis, 56 -, on root formation in bean stem segments, 56 -, o n soil fertility and productivity, 56 -, respiratory catalysts, 55 pi bonding, 52 picloram, 142, 156 plant nutrient, 173,193 -, availability of, 174-248-256 -, essential, 173-1 74 -, macro, 173-174 -, micro, 173-174 -, sources of, 175 -, uptake of, 174 317 polysaccharide decomposition, 85 polysaccharides in soil, see soil polysaccharides polysaccharide-tannin complex, 86 polyvinylpyrrolidone, 72,117, 126 pore clogging, 91 porphyrin, 11 priming effect, 213-220 -, effect of soluble salts and fertilizers, 215-220 -, protolyfic theory, 219, 224 profluralin, 160 prometone, 155, 162 prometryne, 155 propazine, 155, 165 propham, 160 protein, 99, 106,116 proteolytic enzyme, 116 proximate analysis, 70, 71 purification of humic substances by, -, dialysis, -, dilute HCI-HF solution, -, exchange resin, -, ultrafiltration, purines, 107, 108,116 pyridyl pyridinium chloride, 154 pyrimidine, 107, 108,116 pyrolusite, 52 -, dissolution by HA, 52 pyrolysis of organic matter, 126 pyrolysis-gas chromatography, 39-4 pyrophosphate, 111 Radiocarbon dating, 41,42, 129,see also carbon dating -, of humic substances, 41-42 Raney nickel reaction, 123, 124 ratios: CINIS, 275, 280, 281, 296,see also C/N ratio CIS, 199,283, 284 C/p, 196 N/S, 196,275-276,279,294-296 NIP, 196 SIP,196 N-availability, 207, 210 reactions of humic substances with organic compounds, 54-55 P04’-, 99,100,101,102,111,113,119, -, amino acids, 55 120 -, sugar, 107,121 -, ammonia, 54 polyamide, adsorption on, 72 -, DDT, 54 polysaccharide-copper complex, 82 -, dialkyl phthalates, 54 318 -, glycocol, 55 -, N-containing compounds, 54 -, urea, 54-55 reduction of HA’s and FA’S, 34-37 “reversion” of fertilizer nitrogen, 207, 210 root exudates, 105, 106 Schweitzer’s reagent, 71, 78 serine, 108, 113, 115 simazitie, 143 small angle X-ray scattering, 17 S04’-, 99,104,107,123,126 -, esters, 125 -, lipids, 123 -, polysaccharides, 107,123 -,hydrolysis of organic, 104 sodium amalgam reduction of HA’s and FA’S, 35-37 soil aggregation and structure, 256-258 soil colloidal properties, 258-261 -, buffer capacity, 259-261 -, cation exchange capacity, 258-259 -, chelation, 261-262 soil enzymes, 203, 206 soil fauna, 203 soil fertility, 173 -, effect of burning on, 198 -, effect of crop residues on, 195 -, effect of legumes on, 190 -, effect of manures on, 193 -, relationship to organic matter, 173 soil genesis, 88-90 soil microbial activity, 197, 199,200, 201, 207,208,209 -, effect of burning on, 197 -, effect of mulching on, 201 -, effect of tillage on, 199,200 soil microflora, 202, 203, 206,213, 224 -, anaerobic, 206, 211 -, autotrophic, 215 -, effect of freezing & thawing on, 226 -, effect of melting & drying on, 224 -, flush of, 220-221 -, rhizosphere, 209,219 -, turnover, 237 soil organic matter, see organic matter soil polysaccharides, 77-91 -, behavior, 84-86 -, charge characteristics, 82 -, composition, 77-78 -, molecular weight, 80-81 SUBJECT INDEX -, optical rotation, 81 -, origin, 82-83 -, properties, 80-82 -, significance, 86-91 -, viscosity, 81 soils, 52 -, dissolution by FA, 52 spectrophotometry in the U V and visible regions, 11-13 sulfatase activity, 292-293, 297 sulfate esters, 287,292,301 sulfolipid, 108-1 10 sulfonic acids, 110 sulfur, 96 -, as nutrient, 273 -, biomass, 110, 11 -, cycle, 274,276,285-286 -, effect of burning on, 197 -, effect of tillage on, 199 -, inorganic fraction of, 278 -,organic, 95-112, 117, 121-130 -, plant tissue, 97 -, roots, 95 -, sources of, 273-275 -, transformations in soil, 285-293 -, volatile, 291-292 sulfur availability index, 302-307 -, acetate soluble S, 305 -, bicarbonate soluble S,305-306 -, heat-soluble S,305 -, organic S,304-306 -, plant assay, 302-303 -, reducible S,306 -, reserve S,306 -, S released on incubation, 306 -, sulfate S,303-304 sulfur fractions, see also forms of organic sulfur -, active organic, 288 -, bicarbonate extractable, 285,305- 306 -, C-bonded, 276-278, 279,282,289 -, heat-soluble, 292, 305 -, HI-reducible, 276-278, 279,280, 282,289,290, 293,301 -, phosphate extractable, 285 -, residual, 276,278 surface tension of HA’s and FA’S, 22-23 synthesis of humic substances, Tannin, 85 techniques of pesticide adsorption, 162 SUBdECT INDEX -, continuous flow method, 162 -, gel filtrations, 163 -, microcalorimetry, 162,163 -, slurry method, 162 teichoic acid, 99 terbacil, 157 terbutryne, 155 theories on the synthesis of humic substances, -, chemical polymerization hypothesis, -, cell autolysis hypothesis, -, microbial Synthesis hypothesis, -, plant alteration hypothesis, thermal methods of degradation of HA’s and FA’S 39-41 thiamine, 110 threonine, 113 tillage, 199-200 -, aggregate disruption by, 199 -, chemical, 200 -, ploughing, 199 tracers, 203,209 210,214-216, 237- 243,264,265 -, 14C, 210,214 215,245-247 -, ”N, 209, 210, 216 319 turnover of organic sulfur, see organic sulfur -, effect of plants on, 296-297 -, relationship between N, C and S, 294-296 Ultrafiltration, uracil, 107 uronic acids, 74, 79 Van der Wad’s forces, 19,46,142 vermiculite, 100 viscosity of HA’s and FA’s, 21-22 vitamines, 110,116 Water repellency, 23 -, role of FA in, 23 X-ray analysis of HA’s and FA’s, 17 Zinc, 48, 50 -, stability constants of Zu’+-FA complexes, 50 zinc dust distillation and fusion of HA’s and FA’S, 34-35 This Page Intentionally Left Blank ... sequence of events appears to be HA - FA , EXTRACTION OF HUMIC SUBSTANCES The organic matter content of soils may range from less than 0.1% in desert soils to close to 100.0% in organic soils In inorganic... F SOIL SURVEYS G.H BOLT (Editor) SOIL CHEMISTRY ( t w o volumes) H.E DREGNE SOILS O F ARID REGIONS H AUBERT and M PINTA TRACE ELEMENTS IN SOILS Developments in Soil Science SOIL ORGANIC MATTER. .. these systems In spite of this, soil organic matter remains a neglected field in soil science and receives but scant attention in soil science courses One of the purposes of this book is t o remedy