Trace Elements in Soils (Developments in Soil Science)

Developments in Soil Science 7 TRACE ELEMENTS IN SOILS Further Titles in thts Series 1 . I. VALETON BAUXITES 2. I.A.H...

Author: Huguette Aubert

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Developments in Soil Science 7 TRACE ELEMENTS IN SOILS

Further Titles in thts Series 1 . I. VALETON BAUXITES 2. I.A.H.R. FUNDAMENTALS OF TRANSPORT PHENOMENA IN POROUS MEDIA 3. F.E. ALLISON SOIL ORGANIC MATTER AND ITS ROLE IN CROP PRODUCTION 4 . R . W . SIMONSON (Editor) NON-AGRICULTURAL APPLICATIONS OF SOIL SURVEYS

5 . G.H. BOLT (Editor) SOIL CHEMISTRY (two volumes) 6 . H.E. DREGNE SOILS OF ARID REGIONS

7. H. AUBERT and M . PINTA TRACE ELEMENTS IN SOILS 8. M . SCHNITZER and S. U. KHAN (Editors) SOIL ORGANIC MATTER

9.B.K.G. THENG FORMATION AND PROPERTIES O F CLAY-POLYMER COMPLEXES

Developments in Soil Science 7

TRACE ELEMENTS IN SOILS H. AUBERT M. PINTA La bora toire de Spectrograph ie Office de la Recherche Scientifique e t Technique Outre-Mer 931 40 Bondy (France)

Preface by GEORGES AUBERT

Translated from the French by LAWRENCE ZUCKERMAN and PIERRE SEGALEN

Published for O.R.S.T.O.M. by

ELSEVIER SCIENTIFIC PUBLISHING COMPANY Amsterdam - Oxford - New York 1977

ELSEVIER SCIENTIFIC PUBLISHING COMPANY 335 Jan van Galenstraat P.O. Box 211,1000 AE Amsterdam, The Netherlands Distributors for the United States and Canada: ELSEVIER/NORTH-HOLLAND INC. 52,Vanderbilt Avenue New York, N.Y. 10017

First edition 1977 Second impression 1980

L i b r a r y of Congress Calaloging in Publication Data

Aubert, Huguettc. Tra e elements i n s o i l s . (1)eveloprnents i n s o i l s c i e n c e ; 7,) T r a n s l a t i o n of Les 616ments t r a c e s dans l e s sols. Bibliography: p. 1. Trace elements i n s o i l s . I . P i n t a , Maurice, j o i n t a u t h o r . 11. France. O f f i c e de l a recherche s c i e n t i f i q u e e t technique outre-mer. 111. T i t l e . IV. Series. S592.6.T7A?13 5 1 . 4 ’ 1/ 77- 5 ‘j(,2 ISBN 0-4144-41 5 i l - J i

ISBN: 0-444-41511-4 (Vol. 7) ISBN: 0-444-40882-7 (Series)

The original edition of “Trace Elements in Soils” was published in French under the title “Les klkments traces dans les sols” by O.R.S.T.O.M. - Paris, 1971.

0 Elsevier Scientific Publishing Company, 1977 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 Scientific Publishing Company, P.O. Box. 330,Amsterdam, The Netherlands. Printed in The Netherlands

V

PREFACE In soils, a certain number of elements are predominant or exist in important quantities: oxygen, hydrogen, silicon, aluminium, iron, carbon, nitrogen, calcium and magnesium, sodium and potassium, phosphorus and sulphur, their contents varying widely from one soil to another. Soil element contents vary widely, for example, in a ferrallitic soil of the lower Ivory Coast, rich in kaolinite, and the same type of soil, essentially composed of iron oxide, in the centre of New Caledonia, or aluminium oxide in some nearby islands. Content also varies from one horizon to another in the same soil profile. Other elements, such as copper, lead, nickel, cobalt, molybdenum, etc, are found only in traces in soils. Nevertheless, the majority of these elements, if not all, play a primary role in plant nutrition and development. Even if it is not usually possible to determine with exactitude the effect of small variations of these elements on plants, at least it is possible, most of the time, to observe the consequences of their deficiency, or their presence in excess, in forms which have a stronger effect on plants or are more “available” to them. Some of these elements can, because of the nature of the parent rock, or climatic or topographic conditions (pedogenic factors) become very abundant in some soils. This phenomenon can reach a point where the soils, or the horizons of particular soils, are transformed into veritable ores, leading to an industrial exploitation (manganese, nickel, cobalt, etc.). In other cases lesser trace element concentrations can play an important part in soil evolution. Therefore, the knowledge of their presence and, also, of their dynamics is very important to pedologists. Although these facts have been known for a long time, trace elements in soils have not been the object of much investigation until recent decades, in spite of the noteworthy work of Gabriel Bertrand, in France, dating from the beginning of the century. This situation may have been due t o the difficulties involved in the analyses of some of the elements. In t h e last thirty years, however, with the development of the use of physical methods in soil analysis, such as spectrography and atomic absorption, trace element research has increased markedly. The development of geochemistry also led t o the establishment of some fundamentals which helped towards a better understanding of the reasons for their presence, associations and evolution. This is illustrated by an article of G. Pedro and A.B. Delmas in an issue of “Annales Agronomiques” recently devoted to oligoelements in the soils of France and the studies of many foreign workers: V.M. Goldschmidt, R.L. Mitchell, V. Kovda, K.K. Turekian, K.H. Wedepohl, A.P. Vinogradov, etc. The task of the pedologists of O.R.S.T.O.M. is to study the soils of various ecological regions of the globe. They deal with soils belonging to numerous classes and groups on extremely varied parent rocks and in very different conditions of evolution. For a long time, trace element determinations have been essentially carried out at the “Services Scientifiques Centraux de

VI

l’O.R.S.T.O.M.”, Bondy, for 1’O.R.S.T.O.M. and for various associated institutes. However, for the last few years, many analyses have been carried out, on the spot, in laboratories established by 1’O.R.S.T.O.M. in many countries. The staff of the Spectrography Laboratory of the “Services Scientifiques Centraux de l’O.R.S.T.O.M.”, Bondy, under the very dynamic leadership of M. Pinta, has accumulated much data in this field and has devoted much time to various studies concerning the presence and geochemistry of some of these elements in several types of soils. I can cite, for example, articles by M. Pinta, L. Nalovit, D. Rambaud. A summary and clarification of all these data appeared necessary, and Mr. M. Pinta and Miss H, Aubert took charge of this project. Since articles concerning trace elements appear very frequently, it is impossible to collect an exhaustive bibliography, even if we do not take into account some articles, written in less common foreign languages, which have not been translated. We are aware of the imperfections of this work, but we hope, however, that it might be of some use to numerous workers, particularly pedologists and agronomists. G . AUBERT Director of the Pedology Division of 1’O.R.S.T.O.M. Member of the “AcadBmie d’Agriculture” and the “AcadBmie des Sciences d’Outre-Mer”

VII

PREFACE TO THE ENGLISH EDITION In 1971, “1’Office de la Recherche Scientifique et Technique Outre-Mer” published in its series “Travaux et Documents” the work entitled “Les Elbments Traces dans les Sols”. This work brought up-to-date the knowledge acquired in this field in 1’O.R.S.T.O.M. laboratories as well as abroad. These data, which were classified element by element, were compiled into synoptic tables. The aim of this compilation, based on scientific work from all parts of the world, was to interest researchers from all countries, and, especially, English-speaking countries. That is why the authors are particularly grateful to Elsevier, who works in strict collaboration with “1’Office de la Recherche Scientifique e t Technique Outre-Mer” for being responsible for the English edition. But it was fitting that this new edition should be adapted to new readers and, at the same time, should take into account work published after 1969, the year in which the bibliography of the French edition ended. As to the first point, the reader will notice that, in the tables, the 7th Approximation (U.S.D.A.) Soil Classification System has been taken into account for the classification of soils. As to the updating of this work, there is at the end of each chapter a list of new bibliographical references concerning papers published between 1968 and 1975. This list does not pretend to be exhaustive. Only a limited number of publications, which appear of value, are included. If these new studies confirm what was already known in 1969, they frequently present characteristics of a different nature. They are often a synthesis or, on the contrary, studies relating to a specific agronomic feature. The new references are classified in a geographical order that seems to be more logical in the general context of the work. The English translation was produced with the collaboration of Messrs. L. Zuckerman and P. Segalen, O.R.S.T.O.M. researchers; the authors especially offer them their congratulations for the quality of their assistance. M. PINTA Research Director

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CONTENTS Preface .................................................. V Preface to the English Edition ................................. VII Foreword ................................................ 1 Boron . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5 Chromium . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13 19 Cobalt . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Copper .................................................. 27 Iodine . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35 39 Lead . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Manganese. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 43 Molybdenum .............................................. 55 Nickel . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 63 69 Selenium . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 73 Titanium . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Vanadium . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 79 Zinc..................................................... 85 Other elements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 95 Rare alkaline elements: lithium, rubidium and caesium . . . . . . . . . . . . 9 5 99 Alkaline earth elements: barium, strontium .................... Bismuth ................................................ 104 Gallium ................................................ 105 Germanium ............................................. 109 S ~ v e.................................................. r 110 112 Tin . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Conclusion ............................................... 115 References up to 1968 ...................................... 119 References 1968-1975 ...................................... 135 Appendix . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . (see Tables)


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FOREWORD The importance of trace elements in different media is now taken for granted, as a result of the vast amount of research work devoted to this field since the beginning of the century and, especially, since 1945. In the field of agronomy, in particular, trace elements play a major role in soil fertility. The absorption of these elements by plants in too low or too high a quantity can bring about deficiency or toxicity diseases in these plants and, ultimately, in the animals which feed upon them. That is why agronomists, geochemists, pedologists and biochemists have been interested in these problems for a long time (Saukov, 1931;Wallace, 1947,1961;MonnierWilliams, 1950; Stiles, 1951; Yoe and Koch, 1957; Goldschmidt, 1954; Swaine, 1955; Mitchell, 1948; Underwood, 1956; Vinogradov, 1959; Pinta, 1971; Shaw, 1964; Sauchelli, 1969; Pedro and Delmas, 1970). Besides the basic works published by these authors, quite a number of papers have appeared and continue t o appear in numerous publications concerning some particular facets of this field. It appeared useful t o summarize and clarify all this information. The data included in this bibliographical study concern, principally, fifteen elements, those most frequently studied in the last ten years. However, this does not mean that the elements not included d o not play an important role. For example, aluminium, iron and silicon are not included in this study, for, although considered as trace elements in plants, they are found in important quantities in soils. For certain elements, such as boron, molybdenum, manganese, cobalt, zinc, copper and nickel, a relatively important number of bibliographical references and publications of quite a different nature were compiled. In most cases, the work concerns systematic research on one or several elements in the different types of soils of a well-defined geographical region, sometimes with the aim of formulating a distribution map of these elements (the U.S.S.R., for example) but one can also find a study limited to only one element of a very large number of soils of different regions of the same country (India, for example) or a study of a very limited number of soils (study of a particular deficiency). For other elements, such as chromium, iodine, vanadium, lead and selenium, the numbers of references and publications are less numerous, which does not mean, naturally, that they are of lesser importance, but that their study is often more recent and the work concerns, essentially, cases of deficiency or toxicity (iodine, in particular). As for the soils of France, Coppenet (1970) has recently published a chronological review concerning the deficiency of trace elements and its effect on plants. This paper, together with the paper of Pedro and Delmas, cited above, makes up a special number of the “Annales Agronomiques” devoted t o trace elements in France.

2

To these bibliographical references were added the analytical data of the Pedology Spectrographic Laboratory of the “Services Scientifiques Centraux” de 1’O.R.S.T.O.M. In fact, since its establishment, this laboratory has fulfilled the requests of agronomists, pedologists, etc. of 1’O.R.S.T.O.M. or other institutes involved in research work in tropical countries for the analyses of trace element contents in a large number of tropical and subtropical soils, principally of Africa and Madagascar. These soils, for which the trace element contents and their possible use for cultivation purposes were little known, have now become the object of a systematic research program with the aim of their development in mind. (These analytical results have been obtained thanks to the technical assistance of Mrs. M.L. Richard.)

PRESENTATION OF THE RESULTS

A table is given for each element. The following headings are used in the tables: origin, parent rock, soil type, total contents, plant-available contents, deficiency or toxicity, etc. These headings are discussed below.

Parent rock and its trace element content Parent rocks play an important part in determining soil trace element contents. These rocks constitute the reserve and primary source of these elements. Most often there is a direct relationship between the respective contents of a given element in soils and rocks, in the same type of soil, formed on different rocks. The differences observed between rock contents and soil contents are due t o some processes which intervene during the formation of soils (illuviation, eluviation and biogenetic accumulation in certain horizons).

T y p e of soil Terms defining the soils studied were taken from the original publications. Some terms belong to the present-day classifications employed by pedologists (American, French, Soviet classifications). Other terms are much less precise, from the pedologic point of view, giving either physical characteristics such as colour (black soil, red soil, etc.) and texture (sandy soil, clayey soil, etc.) or a chemical characteristic (calcareous soil, acid soil, alkaline soil, etc.); therefore, these soils cannot be linked t o any one particular group of classification. With the aim of homogeneity in mind it seems useful, for the understanding and utilization of the results and for future work, to translate, as much as possible, the characteristics of the soils studied into the terms of the French classification. In some cases it is not difficult because the terms used are clearly defined, even if not in a very precise way, on an international

3

level (rendzinas, chernozems, regosols, etc.); sometimes there is a rather satisfactory relationship between the different classifications, but, a t other times, it was necessary to interpret these terms, particularly in relation t o climatic and geographic information, in order t o determine, with some degree of certitude, the type of soil studied.

Horizon This heading includes information concerning the horizons in which the sampling took place: surface horizon, cultivated horizon, humiferous horizon, etc. Data of other columns, corresponding to these horizons, include total trace element contents and plant-available contents. The distribution of the element in the profile is also indicated.

Total element content The expression used t o signify contents varies according t o the different authors. Most of the time, however, results are evaluated as n X %, mg/kg or p.p.m., of air-dried soil. To facilitate comparison between different data, all the results were converted to parts per million (p.p.m.), the unit most commonly used. The contents are expressed in p.p.m. of the element itself and not of oxides or other compounds. According t o the different publications, the minimum or maximum values and the average values of the whole soil or horizon have been given if there was a limited number of soils. In some cases, the minimum value was given as being below a certain limit, for this limit was due t o the method of determination employed. Sometimes, notations are given (low, average and high contents) instead of data. Whenever it was possible, the number of samples studied by the authors was indicated.

Trace element content “available” to plants Plant-“available” element contents are also expressed in p.p.m. of air-dried soil. Usually the extraction reagent is indicated. Among the proposed and most often used reagents, either for the extraction of an element or several elements at the same time, the following can be cited: water at 100°C (boron extraction, Berger and Truog, 1939), oxalic acid-ammonium oxalate buffer, pH 3.3 (molybdenum extraction, Grigg, 1953), 0.1 N hydrochloric acid (zinc extraction, Bonig and Heigener, 1956), 1 N ammonium acetate, PH 7 (copper, zinc, cobalt, molybdenum, manganese, etc. extractions, Mitchell, 1948), 2.5%acetic acid, pH 2.5 (manganese, copper, zinc, nickel, cobalt, chromium, etc. extractions, Mitchel, 1948), 0.05 M E.D.T.A., pH 7 (copper and zinc extractions, Mitchell, 1948), 1 N hydrochloric acid and 1 N nitric acid

4

(copper, zinc, nickel, cobalt extractions, Peyve, 1958). This notion of element “available” to plants or “assimilable” (considered “exchangeable” element by some authors) is of primary importance. Its quantitative determination is difficult, considering the complex environment in which plants live. It appears, however, that weak acids (such as 2.5% acetic acid) and their salts often act in a manner similar to that of nature. The ability to determine plant-“available” element contents is very important in agronomy because a plant deficiency or toxicity can then be diagnosed. However, the interpretation of the data depends upon the method used. All the analytical results cited in this work are from clearly defined methods. As is the case with total contents, the maximum and minimum contents and average contents for the whole soil or horizon were given. Variations o f element content

Under this heading, the content variations of an element are classified in relation to the following factors: position of the horizon in the soil profile and soil characteristics (pH, organic matter content and fine fraction contents: clay and loam). The effect of these factors is often of primary importance, and different for each element. Deficiency or toxicity

Data concerning toxicity or deficiency of trace elements were taken from specific cases where the growth of plants and, consequently, of animals, was affected (cobalt deficiency, boron toxicity, etc.). The minimum and maximum contents necessary vary with the element, soil type, pH and plant variety. Action of fertilizers containing trace elements

The action of these particular fertilizers has been most often studied in connection with deficiency or toxicity symptoms. These toxicities or deficiencies are corrected either by liming or by fertilizer supplies containing the element in question. These fertilizers are more or less active according to the form in which they are applied (spraying of a solution, spreading of a solid element). Bibliographical references

The list of bibliographical references is found in the last column of each table.

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BORON* All the rocks of the earth’s crust contain boron in concentrations varying with the nature of the rock:Basic eruptive rocks (basalt, dolerite ... . ) : 1-5 p.p.m. Acid eruptive rocks (granite, rhyolite.. . ) : 3-10 p.p.m. Metamorphic rocks (schists) and sedimentary rocks of continental origin (sands, clays, limestones, alluvions ... ) : 5-12 p.p.m. Sedimentary rocks of marine origin are clearly differentiated by their very high boron content, which can attain 500 p.p.m. and more. The average boron content of the earth’s crust is about 50 p.p.m. (Vinogradov, 1959; Kovda et al., 1964). Parent rocks, corresponding t o the soils studied, have been rarely analyzed, but the few results obtained agree closely with the average values given above:Low contents: 2.5 p.p.m., in the ancient alluvial sands of Bielorussia (U.S.S.R.) Average contents: 8-10 p.p.m., for different limestones of Germany and for granite and sandy alluvions of the Amur region of the U.S.S.R. The highest concentrations cited by authors, excluding some exceptionally rich marine sediments (see above) have been found in the U.S.S.R. (Bielorussia and the Amur region) in glacial clays, lacustrine alluvions and stratified plain deposits: 35-70 p.p.m.; and in Germany in red muschelkalk and Paleozoic schists: 80-100 p.p.m.

TOTAL BORON CONTENT OF SOILS

The total boron content of soils ranges from 1-2 p.p.m. (podzols of Bielorussia) to 250-270 p.p.m. (eutrophic peaty soil of Israel), the average ranging from 20 to 50 p.p.m. The variations are partly due to the parent rocks on which the soils were formed and, mostly, to soil types which reflect the differences between the diverse geographical regions and climatic zones.

Temperate and boreal regions The lowest contents have been determined in various types of soils on sands, particularly in the podzols and podzolic soils:In the U.S.S.R. (Latvia) sandy coastal soils: 5 p.p.m.; Bielorussia, slightly podzolic leached soils and podzols on clayey loams and fluvio-glacialsands: 1.3-4.3 p.p.m.; Estonia, podzols: 6.5 p.p.m. The contents are average in the brown forest soils: in northeastern China, ~~

*See Tables, pp. 144-165

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on basalts: 45 p.p.m.; in the Amur region, on granite: 65 p.p.m. In this latter region, the boron content of hydromorphic meadow soils on stratified plain deposits ranges from 55 t o 85 p.p.m. Concentrations can be high in the rendzinas and brown calcareous soils as, for example, in the latter soils on marl, in Israel: 100-145 p.p.m. Arid and semiarid regions

The soils of these regions generally have average t o high total boron contents. In chemozems analyzed in: Yugoslavia (Serbia): 25-40 p.p.m.; Northem Bulgaria: 28-53 p.p.m.; and U.S.S.R. (Armenia): 30 p.p.m. (average). Brown isohumic soils have boron contents of the same order:In Israel, brown isohumic soils formed on alluvions, coming from “terra rossa”, mixed with aeolian deposits, contain from 25 to 40 p.p.m. of total boron. Generally the contents are average in the vertisols: in India, vertisols on basaltic rocks, schists or coastal alluvions contain from 25 to 50 p.p.m. On the other hand, saline soils (solonetses and saline alkali soils) often have higher than average and, sometimes, even very high concentrations :Yugoslavia (Serbia) solonetses: 4 0 - 6 5 p.p.m.; U.S.S.R. (Uzbekistan) saline alkali soils on loess and marine clays: 160 p.p.m.; and Israel, saline alluvial soils: 150-170 p.p.m. Slightly developed soils on alluvions (alluvial soils) are often rich in total boron:In India, alluvial soils on sandy, clayey or calcareous alluvions: 15-50 p.p.m. In Israel, alluvial soils derived from “terra rossa”: 50-85 p.p.m. Also in Israel, mediterranean red soils, formed on limestone, are very rich in total boron: 190 p.p.m. Tropical hum id regions

The soils of these regions show the same lower concentration limit as the soils of the temperate and boreal regions: 1-2 p.p.m. In New Caledonia, brown eutrophic soils on calcareous-cemented flysch contain 2-3 p.p.m. of boron. The following boron contents were determined in ferrallitic soils: China (Che-Kiang): 0.4-3.3 p.p.m.; and Polynesia, on basalts and andesitic basalts: 2-3 p.p.m.

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BORON CONTENT O F SOILS “AVAILABLE” TO PLANTS

Boron deficiency or toxicity symptoms in plants are well known, and workers most often analyze the boron “available” t o plants without taking into consideration the concentration of total boron. The method most frequently used for this determination is that of Berger and Truog (1939): boron soluble in hot water. According to numerous data the average concentration of water-soluble boron of different soil types of temperate, boreal, arid, semiarid and tropical zones ranges from 0.1 t o 1-2 p.p.m. Thus, in:France, brown calcareous soils of Gascony, on Miocene sandstones: 0.31-0.91 p.p.m.; leached brown soils on the loams of the “Pays de Caux”: 0.1-1 p.p.m.; acid brown soils with a podzolic tendency, on schists, of the Armorican Massif: 0.5-1.25 p.p.m., and in the podzolic soils on granite of this same region: 0.45-1.3 p.p.m. The Rhone Valley and the southeast, in acid brown soils, 0.12 p.p.m. of water-soluble boron were determined for 8.5 p.p.m. of total boron; in red fersiallitic soils: 0.3 p.p.m. of water-soluble boron for 21 p.p.m. of total boron; in saline soils: 1.3 p.p.m. of soluble boron for 3 5 p.p.m. of total boron. Germany, calcareous soils and acid brown podzolic soils on highly weathered slates and bunter sandstone: 0.4-1.2 p.p.m. Bulgaria, on marine clays and loess, rich in boron: leached soils about 0.3 p.p.m.; chernozems: 0.7-0.9 p.p.m. Canada (Saskatchewan), chemozems: 0.1-2 p.p.m. U.S.S.R. (Armenia), chernozems: 0.55-1.05 p.p.m. India, more or less developed soils on alluvions and different types of sandy, loamy and clay-loam soils: 0.3-2 p.p.m. The lowest concentration was found in Latvia, in coastal sandy soils: 0.04 p.p.m. Under these conditions, water-soluble boron represents 0.1-3.5% of total boron, apart from a few exceptions: 3.7% in the podzols of Estonia, although often deficient; 6.4-8.5% in the soils of Poland; and 5.5--16.3% in the pelosols of the Fayoum Oasis in Egypt. On the other hand, important quantities of water-soluble boron, whose proportion in relation to total boron can be very high, correspond to the high concentrations of total boron in saline soils (solonetses, sierozems, and saline alkali soils) of the semiarid and arid regions. Thus, in the U.S.S.R., for the saline alkali soils of the Krasnodar and Turkmenistan regions, values of 32-37 p.p.m. of water-soluble boron were determined. In India, in the Punjab, contents range from 3-11 p.p.m. in the surface horizons of the saline alkali soils. In these types of soils, the percentage of

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water-soluble boron in relation t o total boron attains 65% in the Crimea and even 81%in Rajasthan, in India.

VARIATIONS OF THE BORON CONTENT O F SOILS

In soils, the concentrations of total and plant-“available” boron vary in relation to the humus and total organic matter concentrations. The distribution of this element between the different horizons of the soil profiles follows that of humus. Therefore, there is an accumulation of boron in the humic horizons of the chemozems, in the humus illuvial horizons of the podzols and in the deep horizons of the peaty soils (in Poland). The boron content varies also in relation to soil texture. The higher the percentage of clay and loam, the higher the boron content. Clays retain boron as has been verified, for example, in the U.S.A., where greenhouse experiments on sandy and clayey soils have shown that alfalfa removes boron more easily in coarse-textured soils. On the other hand, there is a very clear relationship between the boron content “available” t o plants and the soil pH. This has been verified in France (Jouis et al., 1960; Maurice and Trocmk, 1963) and in Denmark where the action of liming on “available” boron has been studied. Likewise, it has been shown in the U.S.A. that alfalfa fixed less soluble boron when the pH was changed from 5 t o 7. In a basic medium, boron is in the form of compounds less easily soluble than those compounds formed in an acid medium. This is one of the causes of the deficiency often noticed in soils having a strongly acid pH (podzols): boron is then carried away by leaching, especially in humid regions. Generally speaking, the soluble boron content of soils tends to increase when rainfall decreases. This has been well observed in Punjab, India, or in the semiarid zone of the U.S.S.R.

DEFICIENCY OR TOXICITY

The range between the upper and lower limits is very narrow for boron useful to plants. Contents range from values of 0.1-0.2 t o 1.5 p.p.m. and vary, moreover, in relation t o the plant variety. Thus in:France, in the more or less podzolic soils of the Armorican Massif, with a pH between 5.5 and 6.5, the deficiency limit allowed for many crops (particularly beets and rutabaga) is 0.5 p.p.m. (Coppenet, 1965). China (Taiwan): beets cultivated on ferrallitic soils and various soils on sandstones, slates and limestones, are deficient when water-soluble boron is lower than 0.2 p.p.m. The limit is the same in Japan, for soils on rhyolite,

9

granite, schlsts, limestones, t u f f . . . Israel, the deficiency limit is reached in brown isohurnic sandy soils on calcareous sandstone for values of 0.3 t o 0.5 p.p.m. India (Rajasthan), the lower limit is fixed at 0.35 p.p.m. in various types of soils of arid regions. This limit is valid for acid soils in which boron is easily soluble in water, but, after certain experimental work, it was shown that the concentrations needed are higher for cultures grown on basic or calcareous soils. Thus, in France, a deficiency is noted in vines cultivated on brown calcareous soils (Diekmann, 1957; Le Mare and Samki, 1969; Tollenar, 1966). boron does not reach a t least 0.75 p.p.m. In Poland, too, a deficiency appears in beets, in the case of soils with a neutral or alkaline pH, with a water-soluble boron content lower than 0.6 p.p.m. Likewise, in Egypt, soils having a pH higher than 8 with values of 2.5 t o 3.5 p.p.m. of water-soluble boron benefit from fertilizers containing boron. Therefore, the deficiency of boron “available” t o plants mostly depends on the type of soil: acid leached soils, coarse-textured sandy soils and calcareous soils (Diekmann, 1957; Le Mare and Samki, 1969; Tollenar, 1966). The deficiency may also be due t o the conditions of cultivation: excessive liming which immobilizes the boron, in acid soils, in particular (Ryan et al., 1967; Charpentier and Martin Prevel, 1967). The toxicity limit settles at 1.5 p.p.m. in the arid and saline alkali soils of India (Punjab and Rajasthan). In Israel, the limit is reached in alluvial soils containing 1.2 p.p.m. of water-soluble boron. For certain plants such as wheat, barley, peas.. . . , the limit is only 0.8 p.p.m. (in Iraq).

ACTION O F FERTILIZERS

The deficiencies of acid soils are corrected by using fertilizers containing boron, generally borax, either in powder or granule form or in solution, which is sprayed (Calton and Vail, 1956; Vail e t al., 1957). Boron is fixed by liming, avoiding an excess of lime which immobilizes it. Concentrated borax also has a beneficial effect on cultures grown on calcareous soils or on soils with an alkaline pH. As organic matter plays an important part in the fixation of boron by soils, organic amendments have a particularly strong action, as has been shown in Poland in experiments with farmyard manure. The increase in the crops harvested (alfalfa, potatoes, grapes. . . ) was very noticeable.

10 CONCLUSION

Soils, particularly in their humiferous horizons, are richer in boron than the majority of parent rocks from which they are derived: 10-15 p.p.m. for rocks and 20-40 p.p.m. for soils. Soils of semiarid and arid regions are clearly differentiated from soils of other climatic zones by their generally high concentrations of total and water-soluble boron. Humus and clay contents and soil pH have a major influence upon the concentrations of total boron and boron “available” to plants. Water-soluble boron generally represents 1-3% of the total boron but sometimes it represents much more. Boron deficiency and toxicity are corrected by fertilizers containing this element and by liming, respectively.

See also the following works published since 1968: FRANCE : Cornillon, P., 1 9 7 0 ; Maurice, J., 1 9 7 3 . ENGLAND: Mitchell, R.L., 1974. GERMAN DEMOCRATIC REPUBLIC : Bergmann, W., Ebeling, R . and Witter, B., 1 9 6 8 ; Klemm, K., 1968a. POLAND: Boratynski, K., Rosczyk, E. and Zietecka, M., 1 9 7 1 ; Ciesla, W. and Kocialkowski, Z., 1 9 7 3 ; Czuba, R., Gaszek, K. and Wlodarczyk, Z., 1 9 7 4 a ; Czuba, R., Duziak, S. and Malinska, H., 1 9 7 4 b ; Dobrzanski, B., Glinski, J. and Cao Thai, V., 1 9 7 1 . HUNGARY: Abrahim, L. and Kovics, M., 1 9 6 8 ; Kereszteny, B., 1973. RUMANIA : Chiriac, A. and Bajescu, I., 1 9 7 4 . CYPRUS : Pagel, H. and Prasad, R.N., 1 9 7 1 . U.S.S.R. : Andrianova, G.A., 1 9 7 1 ; Do-Van-Ay, Borovik-Romanova, T.F., Koval’skii, V.V. and Makhova, N.N., 1 9 7 2 ; Grabarov, P.G., 1 9 7 0 ; Gyul’akhmedov, A.N. and Peysakhov, Y.A.M., 1 9 6 8 ; Shirokov, V.V. and Panasin, V.I., 1 9 7 2 ; Zborishchuk, Yu.N. and Zyrin, N.G., 1 9 7 4 ; Z y r i n , N.G., Motuzova, G.V. and Sokolova, T.A., 1 9 7 3 . ALGERIA: Lomov, S.P., 1 9 7 3 . EGYPT: Abdel Salam, M.A., El-Demerdashe, S., Abdel-Aal, Sh.1. and Ibrahim, M.G., 1971. CAMEROUN : NaloviE, Lj. and Pinta, M., 1 9 7 2 . TANZANIA: Kocialkowski, Z. and Dzieciolowski, W., 1 9 7 2 . MADAGASCAR : Berger, M., 1 9 7 2 ; Oliver, R., Damour, M., Velly, J. and Razafindramonty, J.B., 1 9 7 4 .

11

NORTH VIETNAM: Glinski, J. and Cao Thai, V., 1971. INDIA: Balasundaram, C.S., Lakshmina Rasimhan, C.R. and Rajakannu, K., 1 9 7 2 ; Rai, M.M., Pal, A.R., Chimania, B.P., Shitoley, D.B. and Vakil, P., 1 9 7 2 c ; Sharma, R.C. and Shucka, U.C., 1 9 7 2 ; Singh, S. and Singh, S.B., 1971;Singh, S. and Singh, R.S., 1972;Singh, R. and Singhal, J.P., 1 9 7 0 . JAPAN : Harada, T. and Tamai, M., 1 9 6 8 . ARID AND HUMID TROPICS : Prasad, R.N. and Pagel, H., 1 9 7 3 . LATIN AMERICA: Cox, F.R., 1 9 7 2 .


13

CHROMIUM* Chromium can be found in all the rocks of the earth’s crust, its distribution being related to the nature of the rocks. Contents range from values of 20-40 p.p.m. in acid eruptive rocks (granite, chamockite.. . .( to 2,000-3,000 p.p.m. in ultra basic volcanic rocks (dunite, peridotite.. .) and in the products of their metamorphism, particularly in serpentinite. The average chromium content, 100-300 p.p.m., cited for basic rocks (basalt, dolerite.. .), as well as for metamorphic and sedimentary rocks (schists, clays.. .), corresponds t o the one given for the whole lithosphere: 200 p.p.m. Clays often seem to be richer than sandstones and, especially, limestones (100-110 p.p.m.) (Vinogradov, 1959; Turekian and Wedepohl, 1961; Kovda et al., 1964). Rocks analyzed in the U.S.S.R. confirm these average values. The following concentrations were found in the Amur basin and Bie1orussia:: 25--35 p.p.m. Granite and ancient alluvial sands Clayey loessic loams : 50 p.p.m. Gladial lacustrine clays and lacustrine alluvial deposits: 115-300 p.p.m. In the Ural mountains, on ultrabasic rocks, chromium turns into an ore; it is the same on serpentinite in Southwestern Rhodesia.

TOTAL CHROMIUM CONTENT OF SOILS

The total chromium content of soils ranges from traces to 3,000-4,000 p.p.m., the mean ranging from 100 to 300 p.p.m. These values are very close to those found in rocks on which soils were formed. Parent rocks play a major role in determining soil content in the case of chromium, a relatively stable element, in comparison to the influence of the main pedological processes which, as a matter of fact, correspond to the differences existing between the principal climatic zones and geographical regions. Temperate and boreal regions

In the soils of these regions, and, particularly, in the different types of podzols and leached soils, the chromium content depends mostly on that of the parent rocks. Thus the determined minimum content (7-20 p.p.m.) and maximum content (3,500 p.p.m.) are found, respectively, in Scotland, in hydromorphic podzols with iron pan, on granite and sandstone, and in a brown podzolic soil on serpentinite. Moreover, also in Scotland, podzols on granito-gneiss *See Tables, pp. 166-173

14

and micaschists, and a brown podzolic soil on gabbro contain, respectively, 150 to 300 p.p.m. of total chromium. Similarly, the chromium content of soils on sands varies with the nature of the sands involved, i.e. soils on fluvio-glacial, alluvial and ancient marine sands: traces-60 p.p.m.; soils on rather recent quaternary sands: 50-120 p.p.m. The influence of the parent rock can also be noticed in Wales, where soils on rhyolite contain 1 5 p.p.m. and those on dolerite 250 p.p.m. Average chromium contents, 100-200 p.p.m., are found in brown forest soils, on basalt, in northeastern China and on andesitic moraine in Scotland. In the Amur region of the U.S.S.R.these soils, on granite, contain from 80 to 100 p.p.m. of total chromium. Rendzina: in Madagascar*, on gritty limestone: 9 5 p.p.m. Hydromorphic soils: in the Amur region, on alluvions: 130-150 p.p.m.; in Scotland, for hydromorphic gley soils on schists: 200 p.p.m. Arid and semiarid regions

The soils of these regions are often rich and even very rich in chromium. Chernozem soils of the Amur region, on stratified flood plain, contain, on an average, 400 p.p.m. of total chromium. Vertisols also have high chromium contents: in Madagascar, on basalt and marl: 200--540 p.p.m.; on alluvions: 190 p.p.m.; in Chad, on sandy-clay sediments: 180-300 p.p.m.; in the Central African Republic, on amphibolite: 300--1,000 p.p.m. The highest content, 2,400 p.p.m., has been found in New Caledonia in a topomorphic vertisol on limestone-cemented flysch. Tropical h umid regions Soil chromium in tropical humid regions shows wide variations: from traces to 4,000 p.p.m. Here too, the parent rock plays an important part, although, except for a few special cases, contents are often rather high. Thus in Ghana, slightly to moderately desaturated ferrallitic soils on granite and sandy material, contain less chromium than the same soils on schists: 20-80 p.p.m. on granite, 10-50 p.p.m. on sandy material and 100250 p.p.m. on schists. In Madagascar ferrallitic soils on basalts and volcanic ashes contain more chromium than the same soils on granite: 200-400 p.p.m. and 70 p.p.m. respectively. *Although rendzina soils have been studied in very diverse climatic regions, they have always been cited with the soils of mediterranean and temperate regions with which these soils are most often associated. Such is the case with the rendzina soils of Madagascar. In the same way, vertisols have always been regrouped with soils of semiarid zones.

15

The lowest contents, traces to 4 p.p.m., were found in New Caledonia in humocarbonated soils and more or less humiferous hydromorphic soils on coralline limestone and volcanic pumices. The highest contents, 650-2,000 p.p.m., were found in tropical soils corresponding to the slightly evolved soils on basaltic debris of Polynesia, and in different types of soils of New Caledonia, such as brown, reddish-brown and slightly evolved erosion or deposit soils on limestone-cemented flysch, basaltic debris and dolerite: 900-2,700 p.p.m. The maximum concentration, 4,000 p.p.m., was found also in New Caledonia, in a humiferous, slightly evolved soil of fluvio-marine origin, on elements of diverse weathered rocks. For many soils, contents range from values of 150 to 300 p.p.m.:More or less leached ferrallitic soils in the Ivory Coast, on granite and schists, contain from 50 to 300 p.p.m. In Chad, these soils on arkose and arkosic sandstone, contain from 100 t o 280 p.p.m. In Madagascar, these soils on acid metamorphic rock and, in Polynesia, on andesitic basalts, contain 185 and 115-260 p.p.m., respectively. In Chad, gray ferruginous soils, on clayey and sandy clay sediments, contain from 100 to 150 p.p.m., and, in Madagascar, these soils on sandstone and limestone contain from 80 to 165 p.p.m. Hydromorphic soils have about the same total chromium contents:In Madagascar, hydromorphic gley soils on alluvions: 220-270 p.p.m. In New Caledonia, hydromorphic soils on basaltic sediments or coralline limestone: 140-220 p.p.m. In Chad, hydromorphic soils on clayey sediments: 80-250 p.p.m. Moreover, in the case of tropical soils, some variations observed in soils of the same group type, formed on a given rock, seem to be due more particularly to detailed pedogenic characteristics such as the intensity of certain phenomena: more or less intensive weathering of the parent rock, more or less accentuated evolution of the soil, leaching. Thus, in the Central African Republic, more or less impoverished ferrallitic soils, more or less leached gray ferruginous soils and more or less hydromorphic pseudogley soils deriving from granite, gneiss or recent alluvions, have chromium contents which can range from low values, 1 0 - 6 0 p.p.m. to higher values, 200-250 p.p.m.

CHROMIUM CONTENT OF SOILS “AVAILABLE” TO PLANTS

Chromium is very slightly soluble in weak reagents: the quantity of chromium extracted with 2.5% acetic acid (pH 2.5) from an iron pan hydromorphic podzol and a brown podzolic soil, on serpentinite, in Scotland, represented 0.01-0.4% of total chromium (less than 0.03-1 p.p.m.).

16

In France, the quantity of chromium soluble in 1 N ammonium acetate (pH 7 ) is a little higher: 0.1-176 of total chromium (Grosman, 1966). According to Bertrand and Vinchon (1964), sometimes relatively high concentrations of “available” chromium are extracted with 1 N ammonium acetate from soils with low total chromium contents. However, valid conclusions on this question cannot be drawn because of a lack of numerous analytical data.

VARIATIONS OF THE CHROMIUM CONTENT OF SOILS

The distribution of chromium between the different horizons of profiles generally follows that of humus. An increase in chromium contents in the upper horizons of soils which are particularly humified (chernozems) can be noticed. In podzols and leached podzolic soils, the accumulation of chromium takes place, on the contrary, in illuvial or gley horizons. Chromium content varies, also, in relation t o soil texture. Concentrations are higher in clayey soils than in easily leached sandy soils (Pasternack and Glinski, 1969). In tropical soils there is a positive relationship between chromium and clay contents. Chromium accumulates in the clayey horizons and increases slightly with depth (soils of Dahomey, Pinta and Ollat, 1961). However, in all cases, the differences between the chromium contents of the horizons of the same profile are of little importance. Finally, in many soils, chromium contents are also relatively proportional to iron oxide contents (Lentschig and Fielder, 1966).

TOXICITY

In France, the conditions which bring about a toxicity of chromium in plants have been studied particularly. According to Grosman (1966), the action of this element depends on its valence, trivalent chromium compounds being among the least toxic. Moreover, Moulinier and Mazoyer (1968) showed that soluble compounds (sulphate and nitrate) react faster in producing toxicity than insoluble compounds (oxide or phosphate). This toxicity becomes more important as the acidity of the soil increases and, at the same time, there is a decrease of soil assimilable phosphoric acid. This toxic action can be avoided by supplying limestone and monobasic calcium phosphate amendments to soils.

17

CONCLUSION

Soils contain on an average 100-300 p-p-m. of total chromium (extreme upper and lower limits: traces and 4,000 p.p.m.). There are no essential differences between the chromium contents of soils of the diverse climatic and geographic regions of the globe. Soil contents are close to those of the parent rocks, especially when these rocks are very rich in this element (soils on serpentinite). However, pedogenic characteristics (soil type), climatic conditions etc., play an important, even though secondary, part regarding total chromium content of soils, particularly in the case of tropical soils.

See also the following works published since 1968: POLAND: Boratynski, K., Roszyk, E. and Zietecka, M., 1 9 7 2 ; Dobrzanski, B. and Glinski, J., 1 9 7 0 ; Dobrzanski, B., Glinski, J. and Cao Thai, V., 1 9 7 1 ; Glinski, J. and Magierski, J., 1971. U.S.S.R.: Lukashev, K.I. and Petukhova, N.N., 1 9 7 1 ; Zborishchuk, Yu.N. and Zyrin, N.G., 1974. U.S.A.: Bradford, G.R., Bair, F.L. and Hunsaker, V., 1 9 7 1 ; Kilpatrick, B.E., 1969. AUSTRALIA: Anderson, A.J., Meyer, D.R. and Mayer, F.K., 1973. NEW ZEALAND: Lyon, G.L., Brooks, R.R. and Peterson, P.J., 1970.


19

COBALT* Cobalt is found in all the rocks of the earth’s crust, the contents varying with the nature of rock:Ultrabasic rocks (dunite, peridotite.. .) and products of their metamorphism (serpentinite): 100-200 p.p.m. Basic eruptive rocks (basalts, andesite, syenite . . .): 30-45 p.p.m. Acid or neutral eruptive rocks (granite, rhyolite . . .): 5-10 p.p.m. Metamorphic rocks (schists) and certain sedimentary rocks (sandstones, clays.. .): 20-30 p.p.m. Sands, limestones and loams have low contents: 1-5 p.p.m. and sometimes even very low contents: 0.1-0.3 p.p.m. The average content of cobalt in the lithosphere is about 30 p.p.m. (Vinogradov, 1959; Turekian and Wedepohl, 1961; Kovda et al., 1964). There are only few data concerning the parent rocks corresponding to the different types of soils studied, but the analytical results cited below confirm these average contents:In Tasmania, Australia, for dolerite: 35-60 p.p.m. In the Black Forest of Germany and in the Guadalquivir Valley of Spain, for Paleozoic slates and Tertiary altered chalks: 4-5 p.p.m. In Bielorussia, U.S.S.R., for lacustrine glacial clays: 13 p.p.m.; for fluvioglacial sands: 3 p.p.m.; and for clayey loess and moraine loams: 8 p.p.m.

TOTAL COBALT CONTENT OF SOILS

The total cobalt contents of soils vary widely: 0.05 p.p.m. (podzols of the U.S.S.R.) t o 300 p.p.m. (vertisols of the Central African Republic). The average content is about 10-15 p.p.m. In soils, these contents vary, on the one hand in relation to those of the rocks from which the soils originate and, on the other hand, in relation to the types of soils whose characteristics are more or less directly related to the climate which has dominated their evolution and, therefore, to the major geographical zones.

Temperate and boreal regions Total cobalt contents for the soils of these regions range from values of 0.05 to 200 p.p.m. They depend closely on those of the parent rocks, even though they tend t o vary from one horizon t o another in relation to certain pedologic processes (podzolization and leaching). Thus, in Wales, soils on dolerite contain 20-30 p.p.m. of cobalt and those *See Tables, pp. 174-209.

20

on rhyolite 3 p.p.m. This is particularly noticeable for soils generally regarded as poor in cobalt: podzols, leached podzolic soils, leached soils and peaty soils.. . In Bielorussia, U.S.S.R., podzols on fine sands have the lowest contents: 0.05 p.p.m., followed by weakly podzolic soils on fluvioglacial sands: 0.21.8 p.p.m. These same soils on clayey loams contain from 0.06 to 6 p.p.m., those on lacustrine clays have higher contents: 1.7-13 p.p.m. Similar examples are found for soils of the U.S.A., especially for leached soils, brown podzolic soils and podzols formed on sands or on glacial deposits derived from granitic rocks such as are found in the southeast of the U.S.A. or in New England. In Scotland, podzols, poor in cobalt, have, on granitic till: traces-3 p.p.m.; average contents on gneiss: 10-40 p.p.m.; and high contents on serpentinite: 200 p.p.m., the highest content determined in the soils of these regions. Another example is that given by Coppenet (1965) for the soils of Brittany, viz. podzolic soils on granite: 1-45 p.p.m. Peaty soils are also poor in cobalt, whether they are those of Brandenberg, in Germany, or those of Israel on papyrus remains: 0.3-1.5 p.p.m. and 3.43.8 p.p.m., respectively. Among other types of soils, average cobalt contents are found in brown forest soils:In northeastern China, on basalts, concentrations attain 23 p-p-m. and in Bulgaria on gneiss 10-20 p.p.m. However, in Scotland, on andesitic moraine and in Bulgaria or in the Guadalquivir valley, in Spain, on granite, these soils contain only 2.5-10 p.p.m. of total cobalt. In Brittany, on schists, acid brown soils with a podzolic tendency contain only 6.4-13 p.p.m. of cobalt. Rendzinas generally have lower contents : in Israel, on marl, contents vary only from 5.9 to 6.7 p.p.m.; in the Guadalquivir Valley, on altered chalks or in Australia (Queensland) on limestone: 10*.8 p.p.m.; in Southeastern Australia concentrations can attain 18 p.p.m. Arid and semiarid regions The soils of arid and semiarid regions have higher average cobalt contents than those of temperate and boreal regions. Chernozems are generally classified among soils rich in this element (Vinogradov, 1959; Kovda et al., 1964):In Bulgaria, in the Ural-Sakmara basin of the U.S.S.R., on serpentinite diluvium, and in the Transural: 10-30 p.p.m. In Azerbaidzhan, U.S.S.R., contents may attain 100 p.p.m. Chestnut soils have average contents:In Bulgaria, for chestnut and chestnut hydromorphic soils: 3-15 p.p.m.; chestnut vertic soils: 15-45 p.p.m. In Azerbaidzhan and Kuban regions of the U.S.S.R.: 10 p.p.m. and up t o

21

80 p.p.m. for an alkalised chestnut soil with a textural B horizon, on alteration products of basic rocks, in the Or-Kumak basin. For brown isohumic soils, total cobalt contents range from values of 8 to 20 p.p.m. :On clayey sediments in Queensland: 12-16 p.p.m.; in Uzbekistan, U.S.S.R.: 17 p.p.m.; in Israel, on alluvions derived from “terra rossas” and aeolian deposits: 8 p.p.m. Vertisols appear as the soils having generally the highest contents of total cobalt, although very variable:In Australia, Queensland and Tasmania, on basalts, dolerite and alluvium: 7-70 p.p.m. In India, on alluvions derived from lavas and basalts: 15-50 p.p.m. In Chad, on sandy clay sediments: 10-95 p.p.m. The maximum concentrations of total cobalt for soils have been determined in hydromorphic lithomorphic vertisols on amphibolite, in the Central African Republic: 100-300 p.p.m. Apart from certain exceptions, in Bulgaria as well as in Spain and the U.S.S.R. (Azerbaidzhan and the Ural-Sakmara basin), saline soils (solonetses, saline alkali soils) have rather low concentrations of total cobalt, about 3 - 9 p.p.m. Occasionally, these values may be a little higher, as in Turkmenistan: 10-30 p.p.m. and, especially, in the Or-Kumak basin on sodic products resulting from basic rock weathering: 80 and even 140 p.p.m. In mediterranean red soils, slightly lower contents were found :In Spain, Guadalquivir valley, on granitic rocks, and in Israel, on hard limestone: 10 p.p.m. In Queensland, Australia, on granodiorite, a value of 3.5 p.p.m. was found, but in the Adelaide region and Southeast contents vary from 1 to 30 p.p.m. Tropical hum id regions In tropical zones, the lower and upper limits, traces to 240 p.p.m., are very close to those of temperate and boreal zones. The influence of the parent rock is equally important here; thus in the Central African Republic, in gray ferruginous soils, traces to 3 p.p.m. have been determined on granite; on migmatite: 30-60 p.p.m.; on amphibolite: 20-100 p.p.m. In Madagascar, the cobalt contents of gray ferruginous soils range from traces to 3 p.p.m. on sandstone and sand and from 15 to 30 p.p.m. on basic rocks. Soils on schists contain 5-12 p.p.m. One can say the same for ferrallitic soils:In the Ivory Coast, for soils on charnockite: 1-10 p.p.m.; on schists: 25 p.p.m. In Ghana, in weakly t o moderately desaturated ferrallitic soils on granite:

22

traces-30 p.p.m.; on B2 basic material: 50-100 p.p.m.; on hornblende: 100-200 p.p.m. However, in the case of ferrallitic soils in particular, other factors besides the parent rocks intervene. These factors may correspond to the presence of certain horizons or t o a more or less advanced state of soil degradation, as in Polynesia, where, in function of these elements, the total cobalt content of ferrallitic soils varies, on basalts and basaltic debris, from 5 to 25 p.p.m. On the contrary, in other cases, the reason for these variations is not apparent. Thus, in the Central African Republic, in desaturated ferrallitic soils, on gneiss and migmatite, concentrations can range, according to particular cases, from traces to 30 p.p.m. or from 30 to 80 p.p.m. Sometimes even, the range of contents in relation to the rock seems to be reversed; in Madagascar, ferrallitic soils on basalts appear abnormally poorer in cobalt (traces-3 p.p.m.) than those on granite or limestone (15-20 p.p.m.). The following are among t5e soils having average or high contents of cobalt:More or less hydromorphic or halomorphic alluvial soils, as in India and Chad: 8-35 p.p.m. In Polynesia, soils derived from elements of volcanic origin and which are very humiferous attain: hydromorphic alluvial soils: 25-75 p.p.m.; slightly evolved well drained soils: up to 120 p.p.m. However in certain “ore soils’’ of New Caledonia (ferrallitic soils on ultrabasic rocks) contents are certainly much higher, but we have no special data concerning these soils.

COBALT CONTENT OF SOILS “AVAILABLE” TO PLANTS

Cobalt is an important element for animals. Its compounds play a role in the formation of haemoglobin, and in several regions of the globe, sheep and cows may become anaemic due to eating vegetation grown in cobalt-deficient soils. Therefore it is interesting to know not only the total cobalt content but also the cobalt content “available” to plants. According to authors, available cobalt is extracted by: 2.5% acetic acid (pH 2.5) or 1 N hydrochloric acid and 1 N nitric acid (in the U.S.S.R.). The upper and lower limits of cobalt soluble in 2.5% acetic acid (pH 2.5) are, respectively, 3.74 p.p.m. (podzolic red soils) and 0.008 p.p.m. (hydromorphic gley podzolic soils) in the U.S.A. Also, in Scotland 4 p.p.m. of cobalt have been extracted by this reagent from the upper horizon of a brown podzolic soil on serpentinite, a soil very rich in total cobalt. Generally, contents range from 0.05 to 1p.p.m. Thus in Brandenberg, Germany, the contents determined for peaty soils were 0.09-0.41 p.p.m.; in Bulgaria, in brown forest soils they were 0.09-

23

0.97 p.p.m.; and in India, in vertic soils, vertisols and alluvial soils: 0.0560.95 p.p.m. In fact, the cobalt “available” to plants represents a widely variable proportion of total cobalt: 0.6-376 in India, 1-876 in Bulgaria, and 17-30% in Germany. The highest percentage, 46%, was determined in leached soils of the U.S.A. Since 1 N nitric acid is a stronger reagent, it extracts greater quantities of cobalt :In chernozems of Rumania: 1.6 p.p.m.; in brown forest soils of Bulgaria: 0.3-3.86 p.p.m.; in mediterranean red soils of Israel: 2.3 p.p.m. The percentage of cobalt extracted increases too: 7-28% in Israel; 31%in Rumania, and 62% in Bulgaria. The maximum cobalt contents which can be extracted by 1 N hydrochloric acid, 6-26 p.p.m., have been obtained from the upper horizons of chestnut soils, solonetses and very saline alkali soils in the Or-Kumak basin of the U.S.S.R., which are very rich in total cobalt, as has been previously shown. In this case, the“availab1e” cobalt corresponds to 16-22% of the total cobalt.

VARIATIONS OF THE COBALT CONTENT OF SOILS

If ones studies the distribution of cobalt between the different horizons of soil profiles, one notices, most of the time, an accumulation of this element in the humiferous horizons. There is a distinct relationship between cobalt contents and humus and organic matter contents. Cobalt seems to be fixed by humus. In chernozems and vertisols, the distribution of cobalt is uniform for the whole profile; in podzols cobalt accumulates in the illuvial B horizon, while the eluvial A2 horizon is generally poor in this element. On the other hand, cobalt is sorbed by clay minerals and its distribution in the profile also follows that of clays. Fine-textured soils are richer in cobalt than coarse-textured soils, as has been observed in the soils of Dahomey and Poland (Pinta and Ollat, 1961; Pasternack and Glinski, 1969). The “available” cobalt content depends, on the other hand, on the redox potentials of the soils. Russian pedologists have given excellent examples in their works concerning alluvial soils of the lower Moskva valley. The influence of soil pH on cobalt contents can also be noticed: an acid pH facilitates the solubilization of cobalt compounds and aids their elimination by leaching. Alkaline pH soils are relatively rich in “available” cobalt: Or-Kumak basin in the U.S.S.R., Chad, etc. However, these different factors have a less important influence than the cobalt content of the parent rock, as has been previously shown (soils on serpentinite in Scotland).

24


According to certain authors (Ravikovitch et al., 1961) soils containing less than 5 p.p.m. of total cobalt are deficient and cannot supply plants with the quantities of cobalt essential to animals. In the U.S.A., it is considered (Alban and Kubota, 1960) that the cobalt contents “available” to plants should not be lower than 0.02 p.p.m., a level which is not attained in many regions. In Europe, the deficient regions correspond to the zones having heavy rainfall, where the soils are most often of the podzolic or leached type, on acid parent rocks, such as moraine deposits (Ryan et al., 1967). This is especially true of sandy podzolic soils of Latvia (Kovda et al., 1964). It is also the case with the podzols, brown podzolic soils and red and yellow podzolic soils of the eastern States of the U.S.A. In France, deficiencies have been iloticed, not only on very leached podzolic soils in many regions, but also, in certain cases, on rendzinas and red fersiallitic soils. In Australia, the very acid leached ferrallitic soils are also deficient or at the limit of deficiency. In Israel, on the contrary, a lack of cobalt is observed in soils having a nearly neutral or basic pH, such as the reddish-brown isohumic soils on calcareous sandstone, desert saline soils and peaty soils. Cobalt deficiency is corrected by fertilizers containing cobalt, the form most often used being sprayed cobalt sulphate. An improvement in the harvest is always noticed.

CONCLUSION

The concentrations of cobalt in the soils of the different climatic zones vary widely: 0.05 to 200-300 p.p.m. The richest soils are those with high humus content (chernozems) and soils with more or less alkaline pH: vertisols (which are often well supplied With humus), B horizons of solonetses and saline alkali soils. Although the pedogenic characteristics influence the cobalt content of soils, the parent rock plays a very important role too. “Available” cobalt is often in insufficient quantities in soils, resulting in deficiency diseases of sheep and cows. It is necessary to correct these deficiencies by using fertilizers containing cobalt.

25

See also the following works published since 1968: ENGLAND: Mitchell, R.L., 1972. DENMARK: Nielsen, J.D., 1969. POLAND: Boratynski, K., Roszyk, E. and Zietecka, M., 1972. RUMANIA: Ababi, V. and Murariu, T., 1970. U.S.S.R.: Krym, I.Ya., 1971;Mursalova,M.G. and Mirzoeva,Z.A., 1973;Panin,M.S., 1 9 7 2 ; Rudneva, E.N., Verigina, K.V. and Dobritskaya, Yu.I., 1972; Stoilov, G. and Atanasov, I., 1971. U.S.A. : Kilpatrick, B.E., 1969. PUERTO RICO: Regus, J.R., 1969. AUSTRALIA: Anderson, A.J., Meyer, D.R. and Mayer, F.K., 1973. NEW ZEALAND: Lyon, G.L., Brooks, R.R. and Peterson, P.J., 1970. CAMEROUN: Naloviz, Lj. and Pinta, M., 1972. INDIA: Singh, L. and Singh, S., 1973.


21

COPPER* All the rocks of the earth’s crust contain copper with contents varying according t o the nature of the rock:Basic eruptive rocks (basalt, dolerite): 100-200 p.p.m. Acid eruptive rocks (granite, rhyolite.. .): 10-20 p.p.m. Metamorphic rocks (schists) and certain sedimentary rocks (clays, loess.. .): 30-40 p.p.m., sometimes a little higher. Sandstone, sands and limestone: 3 t o 10-15 p.p.m. The average concentration of the lithosphere is about 100 p.p.m. (Vinogradov, 1959; Turekian and Wedepohl, 1961; Kovda et al., 1964). The parent rocks of the soils studied in the “Services Scientifiques Centraux de 1’O.R.S.T.O.M.” or the analyses of which have been found in the cited bibliography, have contents corresponding t o these average contents:U.S.S.R. (Bielorussia), ancient alluvial and fluvio-glacial sands: 3.6 p.p.m.; loessic clay loams: 11.3 p.p.m. Czechoslovakia: loess and loessic loams: 24 p.p.m.; clayey rocks: 49 p.p.m.; micaceous paragneiss: 95 p.p.m. Tasmania: dolerite: 60-100 p.p.m. In the West of the Armorican Massif the concentrations found are about the same, although often a little lower, in relation to the rocks: 1.5 p.p.m. in sandstones; 4.8-20 p.p.m. in the various types of granite; 17.8 p.p.m. in gneiss; 22.7 p.p.m. in loamy schists and 88.5 p.p.m. in amphibolites. However, in the Kola peninsula of the U.S.S.R., values of up to 1,000 p.p.m. of copper, quite exceptional contents, have been found in crystalline schists with norite intrusions. Values of this order and even higher have been determined in rocks used in extraction of copper ore, in Mauritania or in Central Africa, for example.

TOTAL COPPER CONTENT OF SOILS

In soils, the total copper content ranges from traces (sandy soils of the U.S.S.R. and certain tropical soils) to 200-250 p.p.m. (vertisols of India); the average ranges from 15 to 40 p.p.m. An average value of 20 p.p.m. has been determined for the soils of France. The variations are mostly due t o the different contents of the parent rocks on which the soils have been formed and, t o a lesser degree, t o the types of soils corresponding t o the differences which exist between the principal climatic zones and geographic regions. Some very high values are to be found locally in zones where extensive farming is practised. *See Tables, pp. 210-243.

28

Temperate and boreal regions The lowest contents have been determined in soils on fluvioglacial and ancient alluvial sands of the lower Volga valley in the U.S.S.R.: traces-8 p.p.m. The influence of the parent rock on the total copper content of soils is particularly obvious with podzols, leached soils and peaty soils. Thus in Bielorussia, peaty podzols and podzolic soils on sandy material contain from 2 t o 10 p.p.m. of copper. On the contrary, in the Kola peninsula, on crystalline schists and on sandy clay moraine, which are materials rich in this element, copper contents attain 50-200 p.p.m. in the weakly podzolized leached soils and 75 p.p.m. in peaty soils. Similar variations have been shown in the podzols of Scotland: those on granite and sandstone are poor in copper: 3-5 p.p.m. and those on micaschists and olivine gabbro have average contents: 25-30 p.p.m. The more or less podzolic soils and podzols of the Armorjcan Massif also have total copper contents varying in relation t o the parent rocks: 3-5 p.p.m. on leucocratic granite and granulite, 15-20 p.p,m. on biotite granite. However, some podzols on sandstone attain concentrations similar t o those of these soils on granulite. Likewise, in Canada (New Brunswick), podzols on sulphide-rich bedrocks contain, in the upper horizons, five to six times more copper than those on other types of sediments: 60 and 10-11 p.p.m. respectively. Average copper contents are found in:Brown forest soils: 26.8 p.p.m. in a brown acid soil on loamy schists in central-west Finistere; 25 and 22 p.p.m. in brown soils on andesitic moraine in Scotland, and on basalt in northeastern China. However, it is necessary to point out that in Tasmania (Australia), on dolerite, the contents observed in these types of soils may be very high: 60-120 p.p.m. Rendzinas: in Israel, on marl, in Czechoslovakia, on sandy marl: 23-35 p.p.m.; in the Adelaide region and in the southeast of Australia: 6-43 p.p.m.; in Madagascar, on gritty limestone: 35 p.p.m. Arid and semiarid regions In these climatic zones the total copper contents in soils are generally average or high. Chernozems have concentrations between 15 and 70 p.p.m.: in the Cluj and Dobrudja regions of Rumania, on loess: 25-45 p.p.m. Bulgaria: on basalt, andesite and gabbro: 15-68 p.p.m. Ural-Sakmara basin of the U.S.S.R.: on secondary sediments: 60-70 p.p.m. Chestnut soils generally have high copper contents: in the Or-Kumak basin of the U.S.S.R., on sodic weathering products of basic rocks: 88-96 p.p.m.

29

Brown isohumic soils have average contents: in Israel on calcareous sandstone and in Uzbekistan (U.S.S.R.), these soils contain 1 6 p.p.m. and 18-22 p.p.m., respectively. Vertisols are more often rich and even very rich in copper:Central African Republic on amphibolite: 11-200 p.p.m. In Chad, on sandy clay sediments, in the soils of Tasmania and Queensland, Australia, on dolerite and basalt: 30-90 p.p.m. In India, Gujarat, on sands and limestone: 80-155 p.p.m.; in Maharashtra: 70-230 p.p.m. Saline soils (solonetses and saline alkali soils) can also be very rich in copper. Thus, the Al horizons of some solonetses of the Ural-Sakmara or OrKumak basins contain 6 0 - 6 4 p.p.m. and those of the very saline alkali soils in the same regions contain 164 p.p.m. Tropical humid regions

Soils of these regions have very variable copper concentrations, the upper and lower limits are very wide: traces t o 200-250 p.p.m. These concentrations often depend on those of the parent rocks. Thus in Ghana, weakly to averagely desaturated ferrallitic soils, on reddish loam derived from basic rocks, are richer than the soils of the same type formed on granite and sandy material: 100 p.p.m. and 20-30 p.p.m., respectively. The lowest copper concentrations, traces-10 p.p.m., have been found in:New Caledonia, in different types of soils (slightly evolved deposits soils, brown eutrophic soils. . . on limestone-cemented flysch), Chad, in soils on sandy material, low-humic hydromorphic gley or pseudogley soils and gray leached ferruginous pseudogley soils, Ivory Coast, in the low-humic hydromorphic pseudogley soils on schists and in an erosion ranker on charnockite. Average copper concentrations, 10-50 p.p.m., were found in:Alluvial or slightly evolved soils, more or less hydromorphic, on alluvions, in Madagascar; on alluvions of volcanic origin in Polynesia, as well as on various alluvions of Logone, in Chad, Gray ferruginous soils on basic rocks, schist and sandstone, in Madagascar, Ferrallitic soils on basalt, granite, gneiss and limestone, in Madagascar; ferrallitic soils with indurated or non-indurated subsoil, on basalt and andesitic basalts, in Polynesia, Saline soils on clayey sediments in Chad, and on alluvions in Madagascar. Total copper contents are often high in the krasnozems, as in Australia (Tasmania and Queensland): 80-140 p.p.m. The contents become very high in the generally rather deep soils formed on “mineralized rocks” and often called mining soils. In Upper Katanga, under similar conditions 1.5’/00 and 6’100 (and exceptionally 10’/00 ) of total copper were determined (Duvigneaud and Denaeyer de Smet, 1960).

30

It appears, on the other hand, that in tropical regions certain factors other than the parent rock or soil type, such as secondary pedogenic processes, generally have an influence on the total copper content in soils: e.g. degree of weathering of the rock, extent of evolution of the soil, degree of leaching. Thus, in the Central African Republic, in relation t o these various processes, gray fermginous soils, derived from charnockite, gneiss or migmatite, have, on each of these rocks, total copper contents either very low: traces-1 p.p.m.; or average: 10-30 p.p.m.; or very high: 100-200 p.p.m. These same observations can be made in the more or less leached ferrallitic soils and the slightly evolved erosion soils. In each of these large climatic zones the total copper content of soils may depend on man’s intervention in addition to these different pedogenic factors. Man can considerably increase the contents of copper by his use of anticryptogamic treatments on cultivated plants. Thus, in France, the copper concentration of vineyard soils, which have undergone intensive anticryptogamic treatments, can attain 850 p.p.m. in the cultivated layer.

COPPER CONTENT OF SOILS “AVAILABLE” TO PLANTS

Copper has an important biological role. Its deficiency brings about certain animal and plant diseases. Thus, it is interesting t o know not only the total copper content of soils but also, the “plant-available” contents. These contents vary, according to the method of extraction. The usual extraction reagents are the following: Strong diluted acid: 1N hydrochloric and 1N nitric acids Weak acid: 2.5% acetic acid (pH 2.5) Salt: neutral ammonium acetate (pH 7),which corresponds t o “exchangeable copper” Chelating agents : E.D.T.A. . . .. From the analytical results obtained, one notices that in Gujarat, India, copper extracted from vertisols, vertic and alluvial soils by 1 N ammonium acetate ranges from 0.3 t o 1.6% of the total copper. In France, in the leached soils of the South-West (vineyard soils), which have undergone intensive anticryptogamic treatments, the concentrations of “available” copper, exchangeable by ammonium acetate are very high: 65-180 p.p.m., i.e. 21% of total copper. By contrast, in the lithic and acid brown soils of Cevennes concentrations are only 3-4 p.p.m. The amount of copper soluble in 2.5% acetic acid is often low: in Scotland, 0.06-0.3 p.p.m. in a brown podzolic soil or 0.8-1.296 of the total copper. The percentage reaches 3-5% in an iron pan peaty podzol (less than 0.10-0.27 p.p.m.). Higher concentrations are obtained by extraction with E.D.T.A. : in the different types of soil in Israel (rendzinas, alluvial soils, saline hydromorphic

31

soils, etc.) 2-7.5 p.p.m. of “available” copper were found, i.e. 7-1796 of total copper; in India, in alluvial soils, vertic soils.. , the corresponding contents vary from 0.45 t o 12.3 p.p.m., i.e. 7-1076 of the total copper. A strong reagent, 1 N hydrochlo-ric acid, is often used by Russian authors. The quantities extracted are often high: brown forest soils of the Krasnodar region contain 21.4 p.p.m. or 33% of the total copper; chestnut soils, solonetses and very saline alkali soils of the Or-Kumak basin, 18-20% of total copper. The percentage attains 60% (100 p.p.m.) in the podzolic soils of the Kola peninsula, which were formed from crystalline schists very rich in copper.

VARIATIONS OF THE COPPER CONTENT OF SOILS

The total copper concentrations of soils seem t o vary in the same way as those of humus and adequately evolved organic matter. An accumulation of this element in the upper humiferous horizons can often be observed, for example, in the weakly podzolic leached soils or in the more evolved surface horizons of the peaty soils of the Kola peninsula. On the contrary, in Scotland, typical podzolic soils have lower contents of total copper in the coarse-humus horizons than in the illuvial horizons. In the chernozems, copper content variations between the horizons are slight. In a number of more or less leached or impoverished soils, the B horizons are richer than the A2 horizons: as a matter of fact, copper contents also vary in relation to the clay content. The element accumulates in the clayey horizons. In certain soils of Chad and Madagascar, a slight increase in copper and clay content is noticed with increasing soil depth. Besides, as Pasternack and Glinski (1969) have shown, in Poland, clayey soils are richer in copper than sandy soils. Soil pH seems t o play an important part in determining “plant-available” copper contents : in Poland and India (Madhya-Pradesh) “available” copper decreases with increasing pH. Certain peaty soils with high concentrations of organic matter such as those of Bielorussia, are deficient in “available copper”; as a matter of fact, the humic acids at pH 2.5-3.5, and the fulvic acids at pH 6, form insoluble compounds with copper which are unavailable to plants.


Toxicity levels are different according to plant varieties. In Rumania (Moldavia) a toxicity for oats and maize cultivated on chernozems and orchard soils containing more than 25-30 p.p.m. of available copper, is noticed. In France, because of intensive anticryptogamic treatments, the

32

“exchangeable” copper content (extraction by 1 N ammonium acetate, pH 7) ranges from values of 50 to 200 p.p.m. in vineyard and orchard soils (Delas et al., 1959). On the other hand, the poor yield of cereals cultivated on a cleared vineyard was noted. A systematic study of copper toxicity in relation t o soil pH, with equal “available” copper contents, showed that this toxicity increased with decreasing pH. For maize, at pH 6, toxicity is noticeable above a value of 50 p.p.m.; growth decreases by one-half for 100 p.p.m. and is strongly inhibited at 200 p.p.m. Toxicity is even greater at pH 5 for the same concentrations. For wheat, toxicity appears at 25 p.p.m. in a soil of pH 4 (Drouineau and Mazoyer, 1962). This copper toxicity in relation to soil pH is due to the fact that the activity of copper ions increases when the pH decreases; on the other hand, the copper retention capacity of organic matter decreases at the same time as the pH. Toxicity is corrected by increasing the organic matter content (manuring) and by increasing the pH (liming and alkaline fertilizers). Thus copper is fixed and becomes insoluble. Copperdeficient soils are most often peaty soils or sandy podzolic soils located in regions with heavy rainfall. Deficiency is also associated with soils derived from parent rocks poor in copper: granite, calcareous limestone (reddish-brown isohumic soils of Israel) and limestone (Ryan et al., 1967). In France, deficiency has been noted particularly on the sandy podzols of the moors of Gascony and in the podzolic soils on granite and limestone of the Armorican Massif (Duval and Coppenet, 1960). The deficiency limit is equal t o 1 p.p.m. in the sandy and clayey soils of Norway and in different soils of India (Madhya-Pradesh). In Japan, this limit is 0.5 p.p.m. In Egypt, soils containing 0.8-3.2 p.p.m. of copper soluble in 1 N nitric acid are regarded as deficient; from 3 to 1 2 p.p.m. they are really no longer deficient but fertilizers containing copper can improve yields. In Latvia, application of copper to soils having only 0.01-3.25 p.p.m. of copper soluble in 1 N hydrochlorid acid increases the harvest. In India, New Delhi, copper spraying increases the fixation of phosphorus and potassium and, consequently, increases wheat harvest for soils containing 22 p.p.m. of total copper and 2.55 p.p.m. of E.D.T.A.-extracted copper. In France and Scotland, a number of authors prefer to use total copper contents as a measure for diagnosing deficiencies. For a number of crops, the threshold showed ranges from 7 t o 8 p.p.m. in distinctly acid soils of the podzolic type.

CONCLUSION

Soils contain on average 20 p.p.m. of copper. Their concentrations depend on those of the parent rocks (particularly rich volcanic basic rocks), humus, organic matter and clay concentrations and on the pH. Basic or neutral pH

33

soils, which are rich in humus, contain more copper than acid pH soils. Chernozems, some saline soils and vertisols are among the soils richest in this element. To a large extent toxicity varies with soil pH. Values of 0.5-3 p.p.m. of “available” copper and 7-8 p.p.m. of total copper can be considered as deficiency limits for a number of crops. Fertilizers containing copper correct these deficiencies. Liming and organic matter supply remove the toxicity.

See also the following works published since 1968: ENGLAND: Mitchell, R.L., 1974. IRELAND: Brogan, J.C., Fleming, G.A. and Byrne, J.E., 1973. BELGIUM: Nair, K.P.P. and Cottenie, A., 1 9 6 9 ; Nair, K.P.P. and Cottenie, A., 1971. SPAIN: Macias, F.D., 1973. YUGOSLAVIA: JekiE, M. and SaviE, B., 1970/1971. GREECE: Apostolakis, C.G. and Douka, C., 1970. POLAND: Andruszczak, E. and Debowski, M., 1 9 7 1 ; Boratynski, K., Roszyk, E. and Zietecka, M., 1 9 7 1 ; Czuba, R., Gaszek, K. and Wlodarczyk, Z., 1 9 7 4 a ; Czuba, R., Dudziak, S. and Malinska, H., 1 9 7 4 b ; Kocidkowski, Z. and Staszewski, T., 1 9 7 3 ; Staszewski, T. and Kociatkowski, Z., 1974. HUNGARY: Kereszteny, B., 1973. RUMANIA: Chiriac, A. and Bajescu, I., 1974. U.S.S.R.: Dobrolyubskii, O.K. and Evestrat’eva, T., 1 9 7 3 ; Do-Van-Ay, Borovik-Romanova, T.F., Kovarskii, V.V. and Makhova, N.N., 1 9 7 2 ; Grabarov, P.G., 1 9 7 0 ; Koval’skii, V.V. and Andrianova, G.A., 1 9 7 0 ; Krym, I.Ya., 1 9 7 1 ; Panin, M.S., Panina, R.I. and Kaverin, V.N., 1970;Panin,M.S., 1972;Shirokov, V.V. and Panasin, V.I., 1972;Stoilov,G. and Atanasov, I., 1 9 7 1 ; Zborishchuk, Yu.N. and Zyrin, N.G., 1974. CYPRUS : Pagel, H. and Prasad, R.N., 1971. U.S.A. : Follett, R.H. and Lindsay, W.L., 1971. PUERTO RICO: Regus, J.R., 1969. BRAZIL: De Santana, C.J.L. and Igue, K., 1 9 7 2 ; Horowitz, A. and Da Silveira Dantas, H., 1974. ARGENTINA: Merodio, J.C., 1970.

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INDIA: Badhe, N.N., Naphade, K.T. and Ballal, D.K., 1 9 7 1 ; Lodha, P.S. and Baser, B.L., 1 9 7 1 ; Mishra, B., Tripathi, B.R. and Dayal, D., 1 9 6 9 ; Rai, M.M., Dighe, J.M. and Pal, A.R., 1972a; Sharma, B.M. and Deb, D.L., 1 9 7 4 ; Singh, D., Denge, R.S. and Dixit, R.G., 1971;Singh, S. and Jain, R.K., 1971. NORTH VIETNAM: Glinski, J. and Cao Thai, V., 1971. JAPAN : Masui, J., Shoji, S. and Minami, K., 1972;Mizuno, N. and Kobayashi, S., 1971. TAIWAN: Tan, L.P. and Ho, C.O., 1972. NEW ZEALAND: Lyon, G.L., Brooks, R.R. and Peterson, P.J., 1970. ALGERIA : Lomov, S.P.,1973. EGYPT: Abdel Salam, M.A., El-Demerdashe, S., Abdel-Aal, Sh.1. and Ibrahim, M.G., 1 9 7 1 ; ElMowelhi, N.M., Mitkees, A.I., Abouhussein, M.A. and Shabassy, A.I., 1 9 7 3 ; Kishk, F.M., Hassan, M.N., Ghanem, I. and El Sissy, L., 1973. CAMEROUN: NaloviE, Lj. and Pinta, M., 1972. TANZANIA: Kocialkowski, Z. and Dziqciolowski, W., 1972.

35

IODINE * The study of iodine has been carried out, above all, in relation to the appearance of goitre in certain regions, this sickness being related to very low iodine contents in soils and waters. Vinogradov (1959) has dealt with this problem and carried out much research work relating to the presence, proportions and evolution of this element in the rocks and soils of the U.S.S.R. Rocks are generally poor in iodine whatever their origin: most rocks have concentrations ranging from 0.2 to 0.8 p.p.m.:Basic eruptive rocks: 0.5-0.8 p.p.m. Acid eruptive rocks: 0.4 p.p.m. Metamorphic rocks (schists) and certain sedimentary rocks (clays) contain slightly higher concentrations: 1-2 p.p.m. However, sands and more or less sandy glacial deposits, as well as certain limestones, have very low contents: 0.2-0.3 p-p-m. On the other hand, sedimentary deposits of marine origin contain extremely high concentrations: 100--1,000 p.p.m. The average concentration of iodine in the lithosphere is about 0.3 p.p.m. (Vinogradov, 1959; Turekian and Wedepohl, 1961; Kovda et al., 1964). Recent bibliographical data, coming exclusively from the Amur basin of the U.S.S.R. and concerning the iodine concentrations of rocks, confirm the average contents cited above: andesite and diorite 0.3 p.p.m.; sands and sandy loams: 0.2-0.4 p.p.m.; clayey loams and clays: 0.6-2 p.p.m.; stratified flood plain deposits: 1-2 p.p.m.

TOTAL IODINE CONTENT OF SOILS

Soils are much richer in iodine than are parent rocks. According to Vinogradov (1959), the total iodine contents of soils might be twenty to thirty times higher than those of the rocks. In the soils analyzed, the concentrations are between 0.7 p.p.m. (leached gray ferruginous soils of Mali) and 25 p.p.m. (humic gley soils of Latvia). The average content ranges from values of 1 to 5 p.p.m. There is a clear relationship between the iodine contents of soils and their texture. On the whole, soils are richer in this element when they are more clayey. Thus in Spain, sandy soils have contents between 0.5 and 4 p.p.m. and clayey soils between 1and 8.9 p.p.m. In the U.S.S.R., hydromorphic meadow soils of the Amur region contain: sandy soils, 0.09 p.p.m.; clayey soils, 1.9-5 p.p.m. Likewise, in Latvia or in the Kaluzha region, the more or less podzolic soils, on sands or sandy clay *See Tables, pp. 244-247

36

deposits, have low contents, often lower than 0.4 p.p.m. or at least than 1 p.p.m.; in Bielorussia, these soils on clayey l o a s and lacustnne clays can contain from 1.6 t o 2.7 p,p.m. Soil iodine contents also seem t o be related in some degree to certain characteristics brought about by the type of evolution.

Temperate and boreal regions Brown forest soils have variable total iodine contents, generally about 1-2 p.p.m. In one case, a maximum value of 1 2 p.p.m. was found. Thus, in the Amur basin of the U.S.S.R., these soils on sands contain from 0.7 to 2.4 p.p.m. and on andesite diluvium and on basalt diluvium they contain, respectively, 1and 1 2 p.p.m. Rendzinas and brown calcareous soils are richer:In Israel, on marl: 4.1-4.9 p.p.m. In Bielorussia: 1.8-3.6 p.p.m. In Latvia: 0.38-3.47 p.p.m. Humic gley soils have much higher contents than average. The maximum iodine concentrations determined in soils (18-25 p.p.m.) have been found in very humiferous humic gley soils of the U.S.S.R. (in Latvia and the Moscow region).

Arid and semiarid regions Isohumic soils of these regions have average iodine contents. Thus, in the Amur basin of the U.S.S.R., chernozems contain 2.6 p.p.m. and chestnut soils contain from 1.7 to 2.9 p.p.m.; related solonetses contain 3.8 p.p.m. of total iodine. Mediterranean red soils on limestones can be very rich in iodine, those of Israel, for example, contain 7.5 p.p.m. Moreover, the highest concentrations found in Israel were in alluvial soils derived from “terra rossa” (10.5-11.6 p.p.m.).

Tropical hum id regions The only recent available data concern the gray femginous and alluvial soils of Mali. They are very poor in iodine.

VARIATIONS O F THE IODINE CONTENT OF SOILS

It appears that the organic matter, humus and clay concentrations have a much greater importance than that of the parent rocks when considering the total iodine content in soils.

31

The iodine content of soils varies, chiefly, in relation t o the concentration of organic matter and humus. If one considers the different types of soils, the soils richest in iodine are those which contain a high content of organic matter (humic gley and very humiferous soils of Latvia and the Moscow region, and even the chernozems of the Amur basin, which have average t o high contents). The distribution of iodine in soil profiles follows that of humus. One generally notices an accumulation in the upper humiferous horizons. In leached podzolic soils and podzols, this accumulation occurs in the illuvial B horizons. As has been shown before, the iodine content of soils also depends on soil texture. Clayey soils are often richer in iodine than sandy soils. The influence of soil reaction also seems t o be important. The content of this element is high in alkali soils or in pH basic soils, as is frequent in the upper horizons of soils in arid and semiarid regions (saline alkali soils of Israel). Similarly, one notices that in partially or totally water-logged soils iodine content increases in relation t o depth. On the other hand, the influence of certain factors which do not depend on the type of soil may have some significance, e.g., closeness t o the sea. According t o some authors (Vinogradov, 1959), because the principal source of iodine is atmospheric iodine coming from the evaporation of sea water, soils of maritime regions have higher iodine contents than continental region soils. Moreover, as vegetation of marine origin is very rich in iodine, soils derived from marine sediments are very rich too, as are those which are supplied with fertilizers of marine origin.

TOTAL IODINE DEFICIENCY IN SOILS

Iodine is an important element for human beings. It is involved in the composition of the thyroid hormone and its absence causes goitre. According t o Vinogradov (1959), it is possible t o tell from the endemic seats of this illness the regions with soil iodine deficiency. Such soils exist in mountainous regions: brown forest soils of Switzerland, forest soils of northern Caucasus and podzolic or very leached plain soils with a strong acid pH; finally, sometimes even, certain strongly acid peaty soils. Ryan et al. (1967) cite deficiency cases in different European countries (Finland, Norway, Poland . . . .) related t o soils on calcareous parent rocks. In Israel this deficiency appears in the reddish-brown isohumic, slightly humiferous, sandy soils on calcareous sandstone.

38 CONCLUSION

Iodine is found in soils in very wide concentrations (0.02 t o 20-25 p-p.m. ). The richest soils are those with high concentrations of developed organic matter and clay, which in a slightly acid medium, fix and hold this element. Conversely, podzolic and leached soils, at least in their upper horizons, as well as slightly evolved sandy or coarse-textured soils, in their whole profiles, have low iodine contents. Soils are generally much richer in iodine than the rocks on which they were formed. Only hydrological, climatic, biological and other factors, leading to the accumulation of slightly acid organic matter and the formation of colloids, have an important role as t o the iodine content in soils.

See also the following works published since 1968: POLAND: Ewy, Z., Bobek, S., Kaminski, J.,Pryska, H. and Styczynski, H., 1972. U.S.S.R. : Babayan, G.B. and Safrazbekyan, E.A., 1 9 7 1; Irinevich, A.D., Rabinovich, I.Z. and Fil’kov, V.A., 1 9 7 0 ; Lazovsii, L.I., 1 9 7 1 ;0 b u k h ova , V.A. and Gololobov, A.D., 1 9 6 9 ; San’ko, P.M., Lozovskii, L.I. and Sinitsa, L.A., 1973a ; San’ko, P.M., Lozovskii, L.I. and Sinitsa, L.A., 197313; Sinitskaya, G.I., 1 9 69; Zborishchuk, Yu.N. and Zyrin, N.G., 1974.

39

LEAD* Recent bibliographical data concerning the distribution of lead in soils are relatively few in number. Moreover, authors seem to have studied this element principally in relation to its toxicity. However, the Pedology Department Spectrography Laboratory of the “Services Scientifiques Centraux de 1’O.R.S.T.O.M.” has determined lead contents in a fairly large number of tropical soils, which has led to a better knowledge of its distribution in these soils. Lead can be found in all the rocks of the earth’s crust:Basic eruptive rocks (basalt, gabbro . . .): 8 p.p.m. Acid eruptive rocks (granite, rhyolite . . .): 20 p.p.m. The contents are about the same in intermediary rocks (diorite and andesite), metamorphic rocks (schists) and certain sedimentary rocks (clays) : 15-20 p.p.m. The contents are average in limestones and sandstones: 7-10 p.p.m. The average concentration of lead in the lithosphere is about 16 p.p.m. (Swaine, 1955; Vinogradov, 1959; Turekian and Wedepohl, 1961). The only analytical data that are available concerning the lead content of parent rocks corresponding t o the soils studied, come from the Kola peninsula, U.S.S.R.: crystalline schists with norite intrusion: 50 p.p.m.; sandy clay moraine covering these schists: 50 p.p.m.

TOTAL LEAD CONTENT OF SOILS

Soils are often richer in lead than the rocks from which they are derived. The concentrations found in the different types of soils studied range from traces (various types of tropical soils) t o 1,200 p.p.m. (podzols of Canada). The average concentration is about 15-25 p.p.m.

Temperate and boreal regions The lead contents of the soils of these regions are often higher than average. Podzols have variable concentrations, generally fairly high, which depend to a large degree on the parent rock. Thus, in Scotland, contents range from 20 p.p.m. in brown podzolic soils on serpentinite and olivine gabbro, to 70-80 p.p.m. in podzols on granitogneiss and micaschists. The same type of soil on granite and gneiss contains 50 and 40 p.p.m., respectively. The highest concentrations, much higher than average, have been deter*See Tables, pp. 248-255.

40

mined in Canada (New Brunswick) in podzols on sulphide-rich sediments (1,041 p.p.m. in L-H horizon and 1,290 p.p.m. in B, horizon). Contents are about the same in hydromorphic soils. In Westphalia, Germany, and in Scotland, values of 11-80 p.p.m. and 50 p.p.m. were found, respectively, in a gley hydromorphic soil on schist. Brown forest soils have contents ranging from 25 t o 40 p.p.m., whether in northeastern China on basalt, or in Scotland on andesitic moraine. Also, in Madagascar, a value of 20 p.p.m. of lead was found in a black rendzina on gritty limestone.

Arid and semiarid regions The lead contents of the different types of soil in these regions are widely variable. On the whole, they are about the same as those given previously. Thus the chemozems of the Ural-Sakmara basin, U.S.S.R., contain an average of 11p.p.m. of lead on serpentinite and 2 5 p.p.m. on Secondary and Tertiary sediments. Contents are lower in the subarid isohumic soils on sandy clay material in Chad (traces-15 p.p.m.). Vertisols have variable contents: topomorphic vertisols on limestonecemented flysch in New Caledonia are poor in lead (less than 2 p.p.m.), whereas in Chad, on sandy clay sediments, as well as in Madagascar, on alluvions, contents range from values of 20 to 45 p.p.m. Variations are about the same in subdesert and saline soils: in the Ustyurt region, U.S.S.R., subdesert soils on clayey loam contain 42-80 p.p.m. of lead. Saline soils, on clayey sediments in Chad and on alluvions in Madagascar, contain, respectively, 1-10 p.p.m. and 22 p.p.m. (on average) of lead.

Tropical humid regions The soils of these climatic zones have the same upper and lower limits of lead concentrations as previously shown (traces and 30-50 p.p.m.). Very low concentrations have been found in eutrophic brown and reddishbrown soils on limestone-cemented flysch in New Caledonia (1-2 p.p.m.) and on basic slags in the New Hebrides (4p.p.m.). Gray ferruginous soils: in the Central African Republic, lead contents range from less than 3 p.p.m. on charnockite to 20 p.p.m. on gneiss, amphibolite and migmatite. In Chad, on sandy clay sediments, the concentrations range from 3 to 30 p.p.m.; in Madagascar, values of up t o 1 7 5 p.p.m. of lead have been found in a gray ferruginous soil on basic rock. Ferrallitic soils also have rather variable lead contents. They are very low in Polynesia, in more or less degraded ferrallitic soils with an indurated or non-indurated subsoil: less than 1 p.p.m. In the Central African Republic,

41

in slightly desaturated ferrallitic soils on different parent rocks (charnockite, gneiss, migmatite . .), they vary from less than 3 p.p.m. to 30 p.p.m. They are higher in Chad on arkose and arkosic sandstone: 10-30 p.p.m.; in Dahomey, on sandy clay Tertiary sediments 23 p.p.m. were determined and in Madagascar 10-50 p.p.m. on limestone, basalt, granite or gneiss. More or less hydromorphic soils on alluvions and more or less humiferous hydromorphic alluvial soils (alluvions of volcanic origin) in Polynesia are poor in lead: 1-3 p.p.m. In the Central African Republic, Chad and Madagascar, lead concentrations found in these types of soils are, respectively, less than 3 p.p.m. to 30 p.p.m., 20-50 p.p.m. and 25-30 p.p.m. Slightly evolved deposit soils: in Madagascar soils on clayey sand material are rich in total lead: 35-50 p.p.m. On the other hand, soils in Polynesia on basaltic drifts, in New Caledonia on limestone-cemented flysch colluvium and in New Hebrides on acid pumices and basic slags have low contents: 1-2 p.p.m. and 2-5 p.p.m.

.

LEAD CONTENT O F SOILS “AVAILABLE” TO PLANTS

The extraction reagent used, according to the case, is 2.5%acetic acid (pH 2.5) or dilute nitric acid. Acetic acid has been used especially in Great Britain. In Scotland 4--12% of total lead was extracted with 2.5%acetic acid from a brown podzolic soil and an iron pan podzol; in Wales, for soils on rhyolite, dolerite, pumice tuff and mixed drifts, acid-extractable lead corresponds to 1-4.3% of total lead. According to Vinogradov (1959) acetic acid would extract about 30% and nitric acid about 60% of total lead. However, it is difficult t o come to positive conclusions about these forms of lead in soils because of the limited data available.

VARIATIONS OF LEAD CONTENT OF SOILS

Generally very wide variations are not noticed in the distribution of lead between the different horizons of soil profiles. However, lead contents vary, more or less, in relation to humus and organic matter concentrations. Most of the time an accumulation of lead is observed in the upper soil horizons. This accumulation of lead in the upper horizons is particularly obvious for the podzols and podzolic soils of Scotland, the peaty soils and the slightly podzolic leached soils of northern Kola peninsula and for some slightly developed chernozems of the Ural-Sakmara basin. According to various authors (Swaine and Mitchell, 1960; Dobrovol’skiy and Aleshchukin, 1964; Krym, 1964) this accumulation may be of biogenetic origin (accumulation by plants).

42

On the contrary, in the well-developed chernozems of the Ural-Sakmara basin, lead content remains constant in the various horizons. On the other hand, lead accumulates in the humiferous illuvial B horizon of podzols (podzols on sulphide-rich sediments in New Brunswick, Canada) and in the slightly humiferous but more clayey gley horizons (podzols of Scotland). As a matter of fact, lead content also varies in relation to the clay content of soils. In tropical soils it was shown that the lead content has a tendency to increase at the same time as the clay content, in relation to the depth of the horizon (soils of Dahomey, Pinta and Ollat, 1961).

LEAD TOXICITY

Certain soils which are located near mines are very rich in this element. Concentrations can readily attain 5,000 p.p.m., bringing about a toxicity in plants and waters used by animals. Experiments performed in the U.S.A. with nutritive solutions showed that lead toxicity in plants varies with the pH: the more alkaline the pH, the more toxic is the lead at low concentrations (Rasmussen and Henry, 1963).

CONCLUSION

Soils have lead contents slightly higher than those of parent rocks. The average content is about 15-20 p.p.m. Soils of temperate and boreal zones have lead contents slightly higher than those of soils of arid, semiarid or tropical zones. Lead accumulates in the humic and clayey horizons of soils.

See also the following works published since 1968: FINLAND: Ervio, R. and Lakanen, E., 1973. WALES : Alloway, B.J. and Davies, B.E., 1971. ITALY: Fidora, B., 1972;Sapetti, C. and Arduino, E., 1973. SWEDEN: Wiklander, L., 1 9 7 0 ; Wiklander, L., 1971. U.S.A.: Bradford, G.R., Bair, F.L. and Hunsaker, V., 1971;Williams, C., 1974. INDIA: Misra, S.G. and Pandey, G., 1973.

43

MANGANESE* All the rocks of the earth’s crust contain manganese in concentrations generally much higher than those of other trace elements. The highest contents are t o be found in basic eruptive rocks (basalt, gabbro .. .): 1,000-2,000 p.p.m. Contents vary widely in acid eruptive rocks (granite, rhyolite.. ..), metamorphic rocks (schists), as well as in certain sedimentary rocks (loam, clay.. ,): 200--1,200 p.p.m. Average contents are t o be found in limestones: 400-600 p.p.m. and contents are relatively low in sands: 20-500 p.p.m. The average manganese concentration of the earth’s crust is about 9001,000 p.p.m. (Vinogradov, 1959; Kovda et al., 1964). The few analytical data cited, concerning the parent rocks studied by different authors, are quite in agreement with the above values, with the exception of some dolerites of Australia (Tasmania), where contents can attain 16,500 p.p.m. In the U.S.S.R., crystalline schists with norite intrusion of the Kola peninsula contain 1,000 p.p.m. of manganese; loess of Uzbekistan: 580-720 p.p.m.; glacial and lacustrine clays of Bielorussia: 500 p.p.m.; granites and sandy deposits rich in gravels of the Amur region: 170 p.p.m., and in the lacustrine alluvions of the same region a value of 900 p.p.m. was found. In the Guadalquivir valley of Spain contents are about 200 p.p.m. in calcareous rocks and 400-600 p.p.m. in the quaternary alluvions. TOTAL MANGANESE CONTENT OF SOILS

Soil manganese has been the object of much research. Bibliographical data concerning this element can be given for practically all regions of the globe. In the U.S.S.R., U.S.A., India and Australia, in particular, many papers have been published about this element in all its different forms. The most recent data are given here, coupled with the latest data of the Pedology Department, Spectrography Laboratory of the “Services Scientifiques Centraux de 1’O.R.S.T.O.M.” concerning the soils of tropical and subtropical countries, principally African countries and Madagascar. Total manganese content of soils varies widely: from traces (podzols of Poland) t o 10,000 p.p.m. (unleached alkali soils of Chad). Most soils contain, on an average, from 500 t o 1,000 p.p.m. of total manganese. The variations noticed can rarely be correlated with soil typology, but they are often high between soils of the same type in a given climatic region.

*See Tables, pp. 256-297.

44

Temperate and boreal regions Concentrations of total manganese range from traces t o 8,800 p.p.m. In the different types of soil of these regions, the lowest concentrations have been found in certain podzols: podzols of Poland, in the Lodz region, contain traces to 50 p.p.m.; podzols of Scotland, on granite, contain 50 p.p.m. and those of Norway, on morainic material 100-220 p.p.m. (iron and iron-humic podzols). On the other hand, in Bielorussia, contents range from 280 to 750 p.p.m. in podzols on sands and from 360 to 1,000 p.p.m. in those on loam and clay. In some cases the total manganese contents of podzols depend closely on those of the parent rocks: in Canada (New Brunswick), podzols on nonsulphide sediments contain 600 p.p.m. of total manganese and the podzols on sediments rich in sulphur contain 1,100 p.p.m.; in Scotland, podzols on granito-gneiss and micaschists have contents varying from 1,000 to 3,000 p.p.m. and a value of 7,000 p.p.m. was found in a brown podzolic soil on olivine gabbro. Important variations of total manganese were found in other types of soils. Leached soils:Slightly podzolic leached gley soils of Bielorussia contain only 6-23 p.p.m., but in Bulgaria and Canada (Nova Scotia) contents range from 740 to 1,700 p.p.m. and from 350 to 1,800 p.p.m., respectively. Hydromorphic gley soils and meadow soils:In Scotland, on schists, and in Spain, on alluvions, values of 300-500 p.p.m. were found; in the Amur region, contents attain 1,300-1,800 p.p.m. A hydromorphic meadow soil of the Amur region had the highest total manganese content found in temperate and boreal regions: 8,800 p.p.m. Brown forest soils also have widely variable total manganese concentrations. These soils are relatively poor in manganese on calcareous rocks, in the Guadalquivir valley (Spain): 250 p.p.m. They are richer in Hungary and Bulgaria: 120-160 p.p.m. and 260-1,380 p.p.m., respectively. These soils are rich in the Kuban region, containing from 400 t o 2,400 p.p.m., and in the Amur region on granite, 3,150 p.p.m. In Tasmania, on dolerite, they contain from 850 t o 3,100 p.p.m. Rendzinas gave values from 200 p.p.m. (on calcareous rocks in Spain) to 1,100 p.p.m. (in the U.S.S.R., Kuban region, as well as in the Adelaide region and the southeast of Australia). Alluvial soils of Poland are often rich in total manganese: 800--4,000 p.p.m.

45

Arid and semiarid regions

The upper and lower limits of the soils of these regions range from traces (chernozems and chestnut soils of the lower Volga valley) t o 10,000 p.p.m. (unleached saline alkali soils of Chad). With the exception of those formed on ancient sandy alluvions of the lower Volga valley, in which the total manganese contents are very low ( t r a c e s 4 0 p.p.m.) chernozems have average contents which appear to be relatively constant: in Bulgaria values range from 520 t o 840 p.p.m. and in the U.S.S.R. (different regions) from 600 t o 1,000 p.p.m. On the contrary chestnut and brown isohumic soils have widely variable concentrations of this element. Chestnut soils: in the lower Volga valley, on sands, contents vary from traces t o 90 p.p.m.; in the Kuban region values between 550 and 600 p.p.m. were found. Brown isohumic soils: in Chad, on sandy and clayey sediments, 60-180 p.p.m.; in Queensland, Australia, on calcareous sandstone and clayey sediments: 550-1,670 p.p.m. Vertic soils and vertisols are often rich and, sometimes, very rich in total manganese: in Spain, on quaternary alluvions, a value of 500 p.p.m. was found; in New Caledonia, on limestone-cemented flysch, 800 p.p.m.; in Queensland and Tasmania, on diorite, basalt, alluvions and dolerite, 1,2502,750 p.p.m.; in Madagascar, on marl and basalt, 700-2,400 p.p.m.; in India, 650-2,950 p.p.m. The highest concentrations were determined in the Central African Republic, in lithomorphic vertisols on amphibolite: 3,000-5,000 p.p.m. Saline soils (solonetses, saline alkali soils) generally have average total manganese contents, but they can contain very high amounts in places. In Spain, on quaternary alluvions, concentrations attain 1,000 p.p.m.; this is so in Turkmenistan and Uzbekistan where, however, contents may decrease to 100 p.p.m. It is the same in Queensland, where values of 60-990 p.p.m. of total manganese were found in solods on granitic rocks or on alluvions. In Chad, saline soils on alluvions contain about 700 p.p.m., but in some unleached saline alkali soils quite exceptional values of up t o 10,000 p.p.m. were determined. Mediterranean red soils show similar variations. Those of Spain on calcareous rocks and Quaternary alluvions rarely attain average contents: 340-390 p.p.m.; in Australia, contents range from 140-270 to 1,100 p.p.m. in mediterranean red soils of Queensland on granodiorite and basalt, and from 180 to 1,400 p.p.m. in those of the Southeast and Adelaide region.

46

Tropical humid regions The upper and lower limits of total manganese contents of the soils of these regions are about the same as those mentioned previously for soils of the other climatic regions: 20-30 p.p.m. and 4,000-5,000 p.p.m.; concentrations are often widely variable for one type of soil. Brown, reddish-brown and brown eutrophic soils on limestonecemented flysch, on slaggy basaltic tuffs and dolerite of New Caledonia and on basaltic slags of the New Hebrides, are generally rich in total manganese: about 8002,500 p.p.m. The same concentration variations are found in gray ferruginous and ferrallitic soils, whose contents are intimately connected with those of the parent rocks. Gray ferruginous soils: in the Central African Republic, contents range from 30-50 p.p.m. on granite, t o 1,500--4,000 p.p.m. on gneiss and amphibolite. Soils on charnockite contain from 100 to 300 p.p.m. of total manganese. Likewise, in Madagascar, these types of soil are very rich on basic rocks: 3,500 p.p.m., but those on schists are poor in this element: 150 p.p.m. Ferrallitic soils. The same can be said concerning weakly to moderately desaturated ferrallitic soils of Ghana: 100-350 p.p.m. on granite, and 2,000-3,000 p.p.m. on debris of basic rocks. Krasnozems of Australia, on dolerite, are also very rich: 1,350-4,250 p.p.m. Secondary pedogenic factors, e.g. more or less accentuated decomposition of the parent rock, more or less accentuated evolution of the soil, leaching and lixiviation, can have a stronger influence on total soil manganese concentrations than that of the rock. This can cause wide variations in the quantity of this element within a family as, for example, among gray ferrughous soils on sandy material in Chad, where contents range from 100 to 300 p.p.m. on the one hand, and from 800 to 1,000 p.p.m. on the other. In Polynesia, ferrallitic soils on basalt contain from 640 to 1,500 p.p.m. of total manganese, whether they are more or less degraded and have an indurated subsoil or not. Hydromorphic and alluvial soils: contents range from 200-250 p.p.m. (low humic hydromorphic gley soils of Chad on clayey and sandy clay sediments, of Polynesia on alluvions of volcanic origin and of the Ivory Coast on schists) to 2,650-3,000 p.p.m. (hydromorphic gley and pseudo-gley soils on alluvions in Madagascar and the Central African Republic). Besides, in the alluvial soils of Chad on loamy clay sediments, contents range from 100--1,000 p.p.m. In India, on sandy, clayey and calcareous alluvions, contents are lower: 350-550 p.p.m. Slightly evolved deposit or erosion soils are often very rich in total manganese : 700-900 p.p.m. in New Caledonia on limestone-cemented

47

flysch, and 2,000 and 4,000 p.p.m. in Chad and the Central African Republic, on amphibole-gneiss and amphibolite. As has been shown, different factors, other than the parent rock, play an important part in determining total soil manganese contents: climatic factors and, in the diverse geographical zones, particularly the tropical zones, secondary pedogenic and biogenetic factors.

MANGANESE CONTENT OF SOILS “AVAILABLE” TO PLANTS

Numerous studies have shown that soil manganese exists principally in two forms: as the divalent cation Mn”, soluble, mobile, easily available, and as the tetravalent cation Mn4+,practically insoluble, non mobile and unavailable. Manganese Mn2+comprises:Water-soluble manganese, which exists in soils in the form of easily solubilized salts (carbonates, bicarbonates, sulphates . . .). Exchangeable manganese extractable by 1 N ammonium acetate, pH 7. It is fixed on the humicclay adsorbent complex. Manganese soluble in dilute acids (2.5%acetic acid, dilute sulphuric and hydrochloric acids) comprises the two preceding forms plus that corresponding t o salts easily soluble at a pH below 6. In well determined oxidation conditions, under the influence of oxygen of the air or soil solutions and in the presence of aerobic bacteria, manganese Mn” is turned into Mn4+.It then becomes MnO, .nH,O and the final oxidation product is the crystallized bioxide MnO, (pyrolusite). As MnO, .nH,O, manganese is easily reducible, particularly by hydroquinone and 2% hydroxylamine hydrochloride in ammonium acetate or else by sodium hydrosulphite, a stronger reducing agent. The trivalent cation Mn3’, as Mnz03 is very difficult to find in soils. It is not soluble in the reagents already mentioned but only in sodium pyrophosphate. According to some authors Mn203may be the first oxidation product of Mn2+ in a weakly alkaline medium (pH 6-7.5) and according to others, it may come from the dismutation of MnO-MnO,. To sum up, according to authors, soil concentrations of manganese “available” to plants are given in : water-soluble or dilute acid-soluble manganese, exchangeable manganese and easily reducible manganese. Soluble manganese and exchangeable manganese make up the “mobile” manganese. Russian authors consider the latter as acid-soluble manganese, particularly manganese soluble in 0.1 N sulphuric acid. The sum of soluble, exchangeable and reducible manganese corresponds to “active” manganese. Water-soluble manganese content is very low: in the soils of India (vertic, alluvial and saline alkali soils) contents range from traces to 3 p.p.m., which

48

represents less than 0.1% of total manganese. However, there is one exception: in the subdesert soils of the Ustyurt region of the U.S.S.R., contents range from 5 to 520 p.p.m., i.e. 7.5-74% of total manganese. This form of manganese is rapidly solubilized in the soil solution at a pH lower than 5, which can cause toxicity phenomena such as that observed in Congo Brazzaville. Exchangeable manganese content is higher: in temperate and boreal zones contents are average in brown forest soils of Poland and Bulgaria: 16-88 p.p.m., i.e. 1.5-13% of total manganese. Contents are high in podzols and podzolic soils: in Siberia, 100-460 p.p.m.; in Norway, in iron and humic-iron podzols, 74-113 p.p.m. i.e. 2564% of total manganese. In arid and semiarid regions, contents are also average in subdesert soils: in Uzbekistan, 7-50 p-p-m. (0.9-7.896 of total manganese); in vertic, saline and alluvial soils of India, contents range from 1 6 to 17.7 p.p.m. i.e. 0.119.5% of total manganese. In tropical zones, ferrallitic soils have average exchangeable manganese contents: Pakistan, 101 p.p.m.; India, 172 p-p-m.; and in Polynesia, 120 p.p.m., which corresponds to 20% of total manganese. Mobile manganese, as defined by authors of the U.S.S.R., often represents 40-50% of total manganese: in the brown forest soils of Bulgaria values of 40-50% of total manganese were determined, and in the podzolic soils of Bielorussia values of 18-68% of total manganese were found. Easily reducible manganese is often found in high concentrations:In Thuringia, Germany, the percentage ranges from 58 t o 75% in relation to total manganese. In India, in saline and alkaline soils of Rajasthan, concentrations vary from 4.6 t o 20.5 p.p.m., corresponding to 1.9-6.4% of total manganese. In different states of the same country, alluvial soils contain from 61 to 258 p.p.m., i.e. 16.6-37.5% of total manganese; vertisols contain from 90 to 730 p.p.m., i.e. 7.5-3076 of total manganese, and ferrallitic soils contain from 220 to 692 p.p.m., i.e. 24-3396 of total manganese. On the other hand, in the soils of Iowa (U.S.A.), the following concentrations were extracted by sodium hydrosulphite: 120 p.p.m. from the A2 horizon of fragipan meadow soils, 1,130 p.p.m. from the A2 horizon of leached soils and 1,250 p.p.m. from the A2 horizon of brown forest soils. Because of the very different values obtained for plant-available manganese when using different extraction reagents, i t is necessary to specify in what form the plant “available” manganese has been determined.

49

VARIATIONS OF THE MANGANESE CONTENT O F SOILS

Although the concentration of this element varies widely from one soil to another in the same group, some relationships can be stressed, however, between contents and some soil characteristics. In temperate and bored, semiarid and arid zones, an accumulation of manganese is observed in the humiferous upper horizons. This positive correlation with the humus and organic matter contents is valid for “available” as well as for total manganese. Manganese concentrations follow the distribution of humus along the profile. Thus, in the podzols of Norway (iron-humic and humic podzols), exchangeable manganese varies, respectively, from 112 ppm in the A, t o 1.5 p.p.m. in the A, horizon, in the one case, and from 74.8 p.p.m. t o 1.9 p.p.m. for the same horizons, in the other case. Similarly, in a brown forest soil on granite of the Amur region, a value of 3,100 p.p.m. was found in horizon A, and 770 p.p.m. in the A/B horizon. In soils with slightly differentiated profiles, the distribution is practically uniform between the different horizons: tundra soils and chemozems of the U.S.S.R. This frequent accumulation of different forms of manganese is, principally, of biogenetic origin: plants with deep roots draw the element from the subsoil and release it during the decomposition of their remains. This manganese is then fixed by organic matter and accumulates in the humiferous horizons (Vinogradov, 1959). Total manganese content varies also in relation t o soil texture: sandy soils are, generally, less rich in manganese than clayey soils. Thus in Dahomey, in gray fermginous and ferrallitic soils, the distribution of manganese along the profile follows that of clays: manganese content increases with depth (Pinta and Ollat, 1961). However, in India, it has been noticed that in different types of soil (ferrallitic, alluvial, desert, saline soils, etc.), on gneiss, sandstone, sands, aeolian deposits, containing more than 40% of clay, there is a negative relationship between the concentrations of manganese and those of clay in the surface horizon of soils. All works concerning the forms of manganese “available” to plants (soluble manganese, exchangeable manganese and easily reducible manganese) have shown a negative relationship between soil pH and the quantities found. That is t o say, the more alkaline the pH, the lower the contents. Above pH 7, as was shown previously, manganese is in very stable oxide forms, difficult t o solubilize with reagents usually employed. Thus, in Spain, on calcareous rocks, and in India, Punjab, manganese contents other than total manganese vary inversely to calcium carbonate; exchangeable manganese of saline alkali soils of the Punjab is very low, representing 0.3--0.7% of total manganese. Likewise, in strongly acid pH podzols, like those of Bielorussia, manganese of the upper horizons bound to

50

organic matter as complexes easily leached away, migrates toward the lower horizons where it is transformed into insoluble oxides. As previously mentioned, pedogenic, climatic (humidity, temperature, season of the year) factors, redox potential and cultivation conditions (virgin soils, soils cultivated with the help of the rain or by irrigation) play a large role in determining the contents of soil manganese “available” t o plants.


Manganese deficiency occurs principally in soils with an alkaline pH or on calcareous parent rocks, where manganese is immobilized as insoluble oxides, but it also occurs in strongly acidic soils where the acidity favours the leaching away of manganese,found there in a “very mobile” form, sometimes, however, insolubilized a t depth (podzols). Ryan e t al. (1967) cite different types of European soils most often deficient in total manganese (podzols, peaty soils, rendzinas, calcareous soils, soils on sands, etc.). Deficiency may also be caused by intensively supplying acidic soils with fertilizers containing lime ;manganese is then immobilized. In India workers have determined the deficiency limits in exchangeable and reducible manganese: 3 and 100 p.p.m., respectively. In hydromorphic pseudogley soils in the U.S.S.R., this limit is equal to 150 p.p.m. of “mobile” manganese (soluble in 0.1 N sulphuric acid). In France the problem of manganese deficiency plays an important part, particularly in the humiferous soils of Brittany. Coic and Coppenet (1949) have dealt with the conditions leading t o this deficiency. They showed that deficiency is found in extremely light humiferous soils, strongly acidic from the outset and very permeable because of their high content of organic matter, which have been supplied with large quantities of calcareous amendments. Deficiency symptoms appear above pH 6.5. It was found that in non-deficient wheat soils, ammonium acetateexchangeable manganese concentrations range from values of 0.97 t o 1.7 p.p.m. and hydroquinone-reducible manganese from 19 t o 30 p.p.m., a t pH 5.9+.7. On the contrary, in deficient wheat soils, the authors have found respectively 0.57-0.90 p.p.m. of exchangeable manganese and 14.2-27 p.p.m. of reducible manganese, a t pH 6.6. Their studies show that 1 p.p.m. is the minimum value of exchangeable manganese necessary for the normal development of wheat. Manganese sulphate sprayings cause general deficiency symptoms t o disappear. This confirms the conclusions found by workers in other regions of France. Toxicity is most often observed in acid soils (Ryan e t al., 1967). It is frequent in tropical humid soils with a pH below 5. In soils of the Niari valley, in Central Congo, Prevot e t al. (1955) and Franquin (1958) pointed out

51

manganese toxicities in cotton and peanuts. This toxicity results, very probably, from the destruction of organic complexes on which manganese is fixed. After many years of cultivation these soils became strongly acid, bringing about the liberation of high quantities of assimilable manganese. These workers noticed that in peanuts there is a negative correlation between manganese concentrations and those of other elements, such as potassium, calcium and magnesium. A case of manganese toxicity can also be cited for certain leguminous plants (cotton, soja and peanuts) in a ferrallitic soil of Madagascar (N Go Chan Bang e t al., 1971). These toxicities can be corrected either by enriching soils with organic matter (which increases the organic fixation of manganese and limits the lowering of the pH by a buffer action), or by raising the soil pH by liming.

CONCLUSION

The different soil types of the diverse climatic regions are generally rich and even sometimes very rich in total manganese; contents can attain 10,000 p.p.m. Accumulation of the different forms of manganese takes place, most of the time, in the upper humiferous horizons; it is essentially of biological origin. Manganese is more easily “mobilized” in acid pH soils than in neutral or alkaline pH soils. Manganese compounds found in soils depend on the pH and redox potential and these two factors depend on each other t o a certain extent. Soil deficiency in manganese “available” to plants is corrected by liming in strongly acidic soils and by fertilizers containing manganese in neutral and alkaline soils. Soil toxicity in manganese “available” to plants can be avoided also by controlled liming or by organic matter supply.

See also the following works published since 1968: SCOTLAND: Mitchell, R.L., 1974. BELGIUM: Nair, K.P.P. and Cottenie, A., 1 9 6 9 ; Nair, K.P.P. and Cottenie, A., 1971 GERMAN DEMOCRATIC REPUBLIC: Beer, K., 1968;Klemm, K., 196813. YUGOSLAVIA: JekiE, M. and SaviE, B., 1970/1971;SaviE, B. and JekiE, M., 1968.

52 POLAND: Boratynski, K., Roszyk, E. and Zietecka, M., 1 9 7 1 ; Ciesla, W., Kociaikowski, Z., 1 9 7 3 ; Czuba, R., Gaszek, K. and Wlodarczyk, Z., 1 9 7 4 a ; Dobrzanski, B. and Glinski, J., 1 9 7 0 ; Kociafkowski, Z. and Staszewski, T., 1 9 7 3 ; Staszewski, T. and Kociaikowski, Z., 1974. HUNGARY : Kereszteny, B., 1971. RUMANIA: Chiriac, A. and Bajescu, I., 1974. U.S.S.R.: Aslanov, N.N., Yatrudakis, S.M., Ablayeva, R.A. and Tashkuziyev, M.N., 1 9 7 3 ; Goletiani, D.G., 1 9 7 0 ; Kruglova, E.K. and Alieva, M.M., 1 9 7 3 ; Lukashev, K.L. and Petukhova, N.N., 1 9 7 1 ; Rudneva, E.N., Verigina, K.V. and Dobritskaya, Yu.I., 1 9 7 2 ; Shirokov, V.V. and Panasin, V.I., 1972: CYPRUS: Pagel, H. and Prasad, R.N., 1971. CANADA: Mallick, K.A., 1 9 7 2 ; R e i d , A.S.J. and Webster, G.R., 1969. U.S.A.: Bradford, G.R., Bair, F.L. and Hunsaker, V., 1 9 7 1 ; Dolar, S.G. and Keeney, D.R., 1 9 7 1 ; Follett, R.H. and Lindsay, W.L., 1 9 7 1 . CENTRAL AMERICA: Fassbender, H.W. and Roldan, J.A., 1973. BRAZIL: De Santana, C.J.L. and Igue, K., 1972. COLOMBIA: Castro, J.P. and Blasco, M.L., 1972, TROPICAL LATIN AMERICA: Cox, F.R., 1972. JAPAN : Higashi, T., 1973;Mizuno, N. and Kobayashi, S., 1971. NORTH VIETNAM: Glinski, J. and Cao Thai, V., 1971. INDIA: Agrawal, H.P. and Reddy,C.J., 1972;Badhe, N.N., Naphade, K.T. and Ballal, D.K., 1 9 7 1 ; Baser, B.L. and Saxena, S.N., 1 9 7 0 ; Lakshmanan, A.R., Bhavanisankaran, N., Rajenran, G. and Indira Raja, M., 1 9 7 2 ; Mishra, B. and Tripathi, B.R., 1972;Mohapatra, A.R. and Kibe, M.M., 1 9 7 2 ; Patel, M.S., Mehta, P.M. and Pandya, H.G., 1 9 7 2 ; Rao, P.S. and Hadimani, A S . , 1 9 7 1 ; Sharma, O.P. and Shinde, D.A., 1 9 6 8 ; Singh, M., 1 9 7 0 ; Singh, M., 1 9 7 1 ; Singh, M. and Pathak, A.N., 1 9 6 9 ; Singh, S. and Singh, L., 1969;SriVasta A.R., Dubey, R.R. and Sinha, H., 1 9 7 0 ; Takkar, P.N., 1 9 7 0 ; Takkar, P.N. and Bhumbla, D.R., 1 9 6 8 . PAKISTAN: Hussein, M.S., Mujib, M.A. and Rahman, S., 1969. ALGERIA : Lomov, S.P., 1973. CAMEROUN : NaloviE, L. and Pinta, M., 1972. TANZANIA: Kocialkowski, Z. and Dzieciolowski, W., 1972.

53

EGYPT: Abdel Salam, M.A., El-Demerdashe, S., Abdel-Aal, S.H.I. and Ibrahim, M.G., 1971; ElDamaty, A.H., Hamdi, H. and Orabi, A.A., 1971; El-Leboudi, A.E., El-Sherif, S. and Ismail, A., 1971; El-Mowelhi, N.M., Mitkees, A.I., Abouhussein, M.A. and Shabassy, A.I., 1973; El-Sherif, S., El-Laboud, A. and Metwally, S., 1970; Ghanem, I., Hassan, M.N., Khadr, M. and Tadros, V., 1971. ISRAEL: Yaalon, D.H., Jungreis, C. and Koyumdjisky, H., 1972. TROPICAL ZONES: Dobrzanski, B., Glinski, J. and Cao Thai, V., 1971.


55

MOLYBDENUM* Molybdenum is found in most rocks of the earth’s crust, generally in low concentrations. Molybdenum contents are low, 0.2-0.4 p.p.m., in ultrabasic rocks (dunite and peridotite), higher, 1.4 p.p.m., in basic eruptive rocks (basalt and gabbro) and still higher, 1.9 p.p.m., in acid eruptive rocks (granite). Metamorphic rocks (schists) and sedimentary rocks (clays) contain the highest molybdenum concentrations, about 2 p.p.m. Contents are often lower, 0.20.4 p.p.m., in sandstones and carbonated rocks. The average molybdenum content of the lithosphere is about 1-2 p.p.m. (Vinogradov, 1959; Turekian and Wedepohl, 1961; Kovda et al., 1964). In spite of much research work dealing with the distribution of molybdenum in soils, there are few data available concerning parent rock concentrations corresponding to the soils analyzed. The latest and most comprehensive data come from works carried out in different regions of the U.S.S.R., particularly in Bielorussia, on sedimentary rocks. These data show that ancient alluvial and fluvio-glacial sands and sandy loams have low molybdenum concentrations, containing from 0.28 to 0.90 p.p.m. Morainic clay loams and loessic loams are richer: 0.9-4.9 p.p.m., the concentrations varying in relation t o the texture of the materials. The highest molybdenum contents have been determined in the U.S.S.R. in clays: 2.8-3.7 p.p.m., and clayey schists: 4.5-5.7 p.p.m. Similar values, 3.3-5.7 p.p.m., were determined in a dolerite, in Tasmania, which makes it quite different from those studied in the U.S.S.R. by Vinogradov and Kovda et al. (see above).

TOTAL MOLYBDENUM CONTENT OF SOILS

Total soil molybdenum contents are relatively low. However, they are often higher than those of the parent rocks. In the soils studied, contents range from traces (different soil types of semiarid and tropical regions) to 24 p.p.m. (brown forest soils of the U.S.S.R.). The average concentrations range from 1t o 2 p.p.m. The variations seem to be due mainly to the types of soil which reflect the differences existing between the diverse climatic and geographical zones, and to some secondary processes of soil evolution. However, in a given type of soil, these variations reflect the relative richness of the parent rocks.

*See Tables, pp. 298-335

56

Temperate and boreal regions The upper and lower limits of molybdenum contents of the soils of these regions are 24 p.p.m. (brown forest soils of the U.S.S.R.) and 0.07 p.p.m. (slightly evolved erosion soils on Tertiary sediments of Spain), respectively. Contents are often lower than 1 p.p.m. The lowest contents are found in diverse soils, most often on sandy material, particularly in podzols or weakly podzolic leached soils. Thus, in acid soils (pH 5.1) of Wisconsin, U.S.A., and weakly podzolized leached soils of Latvia, on sandy material, concentrations range from 0.2 to 0.47 p.p.m. However, even in these podzols and weakly podzolized leached soils, concentrations may vary in relation to those of the parent rocks on which they were formed. Thus, in Scotland, contents are lower than 1 p.p.m. in podzols on granite and sandstone and equal t o 5 p.p.m. in this soil type on micaschists. Likewise, in Bielorussia, podzols and podzolic soils on loessic clays and fine sands have low total molybdenum contents (0.12-0.35 p.p.m.), whereas the same soils on fluvio-glacial sands are richer (0.2-1.9 p.p.m.) and those derived from loessic clayey loams, a material which is particularly rich in molybdenum (1.3-4.9 p.p.m.), have much higher concentrations: 2.2-4.8 p-p-m. In Australia, podzols on doleritic rocks also contain relatively high total molybdenum contents: 2.6-3.7 p.p.m. Brown forest soils have widely variable concentrations: in Bulgaria 0.32 p.p.m. (on granitic rocks) t o 4.5 p.p.m. (on gneiss and schists); in northeastern China 2.2 p.p.m. on basalt; and in Australia (Tasmania) 3.9-5.1 p.p.m. on dolerite. The highest contents were found in the brown forest soils of Kuban (U.S.S.R.), attaining a value of 24 p.p.m. Peaty soils are generally rich in total molybdenum: 4 p.p.m. in Italy: 1.54 and 7.5 p.p.m. in Bielorussia and Kuban, respectively. In Bulgaria, a value of 101 p.p.m., a quite exceptional concentration, was found in a peaty soil of the Varna region. More or less hydromorphic alluvial soils have variable total molybdenum contents, often lower than 1 p.p.m. Values range from 0.35 to 1 p.p.m. in a hydromorphic soil on schists in Scotland, and in hydromorphic pseudogley soils on schists in Bosnia, Yugoslavia. By contrast in Transural (U.S.S.R.), contents are high: 10 p.p.m. Rendzinas and calcareous brown soils generally have slightly higher than average concentrations: 0.5-2.9 p.p.m. in Bielorussia and Kuban; 3.5 p.p.m. on marl in Israel; 2 p.p.m. on limestone in Queensland; and from 5 to 7 p.p.m. in the Adelaide region. Much higher values have even been cited for the calcareous brown soils of eastern France.

57

Arid and semiarid regions The different types of soil in these regions generally have higher total molybdenum contents than those of temperate and boreal regions. Contents range, on an average, from 2 t o 5 p.p.m. Concentrations range from values of 0.5 to 3.3 p.p.m. in the chemozems of the southern Poland and the coastal plain; in the U.S.S.R. values range from 1 to 5 p.p.m. for the chemozems of Kuban on loessic clayey loams and for those of the Caucasus, whereas they attain 10 p.p.m. in chemozems and 20 p.p.m. in a leached brunizem in the region east of the Urals. Isohumic brown soils are generally rich in total molybdenum. In Israel on different parent rocks (calcareous sandstone, alluvions and aeolian deposits) and in Queensland on clayey sediments, values of 4.6-6 p.p.m. and 3-12 p.p.m., respectively, of total molybdenum were determined. Vertisols have variable total molybdenum contents. In the Central African Republic, hydromorphic lithomorphic vertisols on amphibolite contain from traces to 6 p.p.m. Likewise, in New Caledonia, topomorphic vertisols on limestone-cemented flysch contain low concentrations, from traces to 1 p.p.m. However, in Gurajat, India, contents vary from 1.2 to 4 p.p.m. in vertic soils and vertisols on sediments derived from basalts and on alluvions derived from lava and limestone. Concentrations are about the same, 2.53.5 p.p.m., on dolerite in Tasmania (Australia). Subdesert and saline soils often have concentrations higher than 2 p.p.m. Thus, in Uzbekistan, subdesert soils formed on loessic clayey loams, and saline alkali soils contain from 2.6 t o 4.5 p.p.m.; in Azerbaidzhan the content reaches 8 p.p.m. in the humiferous horizons of these soils. The upper and lower limits are the same as those cited above for the solods of Queensland on granitic rocks and alluvions. However, in New Caledonia, solods on limestone-cemented flysch are poor in molybdenum : traces-1 p.p.m. Values determined in mediterranean red soils of Australia and of Israel vary from 2 to 8.5 p.p.m.

Tropical hum id regions The upper and lower limits of total molybdenum contents of the soils of these zones are about the same as those of the climatic zones cited above: from traces t o 17 p.p.m. Gray femginous soils often have concentrations lower than 1 p.p.m. In Mali, contents range from values of 0.50 to 0.75 p.p.m.; in Chad, on sandy clay material, and in the Central African Republic, on granite and gneiss contents range from traces to 1 p.p.m. However, in Madagadcar, gray ferruginous soils, on limestone or schists, contain from 2.6 to 9 p.p.m. of total molybdenum.

58

Ferrallitic soils have variable total molybdenum contents: these soils in Dahomey and the Central African Republic are poor in total molybdenum: traces-3 p.p.m. In Queensland, humiferous ferrallitic soils on igneous rocks and alluvions and, in Tasmania and Queensland, krasnozems on granodiorite and basalt or dolerite are rich: 3.3-6.9 p.p.m. In Madagascar, the highest contents were determined in ferrallitic soils on granite (14 p.p.m.) and on cipolin (17 p.p.m.). In some ferrallitic soils, total molybdenum concentrations seem to be linked t o various secondary processes of soil evolution: more or less marked evolution of the soils, degree of leaching and lexiviation, degree of hydration, etc. Thus, in the Ivory Coast, less total molybdenum (0.5 p.p.m.) was found in the leached or impoverished yellow ferrallitic soils on schists than in the red soils of the same type (1.5-2.5 p.p.m.). In Polynesia also, ferrallitic soils on basalt and andesitic basalts, contain from traces t o 2 p.p.m., depending on whether or not these soils are degraded. Total molybdenum contents are variable for hydromorphic and slightly evolved soils of these regions. A value of 2 p.p.m. of molybdenum was found in a humic-gley soil of Polynesia. In Uttar-Pradesh and Gujarat, India, contents of slightly humiferous hydromorphic soils on alluvions of basaltic debris range from values of 0.4 to 3.1 p-p-m. However, in the Central African Republic, in the same type of soils, on material varying from clayey sand t o sandy clay, molybdenum contents range from traces to 3 p.p.m. In the same country, too, slightly evolved erosion soils on amphibolite contain only traces-1 p.p.m. of total molybdenum, whereas on itabirite, they are much richer: 4-5 p.p.m. In the New Hebrides and Chad, slightly evolved deposit soils on acid pumices are rich in this element: 3 p.p.m., but in Madagascar, flood terrace and alluvial bank soils are poor: traces-2 p.p.m., as are soils on colluvia of limestone-cemented flysch, in New Caledonia: traces--1 p.p.m.

MOLYBDENUM CONTENT OF SOILS “AVAILABLE” TO PLANTS

Molybdenum plays a very important biochemical role in plants. It intervenes in the nitrogen cycle, making easier the reduction of NO, t o N, and leguminous plants accumulate it in their nodules (Evans, 1956). A molybdenum soil deficiency or toxicity causes plant and animal diseases. That is why it is very important to know, besides the total molybdenum soil contents, the plant-available molybdenum soil contents. According to various authors, this form of molybdenum is extracted by different reagents such as: 1N ammonium acetate or oxalate, pH 7 2.5% acetic acid, pH 2.5

59

an oxalic acid-ammonium oxalate buffer solution, pH 3.3 (Grigg’s reagent ) The above are all weak reagents and extract only the molybdenum fraction easily solubilized. A number of workers also use biological methods, such as the Aspergillus niger method, to obtain an estimation of this form of molybdenum in soils. In the soils studied, the concentrations of plant-available molybdenum are rarely higher than 1 p.p.m. There is a positive relationship between total molybdenum soil contents and “available” molybdenum: soils richest in “available” molybdenum are generally those having high total molybdenum contents. Soils containing the lowest “available” molybdenum contents (0.01-0.1 p.p.m.) are found in diverse climatic zones, for example: podzols and podzolic soils in Scotland and the U.S.S.R.: 0.015-0.053 p.p.m. and 0.09 p.p.m. ; certain chemozems of Bulgaria: 0.06-0.10 p.p.m.; slightly evolved soils on alluvions of Gujarat, India: 0.04-0.13 p.p.m.; most tropical soils, such as the gray ferruginous soils of Mali and ferrallitic soils of the Ivory Coast: 0.02-U.06 p.p.m. and 0.02-0.11 p.p.m. Higher contents of “available” molybdenum (0.1-1 p.p.m.) were found, particularly, in the peaty soils of Italy and rendzinas of Israel: 0.8 p.p.m.; in hydromorphic soils of the U.S.S.R. and Yugoslavia: 0.10-1.23 p.p.m.; in the brown isohumic and saline soils of Israel and the U.S.S.R.: 0 . 1 4 . 6 p.p.m.; and in saline alluvial soils of India: 0.15-1.38 p.p.m. Some brown forest soils of the U.S.S.R. and mediterranean red soils of Israel contain up to 24 p.p.m. Moreover, rather exceptional contents of 1 2 and 27 p.p.m. of “available” molybdenum have been determined, respectively, in a leached brunizem in Transural (U.S.S.R.) and in lithosols on black clay in the U.S.A. (Kentucky). For the entire group of soils studied, plant-available molybdenum represents on an average 2-20% of total molybdenum. This is the case for the more or less leached yellow ferrallitic, reddish-brown and red soils of the Ivory Coast. In Italy, “available” molybdenum represents 9% of total molybdenum in the slightly evolved soils on alluvions and 20% in peaty soils. In the U.S.S.R., the percentage varies from 7 t o 15% in podzolic soils and podzols and is about 20% in peaty soils. Percentages are higher in the hydromorphic soils of Yugoslavia and Israel, from 27 to 31% and 35.8%,respectively. They reach 59% in the podzols of Bielorussia and 50 and 65% in some saline alkali soils on alluvions in Uttar-Pradesh, India.

VARIATIONS O F THE MOLYBDENUM CONTENT O F SOILS

If one studies the distribution of molybdenum between the different horizons of soil profiles, i t is generally noticed that there is an accumulation

60

of this element in the upper horizons and, in particular, the humiferous horizons. Molybdenum is fixed by organic matter and humus, and its content varies in relation to humus content. That is why distribution in chernozems is uniform all along the profile. In podzols and podzolic soils an accumulation occurs in the B illuvial horizon. In this horizon molybdenum is fixed by iron and aluminium oxides, and its content increases at the same rate as those of hydrates. Molybdenum content also varies with soil texture. Clayey soils are richer in this element than sandy soils, and the distribution of molybdenum along the profile follows that of clayey materials. This is particularly distinct in certain tropical soils in Dahomey and the Ivory Coast (Pinta and Ollat, 1961; Riandey, 1964). The influence of parent rocks on soil molybdenum contents has already been demonstrated: soils developed on acid parent rocks can have higher molybdenum contents than those developed on basic parent rocks. The effects of soil cultivation and rainfall play an important part in determining “available” molybdenum : “available” molybdenum decreases when rainfall is heavy, and virgin soils are often richer in this form of molybdenum than cultivated soils. However, in some podzols molybdenum seems to accumulate during the cultivation period. Plant-available molybdenum also varies in relation to soil pH: the more alkaline the pH, the higher the percentage of “available” molybdenum. In acid pH soils, molybdenum is strongly fixed by iron and aluminium hydrates, phosphates and clays.


Many factors play a part in causing molybdenum deficiency, pH being one of the most important (Davies, 1956). Deficiency is most frequently found in acid and strongly acid soils which contain molybdenum in the form of very slightly soluble compounds: podzols, podzolic soils and iron pan soils. Coarse-textured soils and certain alluvial soils can be deficient in molybdenum, as well as soils with a low humus content (tropical soils). In France, serious molybdenum deficiencies have been found in fersiallitic soils of the “Costi6re du Gard”, in decalcified soils of the Crau, in the counterfort of the Vaucluse plateau and in detritus soils (pH 7) without limestone. Exchangeable molybdenum values of 0.10-0.14 p.p.m. were found in the soils of the “CostiGre du Gard” and 0.28 p.p.m. in the soils of Vaucluse. Deficiency is corrected by liming, which has an effect on the pH, and by supplying fertilizers containing molybdenum, principally in the form of

61

pulverized sodium molybdate; harvests are then notably improved (Gouny and Cornillon, 1970). Toxicity is often found in heavy-textured soils formed on calcareous material, marine sediments or clayey schists; it is also found in peaty and certain gley soils (Ryan e t al., 1967).

CONCLUSION

Molybdenum, an element indispensable for plants and animals, is found in soils in concentrations ranging from traces to 20 p.p.m. Soils with a high humus content and soils of semiarid zones generally contain the highest concentrations of this element. Certain pedogenic processes cause the accumulation of molybdenum in soils and seem to play a more important part than parent rocks in determining the total molybdenum contents. The plant-available molybdenum content of soils ranges from values of 0.01 to 1 2 p.p.m. Soil pH plays an important part in determining plant-available molybdenum contents. Molybdenum deficiency is found in acid pH and coarse-textured soils. Deficiency is corrected by fertilizers containing molybdenum and by liming. Toxicity is corrected by acid amendments.

See also the following works published since 1968: IRELAND: Brogan, J.C., Fleming, G.A. and Byrne, J.E., 1973. SCOTLAND: Mitchell, R.L., 1974. ENGLAND : Thomson, I., Thornton, I. and Webb, J.S., 1972. SPAIN: Barragan-Landa, E. and Herrero, J.I., 1973. GERMAN DEMOCRATIC REPUBLIC : Klemm, K., 1970. POLAND: Andruszczak, E. and Debowski, M., 1971; Boratyiiski, K., Roszyk, E. and Zietecka, M., 1972; CieSla, W. and Kociantowski, Z., 1973; Czarnowska, K., 1968; Czuba, R., Gaszek, K. and Wlodarczyk, Z., 1974a; Czuba, R., Dudziak, S . and Malinska, H., 1974b; Dziqciolowski, W. and Kociantowski, Z., 1973; Gorlach, E., Compala, A. and Wojtas, R., 1970; Kocialkowski, Z. and Staszewski, T., 1973;Sadowski, S. and Dunat, S., 1968. HUNGARY: Kereszteny, B., 1968; Kereszteny, B., 1973.

62 U.S.S.R.: Daerbaev, A.A., 1973;Gorbacheva, A.E., 1971;Grabarov, P.G., 1970;K rym, I.Ya., 1 9 7 1 ; Sharova, AS., Sklyarov, G.A. and Arte M’eva, K.A., 1970;Shirokov, V.V. and Panasin, V.I., 1 9 7 2 ; Tonkonozhenko, E.V., 1970; Zborishchuk, Yu.N. and Zyrin, N.G., 1974. CYPRUS: Pagel, H. and Prasad, R.N., 1971. CANADA: Cheng, B.T. and Ouellette, G.J., 1973. U.S.A.: Bradford, G.R., Bair, F.L. and Hunsaker, V., 1971. BRAZIL: De Santana, C.J.L. and Igue, K., 1972. TROPICAL LATIN AMERICA: Cox, F.R., 1972. JAPAN: Mizuno, N. and Kobayashi, S., 1971. NORTH VIETNAM: Glinski, J . and Cao Thai, V., 1971. INDIA: Balaguru, T. and Mosi, A.D., 1 9 7 3 ; Misra, S.G. and Misra, K.C., 1 9 7 2 ; Rai, M.M., Pal, A.R., Chimania, B.P., Shitoley, D.B. and Vakil, P., 1972c ; Rai, M.M., Pal, A.R. and Shitoley, D.B., 1 9 7 2 b ; Rai, M.M., Shitoley, D.B., Pal, A.R., Vakil, P. and Gupta, S.K., 1970;Verma, K.P. and Jha, K.K., 1970. TANZANIA: Kociafiowski, Z. and Dziqciolowski, W., 1972.

63

NICKEL* Most rocks of the earth’s crust contain nickel, the contents varying with the type of rock. Thus, nickel contents are highest in ultrabasic rocks (dunite, peridotite.. .) and in the products of their metamorphism (particularly serpentinite) : 1,200-2,000 p.p.m. and 500 p.p.m., respectively. In some cases where these rocks have produced nickel ores, such as certain dunites, the values obtained are even higher and exceed 3,000 p.p.m. (New Caledonia). Contents are high in basic eruptive rocks (basalt, gabbro.. .) and relatively low in acid eruptive rocks (granite): 150 p.p.m. and 5-10 p.p.m., respectively. Metamorphic and sedimentary rocks contain average contents: certain complex sandstones contain 90 p.p.m., loams and clays contain from 90 to 100 p.p.m. and loessic loams from 20 to 30 p.p.m. Calcareous rocks are less rich in this element: 10-20 p.p.m., as also are certain quartz-like rocks whose contents can be as low as 2 p.p.m. The average nickel concentration of the lithosphere is about 100 p.p.m. (Vinogradov, 1959; Turekian and Wedepohl, 1961; Kovda et al., 1964). Recent bibliographical data concerning the nickel content of rocks confirm these average values: in Tasmania (Australia) in dolerite, nickel ranges from values of 8 t o 140 p.p.m. (average 50 p.p.m.); in Bielorussia (U.S.S.R.), contents vary from 20 to 40 p.p.m. in loessic clayey loams and lacustrine glacial clays; in the Amur region (U.S.S.R.) granites contain less than 5 p.p.m. and very ancient sandy alluvions about 1 2 p.p.m. On the contrary, in the Kola peninsula, crystalline schists with norite intrusions are very rich: 300 p.p.m. for the schists and 85 p.p.m. for the clayey moraine which covers them.

TOTAL NICKEL CONTENT OF SOILS

Soil total nickel contents vary within wide limits. The upper and lower limits range from unanalyzable traces (in different soil types of diverse climatic regions) to 5,000 p.p.m. (B2 horizon of a brown podzolic soil in Scotland). The latter concentration is often exceeded in nickel ores which are only indurated pedologic horizons, as in certain regions of New Caledonia. These variations occur, on the one hand, in relation to the rocks on which the soils were formed and, on the other hand, in relation to the diverse types of soils, and, consequently, to a certain extent, in relation to the major climatic and ecological zones. *See Tables, pp. 336-349.

64

Temperate and boreal regions

Total nickel contents of the soils of these regions range from traces to 500 p.p.m. The average content is about 20-30 p.p.m. Slightly evolved soils on sandy material, peaty soils, podzols and leached podzolic soils often contain the lowest nickel contents: in the U.S.S.R. soils on fluvio-glacial or ancient alluvial sands in the lower Volga valley and slightly podzolic leached soils in Bielorussia contain from traces t o 20 p.p.m. of nickel; soils on Quaternary marine sands are richer, containing from 7 to 30 p.p.m. In the Olt region of Rumania, podzols are poor in total nickel: only 2.7 p.p.m. were determined. The influence of the nickel content of the parent rock on that of soils is particularly obvious within these types of soils. Thus in Scotland, contents are low in hydromorphic podzols with iron pan and A. peaty horizon, on granite or sandstone: 4 and 8 p.p.m.; contents are high in the same type of soil on granito-gneiss and micaschists: 40-80 p.p.m., and a brown podzolic soil on serpentinite is particularly rich: 600 p.p.m. in the surface horizon and 500 p.p.m. in the B2 horizon. Likewise, in the U.S.S.R., in the Kola peninsula, slightly podzolic leached soils derived from crystalline schists, a material very rich in nickel, have nickel concentrations much higher than average: 300 p.p.m. in the A. horizon. In these regions other types of soils have average contents:Brown forest soils: in the Amur region (U.S.S.R.) on lacustrine alluvions and in Scotland on andesitic moraine, these soils contain from 18 to 25 p.p.m.; in northeastern China on basalt and in Tasmania (Australia) on dolerite, contents are higher: 20-51 p.p.m. Rendzinas contain about the same concentrations: in the southeast and Adelaide region of Australia, contents vary from 1 2 t o 38 p.p.m., and in Madagascar on gritty limestone, a value of 59 p.p.m. was determined. Hydromorphic meadow soils have average or high total nickel contents: in the Amur region on stratified plain deposits these soils contain from 25 to 42 p.p.m., and along the Moskva banks they contain 70-110 p.p.m. Arid and semiarid regions

Soils of these climatic zones have total nickel contents generally higher than those of the soils of temperate and boreal regions. Contents range from values of 5 t o 300 p.p.m., and the average content is about 50 p.p.m. In Rumania and the Amur region on lacustrine alluvions, chernozems contain from 17 to 30 p.p.m. and 50 p.p.m., respectively. However, in the UralSakmara basin of the U.S.S.R., on serpentinite deluvium, contents attain 133 p.p.m. Vertisols have variable concentrations, but often equal to or higher than

65

average: in New Caledonia in a vertisol on limestone-cemented flysch, and in Tasmania on dolerite, 24 and 30 p.p.m. of total nickel were found, respectively. In India and Madagascar on marls and basalts, and in Chad on sandy clay sediments, vertisols contain from 30 to 90 p.p.m. Concentrations are higher in Madagascar in this type of soil formed on alluvions: 115 p.p.m., and in the Central African Republic in lithomorphic vertisols on amphibolite, values of 60-300 p.p.m. were found. Saline soils (solonetses and saline alkali soils) contain about the same concentrations: in Australia and in New Caledonia, on limestone-cemented flysch, solods contain from 1 to 20 p.p.m. of total nickel. In the Or-Kumak basin on decayed basic rock crust, in Turkmenistan, and in Chad on clayey sediments, solonet,ses and saline alkali soils are richer, containing 50-75 p.p.m., 40-100 p.p.m. and 10-50 p.p.m., respectively. In Australia the nickel contents of red mediterranean soils vary from 5 to 54 p.p.m.

Tropica 1 h urnid regions The upper and lower limits of total nickel contents of the soils of these regions are about the same as those of other climatic regions: 500 p.p.m. (in the alluvial soils on volcanic alluvions in Polynesia) and even more in certain parts of New Caledonia, and traces (in the hydromorphic humocarbonated soils on limestone-cemented flysch in New Caledonia). The influence of the nickel content of the parent rock is very marked in tropical soils. Thus in Ghana, slightly t o moderately desaturated ferrallitic soils have total nickel contents which vary with the parent rock: 10-20 p.p.m. on granite, 25-50 p.p.m. on phyllite and 100 p.p.m. on material derived from basic rocks. The same variations can be found in Madagascar, in ferrallitic soils on different parent rocks: on granite, basalts, cipolin, these soils contain 26 p.p.m., 85 p.p.m., and up t o 230 p.p.m., respectively, and on gneiss up t o 250 p.p.m. This is also the case with gray ferruginous soils. In Madagascar soils derived from basalt are richer than those derived from sandstone: 60 and 20 p.p.m., respectively . Contents are often very high in the krasnozems of Australia: in Tasmania on dolerite, 100 p.p.m. and in Queensland on the same parent rock, from 290 to 300 p.p.m. It has also been noticed that, in a given region, for the same type of soil on the same parent rock, concentrations may vary widely. Thus in the Central African Republic, ferrallitic soils contain on: migmatite: 2-10 p.p.m. and 300 p.p.m. gneiss: 3-15 p.p.m. and 60-100 p.p.m. amphibolite: 25 p.p.m. and 60-100 p.p.m.

66

Gray ferruginous soils also show important differences: these soils on gneiss and amphibolite, according to the location, contain from 1 0 to 60 p.p.m. in some cases, and 100-300 p.p.m. in others, no matter what the rock was. These differences could be due to secondary evolution processes: extent of weathering of the parent rock, leaching, more or less accentuated lixiviation or impoverishment of the soil, etc. Thus in Polynesia, ferrallitic soils formed on basalts and on andesitic basalts, contain from 15 to 25 p.p.m. and from 100 to 290 p.p.m. of nickel, respectively, whether they are very degraded or not. More or less hydromorphic alluvial soils generally have average nickel contents. In the Central African Republic on alluvions, in Chad on sandy clay sediments and in Madagascar on alluvions, hydromorphic gley or pseudogley soils contain from 20 t o 30 p.p.m. and from 45 t o 60 p.p.m. of total nickel. In the Ivory Coast, hydromorphic pseudogley soils on schists have concentrations ranging from 5 to 50 p.p.m., but in Polynesia, total nickel contents can attain 500 p.p.m. in the hydromorphic gley soils on alluvions of volcanic origin. In slightly evolved deposit or erosion soils, total nickel contents vary widely. They are relatively low in Chad, in soils on gneiss: 1 0 p.p.m.; they are average in the Central African Republic in slightly evolved erosion soils on amphibolite: 25-30 p.p.m.; and in the New Hebrides, in slightly evolved deposit soils derived from acid pumices covering basic slags: 1 0 - 9 0 p.p.m. However, contents are high in Madagascar, in flood terrace and alluvial bank soils, on sandy loams and sandy clay sediments: 178 and 120 p.p.m.

NICKEL CONTENT OF SOILS “AVAILABLE” TO PLANTS

Nickel “available” t o plants has rarely been studied, and the extraction reagents vary from one author t o another: 2.5% acetic acid and 1 N hydrochloric acid are the two reagents used in Scotland and the U.S.S.R., respectively. The quantity of nickel extracted by 2.5% acetic acid, a relatively weak reagent, represents about 2% of total nickel. In Scotland, concentrations range from 0.09 p.p.m. in an iron pan hydromorphic podzol on granite, t o 1-4 p.p.m. in a brown podzolic soil on serpentinite very rich in total nickel. The percentage of nickel extracted by 1 N hydrochloric acid is higher: from slightly podzolic leached soils and peaty soils of the Kola peninsula (U.S.S.R.) 7-20% of total nickel (2.1-60 p.p.m.) and 9-40% of total nickel (4.2-4.9 p.p.m.) were extracted, respectively. Chestnut soils, saline alkali soils and solonetses of the Or-Kumak basin also have relatively high concentrations of “available” nickel: 14 and 9.8 p.p.m. in the upper horizons, i.e., 13-1876 of total nickel.

67 VARIATIONS OF THE NICKEL CONTENT OF SOILS

The distribution of nickel between the different horizons of soil profiles follows that of humus and organic matter. Generally there is an accumulation of nickel in the upper horizons. Thus, in Polynesia, in slightly evolved stony brown soils, a value of 25 p.p.m. of total nickel was found in the upper horizons if they were slightly humiferous, and 250 p.p.m. if they were very rich in humus. Nickel is uniformly distributed in the chernozems all along the profiles, as is organic matter. In podzols and podzolic soils, concentrations are higher in the B illuvial horizons which are rich in humus. Contents are also rather high in the low-humic but clayey gley horizons of hydromorphic soils, for they vary in relation t o soil texture: clayey soils are richer in nickel than sandy soils. (Pasternack and Glinski, 1969). Clays fix nickel and, in tropical soils (ferrallitic soils of Dahomey, Ivory Coast and Australia), there is an increase in nickel content with depth at the same time as an increase in clay content. There also may be an accumulation of nickel in certain horizons very rich in iron or aluminium sesquioxides. The importance of the role of the nickel content of parent rocks in soil nickel content has already been shown.

NICKEL TOXICITY

Some cases of nickel toxicity have been pointed out, particularly in the brown podzolic soils, hydromorphic gley soils on serpentinite and schists in Scotland (Ryan e t al., 1967), and in some ferrallitic soils on ultrabasic rocks in New Caledonia.

CONCLUSION

Nickel is found in different concentrations in all types of soils of the diverse climatic regions of the globe. Contents range from traces to 500 p.p.m. Soils of arid and semiarid regions often have higher concentrations than soils of temperate and tropical regions. Nickel contents of soils vary chiefly in relation to those of parent rocks, but other factors also intervene in the distribution of this element, such as soil type, degree of evolution, fine fraction and metallic sesquioxide contents and, above all, humus content, nickel being essentially a biogenic accumulation element. Soils richest in nickel are often derived from basic rocks and contain high concentrations of humus.

68

See also the following works published since 1968: BELGIUM : Nair, K.P. and Cottenie, A., 1 9 6 9 ; Nair, K.P. and Cottenie, A., 1971. POLAND: Boratyfiski, K., Roszyk, E. and Zietecka, M., 1 9 7 2; Dobrzanski, B. and Gliiiski, J., 1 9 7 0 ; Dobrzanski, B., Gliiiski, J. and Cao Thai, V., 1 9 7 1 ; Gliiiski, J. and Magierski, J., 1971. U.S.S.R.: Lukashev, K.I. and Petukhova, N.N., 1971. U.S.A.: Bradford, G.R., Bair, F.L. and Hunsaker, V., 1 9 7 1 ; Kilpatrick, B.E., 1969. JAPAN : Higashi, T., 1973;Mizuno, N. and Kobayashi, S., 1971. AUSTRALIA: Anderson, A.J., Meyer, D.R. and Mayer, F.K., 1973. NEW ZEALAND: Lyon, G.L., Brooks, R.R. and Peterson, P.J., 1970. INDIA: Misra, S.G. and Pande, P., 1972. CAMEROUN: NaloviE, Lj. and Pinta, M., 1972.

69

SELENIUM* Selenium is an element not widely distributed in rocks. It is mostly found as an impurity in sulphide rocks. Vinogradov (1959) cites only one value: 0.5 p.p.m. in eruptive rocks, whether acid or basic. In metamorphic and sedimentary rocks (clays), the average content is slightly higher (about 0.6 p.p.m.) with the exception of carbonated rocks where i t attains 0.8 p-p-m. (Turekian and Wedepohl, 1961). The average content of the earth’s crust is about 0.8 p.p.m. However, in various regions of the globe, particularly in the U.S.A., rocks whose selenium contents are relatively high are found. Most of these rocks are schists and ancient clays. According to Vinogradov (1959), the enrichment of these rocks in selenium might have been due to the fixation of this element by Fe(OH), during the formation of these rocks in the Secondary era, either directly from the sea where they formed deposits, or indirectly from sulphide and other emissions rich in selenium, abundant in this geological period. A large number of analyses showed that the pyrites and limonites in these schists can contain up t o 200 p.p.m. of selenium. The following bibliographical data, concerning the selenium content in rocks confirm the above values:In New Zealand, the average content is about 0.4 p.p.m. In England and Wales, values ranging from 2 to 24 p.p.m. were determined in schists emanating from the metamorphism of marine deposits, 4.5-6.5 p.p.m. in black pyritic slates and 2.5--6 p.p.m. in pyritic schists.

TOTAL SELENIUM CONTENT OF SOILS

Total selenium content of soils depends essentially on the content of the parent rocks. Most of the time the content is very low: the average concentration in the soils of the U.S.S.R., according t o Vinogradov (1959), is about 0.01 p.p.m. Swaine (1955) collected a large number of analytical results mostly coming from the U.S.A. and countries bordering the Pacific Ocean. Thus, in Japan, in soils derived from alluvions, contents are between 0.4 and 0.9 p.p.m. on the surface, and between 0.8 and 1.2 p.p.m. at depth. In Mexico, the average concentration ranges from 0.4 to 3.5 p.p.m. on the surface and from 0.03 to 2.1 p.p.m. at depth. In New Zealand, on rocks having average concentrations of the order of 0.4 p.p.m., a value of 0.6 p.p.m. was determined in the A horizon and a value of 1.4 p.p.m. in the B horizon. In regions where parent rocks are very rich in selenium, soils also have *See Tables, pp. 350-351.

70

high contents of this element, which is the case for certain soils of Canada or the U.S.A. In Canada (Manitoba, Alberta, Saskatchewan), values ranging from 0.1 t o 6 p.p.m. of selenium were determined. In the U.S.A. (central and western States), the average concentration found is between 1 and 7 p.p.m. In Puerto Rico, in clayey loam soils on schists, contents vary, on the surface from 2 to 10 p.p.m. and at depth from 3 to 12 p.p.m. In England and Ireland, one also finds soils rich in selenium. In England and Wales, poorly drained soils formed on marine schists coming from the metamorphism of marine muds contain from 1.5 to 7 p.p.m. and soils, also poorly drained, on pyritic schists, 0.2-4 p.p.m. In Ireland, soils were formed on glacial lake deposits: selenium concentrations are between 0.3 and 1.9 p.p.m. in the mineral soils and between 2.5 and 3.7 p.p.m. in organic soils. Values ranging from 360 t o 1,200 p.p.m., quite exceptional contents, have been found in the horizons 0-15 cm and 15-30 cm of a peaty soil.

VARIATIONS OF THE SELENIUM CONTENT OF SOILS

This study has previously shown the major influence of the parent rock on soil selenium contents, but a number of soil characteristics also play a part in influencing the concentration. Selenium contents vary in relation to organic matter and humus contents: in Ireland organic peaty soils are richer than mineral soils, and the highest concentrations are found in horizons in which the organic matter is only partially decomposed. Contents also vary in relation to soil texture. Heavy soils are richer than light soils (Gardiner and Gorman, 1963). Contents often increase with depth, particularly in the clayey accumulation horizons, that is t o say, if selenium is found there (Wells, 1967). The influence of topography can also be noticed: in Ireland (Fleming, 1962), the highest selenium concentrations have been generally extracted from the poorly drained lowlands, where are found soils of the humic gley type. On the other hand, contents vary inversely to the amount of rainfall: in arid and semiarid regions, selenium increases when the rainfall decreases (Gardiner and Gorman, 1963).

DEFICIENCY OR TOXICITY OF SELENIUM

Seleniferous soils have been extensively studied because of the serious consequences of abnormal selenium contents on vegetation and, consequently, on animals.

71

As a matter of fact, natural (leguminous plants, 'compositae.. .) and cultivated (cereals) vegetation, adapts itself to the particular conditions of seleniferous soils. Plants accumulate this element and consequently become toxic for livestock. Workers have mostly dealt with the conditions under which toxicity appears. In Australia (MacCray and Hurwood, 1963),certain pasture varieties were used as test plants: the development of livestock is normal for selenium values ranging from 20 t o 50 p.p.m., the soils do not contain excessive contents; above a value of 50 p.p.m. the livestock is poisoned. Moreover, these studies showed the selenium concentration necessary for the normal development of livestock: in New Zealand (Watkinson, 1962), the supply of this element favours the development of lambs if the soils contain less than 0.45 p.p.m. These animals may even suffer from a deficiency disease. According t o the investigations of Gardiner et al. (1962), in Australia, deficiency occurs when the selenium content of the pastures goes below 0.03 p.p.m. Similar observations have been made in Sweden and the U.S.A. In certain regions of central France, diseases due to selenium deficiency seem t o be bound to its content in hay (about 0.01-0.04 p.p.m.) (Perigaud, 1970).

CONCLUSION

Although selenium is usually rare in soils (average content: 0.01 p.p.m. in the soils of U.S.S.R.), very high contents are found in certain fairly humiferous soils formed from schists and marine clays, or in certain peats. Vegetation can accumulate it and become toxic for livestock. On the other hand, selenium is necessary in small quantities for the normal development of livestock.

See also the following works published since 1968: SWEDEN: Lindberg, P. and Bingefors, S., 1970. BULGARIA: Stoyanov, D. and Stefanova, V., 1969. CANADA: Levesque, M., 1974. U.S.A.: Lakin, H.W., 1 9 7 0 ; Oldfield, J.E., 1970. INDIA: Misra, S.G. and Tripathi, N., 1 9 7 1 ; Misra, S.G. and Tripathi, N., 1972; Patel, C.A. and Metha, B.V., 1970. UGANDA: Long, M.I.E. and Marshall, B., 1973.


73

TITANIUM* Titanium is not a trace element by nature. As a matter of fact it is found in high concentrations in most rocks of the earth’s crust. However, these concentrations vary with the type of rock. Titanium contents are highest in basic eruptive rocks (basalt, gabbro.. .): 3,900-37,900 p.p.m. (average 13,000 p.p.m.). Titanium contents are lower in acid eruptive rocks (granite, rhyolite.. .): 400-5,400 p.p.m. (average 2,000p.p.m.). Metamorphic rocks (schists) and certain sedimentary rocks (clays and loams) contain average contents: loams have values ranging from 1,300 to 8,000 p.p.m. (average 2,800 p.p.m.) and clays from 400 to 6,600 p.p.m. (average 3,200 p.p.m.). The lowest values are found in sands: 70-3,000 p.p.m. (average 1,100 p.p .m. ) . The average concentration of the lithosphere is about 6,000 p.p.m. (Kovda et al., 1964). A limited number of analytical results, concerning titanium content of parent rocks and coming from the U.S.S.R., such as those cited above, confirm these data. Thus, in Bielorussia, the following values were found in:Ancient alluvial and fluvio-glacial sands : 860 p.p.m. Morainic clay loams : 3,800 p.p.m. : 4,400 p.p.m. Loessial and loess-like clay loams Lacustrine glacial clays : 4,600 p.p.m. TOTAL TITANIUM CONTENT OF SOILS

For nearly a century, the soil titanium content of the different regions of the globe has been extensively studied, and this has led to very numerous and varied data. Soils are very rich in titanium, as are rocks, and according to Swaine (1955), the most widely distributed soils contain 100--10,000 p.p.m. The latest data, including those from tropical soils obtained from the Spectrography Laboratory of the “Services Scientifiques Centraux de 1’0.R .S .T.O.M .” are discussed below. Contents range from unanalysable traces (humocarbonated soils of New Caledonia) to 25,000 p.p.m. (brown podzolic soil of Scotland). The average content is about 4,000--5,000p.p.m.


Temperate and boreal regions The total titanium concentrations of the soils of these regions range from 150 t o 25,000 p.p.m. There is a clear relationship between the soil contents and those of the parent rocks. Soils which are the poorest in titanium seem to be those formed on sands or sandy material. Thus, in Poland, soils on sands of the Lodz region contain only 150 p.p.m. of titanium. In the lower Volga valley of the U.S.S.R., titanium contents depend on the origin of the soil: soils on ancient alluvial and fluvio-glacial sands contain from 200 t o 1,000 p.p.m. and soils on marine sands from 280 to 3,200 p.p.m. In the case of podzolic soils and podzols, the influence of the parent rock is very important: in Poland, values ranging from 720 to 2,300 p.p.m. in the podzols on sands of the Yaroslavl region were reported and values from 2,160 to 5,940 p.p.m. in the soils of this type on clay loam. In Scotland, contents range from 1,000 p.p.m. in a peaty gleyed podzol with iron pan on granitic till to 12,000 and even 25,000 p.p.m. in brown podzolic soils on serpentinite till or olivine gabbro till. Podzols on gneiss and micaschist tills contain from 700 to 9,000 p.p.m. of total titanium. Brown forest soils are very rich in titanium: 6,500 p.p.m. in northeastern China, on basalt. In Scotland, on andesitic moraine a value of 10,000 p.p.m. was found. About the same concentration was found in Madagascar, in a black rendzina on gritty limestone: 9,300 p.p.m.

Arid and semiarid regions Total titanium concentrations of the soils of these regions range from values of 170 to 20,000 p.p.m. On the whole, concentrations are higher than 2,000 p.p.m. In the New Hebrides, values of 4,500-5,400 p.p.m. were found in reddish-brown fersiallitic soils on basic slags. Vertisols have high and more widely variable contents: in New Caledonia, on limestone-cemented flysch, values of about 3,000 p.p.m. were found; in Madagascar, contents are higher in the vertisols on alluvions: 5,000-7,000 p.p.m. Concentrations are highest in hydromorphic lithomorphic vertisols on amphibolite, in the Central African Republic: 10,000-20,000 p-p-m. Subdesert soils, on recent clay loam deposits of the Ustyurt region of the U.S.S.R., have the lowest content in arid and semiarid regions: 170-900 p.p.m. On the contrary, saline soils are generally rich in titanium: saline alkali soils of Turkmenistan, U.S.S.R., contain from 100 t o 6,000 p.p.m. In Madagascar, a value of 6,000 p.p.m. was found in a saline soil, and in New Caledonia, in a solodized solonetz on limestone-cemented flysch, a value of 3,000 p.p.m. was determined.

75

Tropical humid regions

Soils of these regions have the same upper and lower limits of titanium contents as in the previously mentioned regions: traces-21,000 p.p.m. In Madagascar, the following values were determined in gray femginous soils: in a soil on sandy hard crust: 650 p.p.m.; soils formed on limestone and sandstone-like material: 3,000--7,000 p.p.m. A value of 10,000 p.p.m. was found when the parent material was a basic crystalline rock. When a hydromorphy exists in these soils, the high titanium contents seem to decrease: in Chad, contents range from 600 to 2,000 p.p.m. in gray ferruginous soils with deep pseudogley developed on sandy clay material, while in the same type of soil on the same parent rock, with better drainage, values attain 3,000--10,000 p.p.m. However, these titanium contents seem to be widely variable in the same type of soil on the same rock. Titanium was determined in the Central African Republic in gray ferruginous soils derived from chamockites, amphibolites or gneiss. On each of these rocks, values ranging from 1,000 to 4,000 p.p.m., as well as from 10,000 to 20,000 p.p.m. were determined. Ferrallitic soils are at least as rich, or often richer, in titanium. In Madagascar, a value of 7,500 p.p.m. was found in a soil on gneiss and 21,000 p.p.m. in another soil on basalt. However, this accumulation of titanium in ferrallitic soils has been pointed out for a long time. Thus, according to Lacroix (1905), the soils of the Loos islands, Guinea, contain 9,000 p.p.m. in the crust, while the underlying nephelinic syenite contains only 2,900 p.p.m. Likewise, in Fourbam, Cameroun, according t o Laplante, basalt contains only 6,000 p.p.m. of titanium, while the horizon with sesquioxide concentrations contains 12,000 and 15,000 p.p.m. Hydromorphic soils have also high titanium concentrations : in the Central African Republic, hydromorphic pseudogley soils on alluvions contain from 3,000 to 10,000 p.p.m. In Chad, on sandy clay material, the hydromorphic gley soils seem to be richer: 15,000 p.p.m., than those with deep pseudogley: 1,000-2,000 p.p.m. In Madagascar, on alluvions, concentrations attain 7,000 p.p.m. in hydromorphic gley soils and 10,000 p.p.m. in hydromorphic soils. Slightly evolved deposit soils or erosion soils have about the same contents as those of the soils previously cited. They vary in relation to the parent rocks. In the Central African Republic, slightly evolved erosion soils on amphibolite contain from 3,000 to 10,000 p.p.m. of titanium, and in Chad, in a slightly evolved deposit soil on amphibole gneiss, the content reaches 15,000 p.p.m. However, in Madagascar, on sandy loams and sandy clay sediments and in the New Hebrides, on acid pumices on basic slags the contents of slightly evolved deposit soils are a little lower: 4,8004,000 p.p.m. In New

76

Caledonia, on limestone-cemented flysch, these types of soil are poorer in titanium: 3,000 p.p.m. It will be noticed also, that in New Caledonia, more or less humiferous humocarbonated soils on coralline limestone contain the lowest concentrations of titanium: traces that cannot be determined. TITANIUM CONTENT OF SOILS “AVAILABLE” TO PLANTS

Titanium seems practically insoluble in weak reagents. Thus, in Scotland, in a brown podzolic soil on olivine gabbro till, containing 12,000 p.p.m. of total titanium, a value of only 0.7 p.p.m. of titanium soluble in 2.5% acetic acid (pH 2.5) was found. However, data concerning “available” titanium are too limited to draw any valid conclusion. VARIATIONS OF THE TITANIUM CONTENT OF SOILS

One generally notices an increase in titanium contents with depth. Upper horizons, particularly those with high humus and organic matter contents, are relatively the poorest in this element. According to Vinogradov (1959), there is an accumulation of titanium in the illuvial horizons in some podzols. This also happens in gley soils: the B and C horizons of a brown podzolic soil contain 20,000 and 25,000 p.p.m. of titanium (Swaine and Mitchell, 1960). The titanium content of soils follows that of clays. Coarse-textured soils have lower concentrations than fine-textured soils. The content also follows that of iron sesquioxides, particularly in gray fermginous soils and, above all, in ferrallitic soils. However, the parent rock plays a major role in total soil titanium contents: soils formed on basic eruptive rocks are richer than those formed on granite, sands, etc. CONCLUSION

The titanium contents of soils approach those of the parent rocks. Contents are often very high: 1,000--10,000 p.p.m. and, in certain cases, they can reach 20,000 p.p.m. Titanium practically does not exist in soluble form in weak acid or in water. Generally, titanium is not very mobile in soil profiles. However, there is an accumulation of this element in the B horizons of some podzol profiles.

77

See also the following works published since 1968: POLAND: Boratyiiski, K., Roszyk, E. and Zietecka, M., 1972; Dobrzaiiski, B.,Gliiiski, J. and Cao Thai, V., 1971.

U.S.S.R.: Lukashev, K.I. and Pethukova, N.N., 1971 ; Tonkonozhenko, E.V. and Kulyupina, M.I., 1974. INDIA: Misra, S.G.and Tripathi, N., 1973.


79

VANADIUM* Vanadium can be found in most rocks of the earth’s crust. Ultrabasic eruptive rocks (dunite, peridotite) and basic rocks (basalt, gabbro.. .) contain maximum concentrations of this element: about 200 p.p.m. Concentrations are much lower in acid eruptive rocks (granite, rhyolite.. .): 30-40 p.p.m. Metamorphic rocks (schists) and certain sedimentary rocks (clays and loams) have about the same contents, 130 p.p.m., as basic eruptive rocks. Vanadium contents are particularly low in sandstones and carbonated rocks: 20 p.p.m. The average concentration of the lithosphere is about 150 p.p.m. (Swaine, 1955; Vinogradov, 1959; Turekian and Wedepohl, 1961). These general characteristics are confirmed by the few analytical results mentioned below, concerning the parent rocks of certain soils studied. In the case of alluvial formations, the results are widely variable according t o the lithologic nature of the river basins where they originated. Thus, in Bielorussia, U.S.S.R., vanadium contents vary from 1 2 p.p.m. in fluvio-glacial and ancient alluvial sands t o 160 p.p.m. in lacustrine glacial clays. Clayey loams, of morainic origin, contain 77 p.p.m. of vanadium. Alluvions of the Amur region, U.S.S.R., are richer, not only those derived from fine clayey loam (values of up t o 600 p.p.m.) but also those which are very sandy, where a content of 100 p.p.m. was determined.

TOTAL VANADIUM CONTENT OF SOILS

Soils have vanadium contents close to those of the rocks on which they were formed and sometimes even higher. In the soils studied, the concentrations range from traces (sandy soils of the U.S.S.R. and some tropical soils) t o 400 p.p.m. (rendzina of Madagascar). The parent rock seems to play an important part in relation to the total vanadium content of soils. However, the influence of the types of soil, with characteristics more or less in direct relation t o the major climatic and geographic zones, must be taken into consideration. Temperate and boreal regions

The total vanadium contents of the soils of these regions have upper and lower limits similar t o those previously cited: traces-400 p.p.m. The average content is about 100 p.p.m. *See Tables, pp. 358-367

80

In these regions the influence of the parent rock is particularly evident in the case of soils generally poor in trace elements, i.e. slightly evolved sandy soils and podzolic soils and podzois on sandy material. In the U.S.S.R., soils on sandy material of the lower Volga valley have total vanadium contents varying with the origin of these sands: they are very low (only traces) in soils on fluvio-glacial and ancient alluvial sands, a little higher (values up to 1 2 p.p.m.) in soils on ancient marine sands, and they reach 29 p.p.m. in soils on Quaternary marine sands. In Scotland, also, contents increase from podzols and brown podzolic soils formed on granitic till (15 p.p.m.) to those formed on olivine gabbro till or micaschists and granito-gneiss till (200 and 250 p.p.m.). Average values (60 p.p.m.) were found in the A. horizon of a peaty iron pan podzol on sandstone till. In Wales, too, similar uncultivated soils on rhyolite are poorer in vanadium, 15 p.p.m., than those on dolerite and other volcanic rocks: 75-150 p.p.m. The other types of soil have high concentrations of this element, often higher than 100 p.p.m., for example leached and hydromorphic soils. Leached soils: in the U.S.S.R., vanadium contents of leached soils attain 100 p.p.m. in the Meshchov plain and 160 p.p.m. (on average) in the Amur basin. Hydromorphic soils: in the Amur region, contents range from 140 to 300 p.p.m. in hydromorphic meadow soils on sandy alluvions and stratified plain deposits. In Scotland, contents are equal t o 200 p.p.m. in a hydromorphic gley soil on Silurian slate till. Brown forest are also rich in total vanadium: these soils, on basalt in northeastern China, contain 92 p.p.m. In the Amur basin, U.S.S.R., on granite, they contain 120 p.p.m. of total vanadium, and in Scotland on andesitic moraine, a value of 150 p.p.m. was determined. Rendzinas have about the same concentrations or a little higher. In Australia, 160 p.p.m. in Queensland and 170-290 p.p.m. in the Adelaide region. In Madagascar, a value of 390 p.p.m. was determined in a black rendzina on gritty limestone. Arid and semiarid regions The upper and lower limits of the total vanadium contents of the soils of these regions are the same as in temperate and boreal zones: traces-300 p.p.m. Contents are often greater than 100 p.p.m. Thus, a value of 290 p.p.m. of vanadium was found in the chernozems of the Amur region and values of 140-180 p.p.m. in the brown isohumic soils of Queensland, in Australia. On the contrary, in Chad, the latter soils on sandy sediments have low contents: t r a c e r 2 5 p.p.m. High contents and sometimes very high contents are found in vertisols: in Chad, the contents of topomorphic vertisols on clayey sediments range from

81

30 to 9 5 p.p.m.; on sandy clay sediments, from 90 to 200 p.p.m. In the Central African Republic, on amphibolite, hydromorphic lithomorphic vertisols have the highest concentrations of total vanadium in arid and semiarid zones: 200-300 p.p.m. Saline soils (saline alkali soils, solonetses.. .) are also rich in total vanadium: in Chad, values ranging from 55 t o 100 p.p.m. were found in saline soils and unleached alkali soils on clayey sediments; in Madagascar and New Caledonia, a value of 90 p.p.m. was determined in saline soils on alluvions and in a solod on limestonecemented flysch; in the solods of Queensland, contents ranging from 86 t o 130 p.p.m. were observed. Mediterranean red soils are often very rich in total vanadium: 70-180 p.p.m. in Georgia, U.S.S.R., on clayey material. In Queensland and the Adelaide region of Australia, values ranging from 82 to 300 p.p.m. were determined.

Tropical humid regions The upper and lower limits of total vanadium contents of the soils of these regions are the same as in other climatic zones: t r a c e r 3 0 0 p.p.m. The average content is about 80+0 p.p.m. The lowest concentrations have been found in the soils of New Caledonia: more or less humiferous hydromorphic humocarbonated soils on coralline limestone contain from traces to 2 p.p.m.; a calcareous anmoor semi-peaty soil on calcareous sand and coralline limestone contains from 2 to 7 p.p.m. of vanadium. These low concentrations correspond to the low concentrations of the parent rocks. The eutrophic brown soils on limestonecemented flysch in New Caledonia and on basaltic slags in the New Hebrides, have total vanadium contents of 70-80 p.p.m. and 40-90 p.p.m., respectively. In gray fermginous soils and ferrallitic soils, the parent rocks also play a major part in determining total vanadium contents. Thus, in the Central African Republic and Madagascar, gray ferruginous soil concentrations vary in relation to parent rock contents. In the Central African Republic, the following values were obtained on:Granite: 3-10 p.p.m. Gneiss: 100-150 p.p.m. Amphibolite: 100-300 p.p.m. In Madagascar, on sandstones and sands, the content is about 30 p.p.m.; on basic crystalline rock it attains 105 p.p.m. In Ghana, slightly t o moderately desaturated ferrallitic soils contain on:Granite: 5 - 6 0 p.p.m. Phyllite: 50-200 p.p.m. B2basic material: 200-300 p.p.m; The same can be said for the ferrallitic soils of Madagascar: 28 p.p.m. on granite, 170 p.p.m. on gneiss.

82

It is also noticed that for the same parent rock, the vanadium content of ferrallitic soils can be either low o r high: in the Central African Republic, on migmatite, values of 10-20 p.p.m. as well as 100 p.p.m. were found; on amphibolite values were 40 and 100-150 p.p.m.; in Chad, on arkose and arkosic sandstone, values range from 20 to 250 p.p.m. Among the soils rich in sesquioxides with high total vanadium concentrations, the krasnozems of Queensland can be mentioned: 120-270 p.p.m. Other types of soils have, on the whole, average contents. This applies t o the slightly evolved deposit soils: in Chad, on amphibole sandstone: 60 p.p.m.; in New Caledonia, on slaggy basaltic tuff or limestone-cemented flysch and in the New Hebrides, on acid pumice basic slags: 7 0 - 9 0 p.p.m. Easily flooded terrace soil and alluvial bank soil on sands and clayey sediments in Madagascar have the same contents. In Polynesia, on basaltic debris, the concentration range is much wider: 50-100 p.p.m. Vanadium content of slightly evolved erosion soils varies, naturally, in relation t o the type of parent rock. Thus, in the Central African Republic, values of 10 p.p.m. on itabirite, and values ranging from 100 to 300 p.p.m. on amphibolite, were found. Hydromorphic gley or pseudogley soils have average vanadium contents. In the Ivory Coast and the Central African Republic, hydromorphic pseudogley soils on schists or recent alluvions contain from 20 t o 80 p.p.m. and from 60 to 8 5 p.p.m., respectively. In Chad, the vanadium contents of hydromorphic soils are, on average, 25 p.p.m. on clayey sediments and 60 p.p.m. on sandy clay material. Halomorphic hydromorphic soils on clayey loam sediments are richer: 100-250 p.p.m. Moreover, in Polynesia, values ranging from 35 t o 110 p.p.m. of vanadium were found in hydromorphic soils on volcanic origin alluvions.

VANADIUM CONTENT OF SOILS “AVAILABLE” TO PLANTS

Vanadium has a certain influence on plants, particularly legumes. Numerous experiments have shown that it favours the fixation of nitrogen by nodules. It also plays a part in reducing nitrates. Its effect is comparable to that of molybdenum. However, vanadium “available” to plants has not been the subject of many studies up to now. It seems t o be slightly soluble in weak acids. In Scotland, vanadium soluble in 2.5% acetic acid (pH 2.5) varies from less than 0.02 t o 0.49 p.p.m., that is t o say, 0.4 t o 0.6% of total vanadium.

83 VARIATIONS OF THE VANADIUM CONTENT OF SOILS

Generally, humiferous horizons are the richest in vanadium. This seems to be particularly true for the isohumic and brown forest soils of the U.S.S.R. Vanadium concentrations also vary in relation to soil texture. Clayey or fine-textured soils are richer than sandy soils. In tropical zones an increase in the concentration is noticed with increasing depth. The distribution of vanadium between different horizons follows that of clays (ferrallitic soils of Dahomey, Pinta and Ollat, 1961). In temperate zones, the B horizon of leached soils and podzols is often richer than the upper horizon (podzols of Scotland, Swaine and Mitchell, 1960). On the other hand, the major influence of parent rock concerning total vanadium concentrations of soils has been pointed out previously.

CONCLUSION

The vanadium contents of soils range from traces to 300 p.p.m. The average content is about 100 p.p.m. There are no important differences between the vanadium contents of soils of diverse climatic regions, and these contents depend essentially on those of the parent rocks.

~

~

~~~~~

See also the following works published since 1968: FRANCE : Bertrand, D., 1968. POLAND: Dobrzaiiski, B., Glinski, J. and Cao Thai, V., 1971; Dobrzaiiski, B. and Glifiski, J., 1970; Gliiiski, J. and Magierski, J., 1971. U.S.S.R.: Dobritskaya, Yu.I., 1972; Lukashev, K.I. and Petukhova, N.N., 1971. U.S.A.: Bradford, G.R., Bair, F.L. and Hunsaker, V., 1971.


85

ZINC* Most rocks of the earth’s crust contain zinc, in varying concentrations depending on the type of rock. Zinc contents are highest in basic eruptive rocks (basalt, gabbro.. .): 70130 p.p.m. Contents are average in acid eruptive rocks (granite, rhyolite.. .): 50-60 p.p.m. Metamorphic rocks (schists) and certain sedimentary rocks (clays) have intermediate contents: 80 p.p.m. on average. The lowest relative contents are found in loessic loams and glacial clays: 30-40 p.p.m., as well as in carbonated rocks and sandstone which contain 20 and 16 p.p.m., respectively. The zinc concentration of the lithosphere is similar t o the average concentration of rocks: 50 p.p.m. (Vinogradov, 1959; Turekian and Wedepohl, 1961; Kovda et al., 1964). Analytical data concerning rocks from different regions of the globe are in agreement with the average concentrations cited above. In the Kola peninsula (U.S.S.R.),crystalline schists with norite intrusion contain 100 p.p.m. of zinc and the sandy clay moraine which covers them only 50 p.p.m.; in the Amur region sandy alluvions are relatively poor in zinc: 10 p.p.m.; on the contrary flood plain deposits are rich, containing 85 p.p.m.; in Bielorussia, morainic clayey loams also have low contents: 8-23 p.p.m. In Czechoslovakia, schists are richer than sands: 23 and 13 p.p.m., respectively. In Gujarat, India, zinc contents show an increase from sandstone (16 p.p.m.) to basic igneous rocks (51 p.p.m.). Limestones and schists have intermediate contents: 24 and 47 p.p.m., respectively. In Australia (Tasmania), dolerite contains from 40 t o 90 p.p.m. In the Hawaiian Islands, basalts and volcanic ashes are very rich in zinc: 110-150 p.p.m. TOTAL ZINC CONTENT OF SOILS

Zinc concentrations of soils vary widely. The lower and upper limits range from traces to 900 p.p.m. The average concentration is from 50 t o 100 p.p.m. Variations are due, principally, to the different concentrations in the rocks from which the soils were derived. The influence of these rocks is major compared to that of the pedogenic processes.


86

Temperate and boreal regions The upper and lower limits of total zinc in the soils of these regions are, respectively, 600 p.p.m. (more or less evolved soils of Canada) and traces (soils of Czechoslovakia). Slightly podzolic leached soils of Bielorussia are very poor in zinc if they were formed on clayey loams: 0.84-8.5 p.p.m. Those formed on ancient alluvial and fluvio-glacial sands have contents ranging from 4.4 to 9.3 p.p.m. These soils are a little richer if they were formed on morainic clayey loams or lacustrine clays: 2.1-13 p.p.m. and 8.3-20.4 p.p.m., respectively. In the Cluj and Olt regions of Rumania, average concentrations of 28 and 46 p.p.m. were found in podzols. In New Brunswick (Canada), where the upper horizons of podzols have much higher concentrations of zinc than average, contents vary greatly in relation to the type of parent rock: a value of 400 p.p.m. was found on sediments rich in sulphur and only 90 p.p.m. on other sediments. In Tasmania (Australia), leached soils on dolerite are richer (39-96 p-p-m.) than those of Karelia (U.S.S.R.) on morainic glacial clays or lacustrine clays: 7.79-66 p.p.m. Brown forest soils have very widely variable zinc contents which follow those of the parent rocks. Contents are low on granite (14p.p.m.) in the Amur region, average on dolerite in Tasmania ( 4 1 - 6 5 p.p.m.) and high on basalt in northeastern China (85 p.p.m.). Hydromorphic soils are generally rich in total zinc: hydromorphic alluvial soils of the Moskva valley contain 80-130 p.p.m. and in the Amur region these soils on flood plain deposits contain 70-100 p.p.m. Rendzinas and calcareous brown soils have, on the whole, concentrations close to average and sometimes higher:In Madagascar, on gritty limestone: 42 p.p.m. In Queensland (Australia), on limestone: 70 p.p.m. In Israel, on marl: 100-130 p.p.m. The highest concentrations found in soils of the temperate and boreal regions correspond t o more or less evolved sandy loam soils of Nova Scotia (Canada): 250-600 p.p.m.

Arid and semiarid regions Soils of these climatic regions have total zinc contents ranging from traces (subdesert soils of the Ustyurt region) to 900 p.p.m. (saline alkali soils of Turkmenistan). Concentrations are often widely variable in a given region and for the same type of soil, but, on the whole, contents are average or a little higher than average. Chernozems contain high quantities of zinc; those of Dobrudja, Rumania, formed on loess, contain 73 p.p.m. and those of the Olt and Cluj regions are still richer: 84-103 p.p.m.

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In the Ural-Sahara basin, the same type of soils derived from ancient sediments contain 45 p.p.m. of total zinc, but in the Rostov region, the widely variable contents of the ciscaucasian chernozems attain 680 p.p.m. Chestnut soils mostly have average contents: in Bulgaria, values ranging from 42 t o 106 p.p.m. were found in chestnut soils and from 62 to 98 p.p.m. in vertic chestnut and hydromorphic chestnut soils. In the Stavropol region of the U.S.S.R., the upper and lower limits are a little lower: 14.4-71 p-p-m. Contents are about the same in the brown isohumic soils of: Uzbekistan: 83 p.p.m. Israel, on calcareous sandstone: 48 p.p.m.; on alluvions derived from “terra rossa” and aeolian deposits: 82-90 p.p.m. Queensland, on calcareous sandstone and on clayey sediments: 45-100 p.p.m. Values ranging from 25 to 30 p.p.m. of total zinc were found in the vertisols of New Caledonia on limestone-cemented flysch; and 60-70 p.p.m. in those of Gujarat, India, on sandstone and igneous rocks. In Chad on sandy clay sediments, in Madagascar on clayey sands and alluvions, and in Queensland on diorite and basalt, contents attain 90,105 and 120 p.p.m. In the U.S.S.R., subdesert soils on clayey loams can be poor (traces-40 p.p.m. in Turkmenistan) or rich (60-112 p.p.m. in Uzbekistan) in this element. Saline soils (saline alkali soils, solonetses.. .) also show widely variable contents. Average contents were found in Bulgaria in saline alkali soils: 4 0 - 6 0 p.p.m., and in Queensland (Australia) in solods on granite and alluvions: 10-50 p.p.m. High contents, 100-200 p.p.m., were determined in Israel also in saline alkali soils, and exceptionally high contents in Turkmenistan (U.S.S.R.) in the same type of soil: 100-900 p-p-m. Similar variations in the contents of alluvial hydromorphic soils can be noticed: in Bulgaria contents are average: 62 p.p.m., and in the Caucasus they are very high, reaching 850 p.p.m. Mediterranean red soils of the different regions of Australia (Queensland, Southeast, Adelaide) have average concentrations of total zinc: 11-86 p.p.m. On the other hand, in Israel, these soils contain much higher quantities: 200-215 p.p.m.

Tropical h urnid regions Tropical soils have about the same total zinc contents as soils of other climatic regions. Contents range from traces (soils of Polynesia) to 400 p.p.m. (soils of the New Hebrides). Eutrophic brown soils: in New Caledonia, these soils on limestonecemented flysch are poorer in zinc (25-30 p.p.m.) than those of the New Hebrides on basaltic slags (250-400 P.P.m.).

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In gray fcrruginous hydromorphic leached soils on gneiss and amphibolite of the Central African Republic the contents determined were hardly average. On the contrary, in Madagascar, gray tropical soils are rich in total zinc: 95 p.p.m. on schists and 135 p.p.m. on sandstone. In Dahomey, the content is average: 6 5 p.p.m. In Chad, concentrations are higher in gray ferruginous pseudogley soils on sandy sediments, 300 p.p.m., than in the same type of soils, with better drainage, on sandy and clayey sediments, 100 p.p.m. The minimum concentrations are identical in the two cases: 25 p.p.m. Ferrallitic soils also have widely variable contents, most often about the same as those cited above. In the Central African Republic, slightly desaturated ferrallitic soils on different parent rocks (migmatite, gneiss, schists, amphibolite, . . .) have relatively the lowest contents: 25-40 p.p.m. In Dahomey and Chad, on arkose and limestone, zinc values of 40-116 p.p.m. and 25-145 p.p.m. were determined. Krasnozems on basalts, and humiferous ferrallitic soils on alluvions of Queensland have about the same concentrations: 42-100 p.p.m. In India, slightly ferrallitic clayey soils contain 65 p.p.m. In Madagascar, contents are often high: 100 p.p.m. in a slightly ferrallitic leached red soil on gneiss. Ferrallitic soils on granite contain 140 p.p.m. and a reddish-brown humiferous ferrallitic soil on cipolin 198 p.p.m. In New Caledonia, ferrallitic soils, on slaggy basaltic tuff and dolerite, basalt and andesitic basalt, have contents varying in relation t o their degree of degradation by erosion: 70-250 p.p.m. In Polynesia these soils contain from traces to 150 p.p.m. of zinc and from traces to 70 p.p.m. if indurated at depth. Hydromorphic alluvial soils generally have average contents, but sometimes they are rather rich: in the Central African Republic, hydromorphic gley soils on clayey sediments contain from 20 to 40 p.p.m. In Chad, more or less saline hydromorphic soils on loamy clay sediments can contain up to 100 p.p.m. In Gujarat, India, alluvial soils on limestone are richer, 76-80 p.p.m., than those formed on schists: 5 0 - 6 0 p.p.m. In Punjab, the range between the upper and lower limits is wider for soils formed on alluvions originating from eruptive rocks, not only rich in quartz and feldspath but also in amphibole (hornblendite) and tourmaline: 18-100 p.p.m. Slightly evolved deposit or erosion soils have widely variable contents depending chiefly on those of the parent rocks:In the Central African Republic, slightly evolved erosion soils, on amphibolite and itabirite, contain from 25 to 40 p.p.m. of total zinc. In Madagascar, in the western alluvial zones, flood terrace and alluvial bank soils contain 100 and 6 5 p.p.m., respectively. In New Caledonia, slightly evolved deposit soils on limestone-cemented

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flysch are poorer in zinc (25-30 p.p.m.) than those formed on slaggy basaltic tuff (70-250 p.p.m.1. In the New Hebrides, slightly evolved deposit soils derived from acid pumice covering basic slags are very rich in total zinc: 250-320 p.p.m.

ZINC CONTENT OF SOILS “AVAILABLE” TO PLANTS

Various plant diseases are due t o a toxicity or a deficiency in zinc, and yet the part played by this element seems to be more important in animal biochemistry, in a similar way to that of copper and cobalt (Vinogradov, 1959). Consequently it is very important to know, not only the total zinc content but also the proportion of total zinc “available” t o plants. Extraction reagents vary according to the different authors:Diluted strong acids (1 N hydrochloric acid and 1 N nitric acid, 0.1 N hydrochloric acid) Weak acids (2.5% acetic acid, pH 2.5) Salts (1 N potassium chloride, 1 N ammonium acetate, pH 7 and 1 N sodium acetate, pH 4.8) Organic complexing agents: E.D.T.A. The proportions of “plant-available” zinc vary, naturally, according t o the reagent used, but still more, it appears, in relation t o the physico-chemical characteristics of the soil and, consequently, the soil type. On the whole, “plant-available” zinc concentrations are relatively high, representing, on an average, 5-2076 of total zinc. In certain quite exceptional cases, the percentage can attain 25% and even 90% of total zinc. Extraction by salts and complexing agents:In Bulgaria, ammonium acetate-exchangeable zinc concentrations of chernozems, chestnut soils and saline alkali soils of the steppe zones range from traces t o 3.8 p.p.m. and represent 1-8.396 of total zinc. In the podzolic and peaty soils of Bielorussia, ammonium acetateexchangeable zinc varies from 0.049 to 0.92 p.p.m. i.e. 5 4 2 % of total zinc. In the hydromorphic alluvial soils of the lower Moskva valley this form of zinc represents 0.2-20% of total zinc (0.2-27 p.p.m.). Sodium acetate buffer solution (pH 4.8) extracted 2.1-3.5 p.p.m. of zinc, i.e. 2.3-5.1% of total zinc from subdesert soils of Uzbekistan, having average contents (60-110 p.p.m.) of total zinc. In Mali, the authors used 1 N potassium chloride t o extract plant-available zinc from slightly leached gray ferruginous and alluvial soils. Values ranging from 0.1 to 0.9 p.p.m., i.e. 4-1876 of total zinc were determined. In Israel, E.D.T.A. was used to extract zinc from different types of soils: concentrations range from 1.9 t o 13 p.p.m., i.e. 1.7-9.6% of total zinc in mediterranean red soils, reddish-brown isohumic soils, rendzinas. . . Extraction by acids:-

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Workers in India mostly use 0.1 N hydrochlorid acid as an extraction reagent. They show that in the alluvial soils analyzed, concentrations range from 1.8 t o 6.3 p.p.m., i.e. 3.6--13.2% of total zinc. Vertisols and vertic soils contain 1.2-3.8 p.p.m. of 0.1 N hydrochloric acid-soluble zinc, i.e. 1.5-5.6% of total zinc. In South Africa, the average concentration of “plant-available” zinc extracted from leached, ferrallitic and brown isohumic soils, using 0.1 N hydrochloric acid as extraction reagent, was about 0.6 p.p.m., i.e. 5.5% of total zinc. In the Hawaiian Islands, in the same extraction conditions, values from 0.1 to 18 p.p.m. of plant-available zinc were determined in acid latosols, representing 0.2--6.3%of total zinc. Higher concentrations are extracted by strong acids : in Turkmenistan (Amu-Daria), 1N nitric acid extracted 15.5-24% of total zinc (5-18 p.p.m.) from hydromorphic meadow soils containing average total zinc contents (30-80 p.p.m.).

VARIATIONS OF THE ZINC CONTENT OF SOILS

Biogenetic factors have a certain influence on the distribution of zinc between the different soil horizons. Total zinc as well as “available” zinc accumulate in the upper soil horizons, particularly in the humiferous horizons. Zinc concentrations increase at the same time as those of humus and organic matter. In podzols and podzolic soils, the distribution depends on the degree of podzolization. Zinc tends t o accumulate in the illuvial horizon. In brown calcareous soils and rendzinas (Kielce region of Poland) an accumulation is produced in the A and (B) horizons in respect to the original material. In chernozems, the distribution of zinc is uniform between the different horizons. Zinc contents also vary in relation t o soil texture; clay holds zinc. Finetextured soils on clay and loam are richer in zinc than coarse-textured soils on sandy material. It was noticed that in tropical soils, particularly in Dahomey, zinc concentrations increase with depth and that there is an accumulation in the more clayey horizons. Oxido-reduction conditions influence zinc dynamism as with iron. Seasonal variations of zinc seem t o follow that of the ferrous-Fe, ferric-Fe relationship in the soil. Studies concerning trace elements of the alluvial soils of the lower Moskva valley in the U.S.S.R., have given good evidence of this fact. Soil pH also has a certain influence on the “available” zinc contents. An acid pH makes easier the solubilization of zinc compounds, which can

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increase the relative contents of this form of zinc, leaving the soil rather rich if this element is not carried away. It also seems, as certain authors have pointed out, that the proportion of “available” zinc increases due t o the influence of cultivation. This has been demonstrated in the U.S.S.R. in slightly podzolic leached soils in the south of the taiga zone as well as in the subdesert soils of Uzbekistan or hydromorphic soils of Turkmenistan. The influence of these different pedogenic factors on total and “available” soil zinc contents, although not t o be neglected, is, however, less than that of the parent rock for all the soil types of the diverse climatic zones, as has been previously shown.


Zinc deficiencies are often noticed in acid pH soils. A pH equal to or lower than 5 facilitates zinc solubilization and, in humid zones, it can be easily carried away (leached soils, podzols and podzolic soils are often deficient). Also, in these acid soils, plants extract more zinc from the soil. Certain crops (cereals, sugar cane.. .) cause a rapid decrease in zinc soil reserves after harvesting. This fact has been pointed out for the latosols of the Hawaiian Islands. Moreover, certain alkaline pH soils also show zinc deficiency, this element being in an only slightly “available” form. For example, in the brown isohumic calcareous soils of New South Wales in Australia, where total zinc concentrations can be considered as sufficient (35-61 p.p.m.), “plant-available” zinc concentrations are very low and often at the limit of deficiency. Zinc deficiency in soils can also depend on a high content of fine clay and silt which strongly hold onto the zinc. In the U.S.A., greenhouse expenments showed that liming clayey soils causes, by the immobilization of zinc, a zinc deficiency in maize, while the same treatment has no effect on a sandy loess soil. According to Ryan et al. (1967) phosphorus applications t o certain soils are also the cause of zinc deficiency in plants. In India, the deficiency limit of “available” zinc, soluble in 0.1 N hydrochloric acid, has been fixed a t 1 p.p.m. In Japan, this limit is equal t o 4-5 p.p.m. of zinc, determined by Aspergillus niger, for alluvial soils. In France, the work of Chabannes et al. (1949), on a slightly clayey and strongly humiferous sandy soil, and that of Dartigues et al. (1963) on sandy loams and loamy sand soils showed that zinc deficiency appears for concentrations lower than 3 p.p.m. of dilute hydrochloric acid-soluble zinc (pH 5) or 0.2 N hydrochloric acid-soluble zinc. Zinc deficiency is corrected by applications of soluble zinc compounds, principally zinc sulphate, sometimes by sprinkling, but most often by spray-

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ing. When the soils are acid, a weak liming can be effective in making zinc less easily soluble. Toxicity is rare, even after successive heavy treatments used t o correct a deficiency. However, some cases of toxicity have been found in Greece (alluvial, peaty and mediterranean red soils) and in Spain (acid soils in a dry region) (Ryan et al., 1967). In India, the toxicity limit of “available” zinc, soluble in 0.1 N hydrochloric acid is estimated a t 100 p.p.m. In the Netherlands, where the quantity of zinc soluble in 2.5% acetic acid is sometimes very high, liming eliminates zinc toxicity in oats and beets.

CONCLUSION

Zinc is found in relatively high concentrations in soils (50 p.p.m. on an average). There are no essential differences between the diverse types of soils in different climatic zones. Zinc contents of soils vary in relation t o those of the parent rocks and to soil humus and clay contents. Zinc mobility depends on soil pH. In rather dry regions, “plant-available” zinc contents increase with increasing acidity of soil pH. Zinc deficiency in acid soils of humid regions is corrected by using soluble zinc compounds, sometimes associated with liming. Toxicities, which appear less often, are also corrected by liming.

~

See also the following works published since 1968: WALES: Alloway, B.J. and Davies, B.E., 1971. BELGIUM: Nair, K.P.P. and Cottenie, A., 1 9 7 1 . SPAIN : Macias, F.D., 1973. YUGOSLAVIA: JeriE, M. and SaviE, B., 1970-1971. GREECE: Apostolakis, C.G. and Douka, C., 1970. POLAND: Czuba, R., Gaszek, K. and Wlodarczyk, Z., 7.974a; Czuba, R., Dudziak, S., Malinska, K., 197413. HUNGARY: Six, L., 1 9 7 0 ; Six, L., 1 9 7 1 a ; Six, L., 1 9 7 1 b ; Six, L. and Lukacsy, D., 1 9 7 1 ; S i x , L. and Nagy, L., 1972. RUMANIA: Chiriac, A. and Bajescu, I., 1 9 7 4 .

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U.S.S.R.: Dubikovskii, G.P. and Anoshko, V.S., 1 9 7 0 ; Sviridov, A S . , Kazakova, Ye.G., Sviridova, E.V. and Belosokhova, N.F., 1969. CANADA: Mallick, K.A., 1972;Matt, K.J., 1974. U.S.A.: Dankert, W.W. and Drew, J.V., 1 9 7 0 ; Dolar, S.G. and Keeney, D.R., 1971;Follett, R.H. and Lindsay, W.L., 1 9 7 1 ; Lindsay, W.L., 1972. BRAZIL: De Santana, C.J.L. and Igue, K., 1972. ARGENTINA: Merodio, J.C., 1970. JAPAN : Mizuno, N. and Kobayashi, S., 1 9 7 1 ; Yoshida, S. and Tanaka, A., 1969. INDIA: Deb, D.L. and Sharma, B.M., 1 9 7 3 ; Meelu, O.P. and Randhawa, N.S., 1973;Prasad, K.G. and Sinha, H., 1 9 6 9 ; Rai, M.M., Shitoley, D.B., Pal, A.R., Vakil, P. and Gupta, S.K., 1 9 7 0 ; Rai, M.M., Pal, A.R., Chimania, B.P., Shitoley, D.B. and Vakil, P., 1972c; Shanker, H. and Dwivedi, K.N., 1972. CYPRUS : Pagel, H. and Prasad, R.N., 1971. EGYPT: Abdel Salam, M.A., El-Demerdashe, S., Abdel-Aal, S.H.1. and Ibrahim, M.G., 1971; ElMowelhi, N.M., Mitkees, A.I., Abouhussein, M.A. and Shabassy, A.I., 1973. ISRAEL: Navrot, J. and Gal, M., 1971. ARID AND HUMID TROPICS : Prasad, R.N. and Pagel, H., 1970. SOUTH AFRICA: Stanton, D.A., Du, T. and Burger, R., 1970. NEW ZEALAMD: Witton, S. and Wells, N., 1974.


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OTHER ELEMENTS This chapter includes the trace elements which have been determined by the Pedology Department Spectrography Laboratory of the “Services Scientifiques Centraux de 1’O.R.S.T.O.M.” from a large number of tropical and subtropical soils, mostly from Africa and Madagascar (about 300). Recent bibliographical data from other sources are very limited. These elements have not been studied a great deal, either because their role as trace elements does not seem to be of primary importance, or because their analysis is often difficult, due t o the inherent limitation of the sensitivity and precision of the methods employed. The soils mentioned above were analyzed by the Spectrography Laboratory using arc spectrography. Because of the limited number of data, there are no synoptic tables. RARE ALKALINE ELEMENTS: LITHIUM, RUBIDIUM AND CAESIUM The average lithium, rubidium and caesium concentrations of different types of rocks are as follows:Ultrabasic eruptive rocks: lithium: 0.5 p.p.m.; rubidium: 2 p.p.m-; caesium: 0.1 p.p.m. Basic eruptive rocks: lithium: 15 p.p.m.; rubidium: 45 p.p.m.; caesium: 1p.p.m. Acid eruptive rocks: lithium: 40 p.p.m.; rubidium: 200 p.p.m.; caesium: 0.5 p.p.m. Metamorphic rocks and clays: lithium: 60 p.p.m.; rubidium: 200 p.p.m.; caesium: 1 2 p.p.m. Sandstone and carbonated rocks: lithium: 1 5 and 5 p.p.m.; rubidium: 60 and 3 p.p.m.; n o data exist for caesium. The concentrations of these elements in the lithosphere are as follows: 6 5 p.p.m. for lithium; 300 p.p.m. for rubidium and 3-7 p.p.m. for caesium (Swaine, 1955; Vinogradov, 1959; Turekian and Wedepohl, 1961; Kovda et al., 1964).

TOTAL LITHIUM, RUBIDIUM AND CAESIUM CONTENT OF SOILS

According t o Swaine (1955), soil lithium contents range from values of 5 to 200 p.p.m. Vinogradov (1959), however, gives a narrower range of values, 10-70 p.p.m., particularly for the soils of the U.S.S.R. Rubidium concentrations are higher: according to Swaine (1955), values range from 20 t o 500 p.p.m. and, according t o Vinogradov (1959), from 1 0 to 100 p.p.m. Values obtained by arc spectrography from soils of arid, semiarid and

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tropical zones reach 400 p.p.m. for lithium and 1,000 p.p.m. for rubidium. Data concerning caesium are lacking. Vinogradov (1959) cites values of about 4-5 p.p.m. for the soils of the U.S.S.R.; the spectrographic method employed was unable t o determine this element with precision. Swaine (1955) cites a few bibliographical references in which the analytical results also appear uncertain. Analyses performed by the Spectrography Laboratory, on soils of tropical and subtropical regions have shown extremely wide ranges in concentration: from 3 to 500 p.p.m., most of them being higher than those cited by Vinogradov (1959).

Temperate and boreal regions The upper and lower limits of lithium and rubidium contents of the soils of these regions are similar t o those cited previously. Thus, in Scotland, values of 8 and 200 p.p.m., respectively, were found in the A,, peaty horizon of an iron pan podzol on sandstone, and a podzol on micaschist till. Also, values of 10 and 20 p.p.m., respectively, were found in a brown podzolic soil on serpentinite till and a podzol on granitic till. In the same soils, rubidium concentrations range from values of 40 p.p.m. (in the A. peaty horizon of an iron pan podzol on sandstone till) t o 500 p.p.m. (in a podzol on gneiss till). Brown podzolic soils on serpentinite till and olivine gabbro till contain, respectively, 60 and 50 p.p.m. of rubidium (Swaine and Mitchell, 1960). In the U.S.S.R., podzols contain average quantities of lithium: 17-40 p.p.m., and higher amounts of rubidium : 80 p.p.m. (Vinogradov, 1959). Data concerning caesium are lacking. Brown forest soils also have average concentrations of these elements. In Scotland, in a brown forest soil on andesitic moraine, lithium and rubidium attain a value of 50 p.p.m. (Swaine and Mitchell, 1960). In the U.S.S.R., values of 40 p.p.m. of lithium and 31 p.p.m. of rubidium were found in the same type of soil (Vinogradov, 1959). Contents are higher in rendzinas: in Madagascar, in the upper part of a black rendzina, on gritty limestone, values of 115 p.p.m. of lithium, 350 p.p.m. of rubidium and 660 p.p.m. of caesium were found (NaloviC!,1969).

Arid and semiarid regions Rubidium and caesium contents (the latter being rarely determined) of some soil types of these regions are sometimes relatively high. In the U.S.S.R., lithium and rubidium contents of chernozems are average; they contain, respectively, 37-46 p.p.m. and 5 7 - 9 0 p.p.m. (Vinogradov, 1959). In Chad, brown isohumic soils on clayey and sandy sediments contain

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20 p.p.m. of lithium and 300 p.p.m. of rubidium (Pias, 1968). Vertisols are most often rich and, sometimes, very rich, in rubidium and caesium :In Chad, topomorphic vertisols on clayey and sandy clay sediments contain from 20 t o 90 p.p.m. of lithium and from 100 t o 1,000 p.p.m. of rubidium (Pias, 1968). In the Central African Republic, lithomorphic vertisols on para-amphibolites contain from 10 t o 15 p.p.m. of lithium, 300 p.p.m. of rubidium and 60-200 p.p.m. of caesium (Boulvert, 1966). Vertisols, on alluvions, in Madagascar, are also rich in these three elements: 70-180 p.p.m. of lithium, 190-680 p.p.m. of rubidium and 280-300 p.p.m. of caesium (NaloviZ!,1969). On the other hand, in New Caledonia, vertisols on limestone-cemented flysch are poor in rubidium, containing only 8 p.p.m. A value of about 24 p.p.m. of lithium was found in these soils (Tercinier, 1966). Also, in the same country, about the same values, 18 p.p.m. of lithium and 8 p.p.m. of rubidium, were determined in a solodized solonetz on limestone-cemented flysch (Tercinier, 1966). In Madagascar, a saline soil on alluvions was found t o be rich in rubidium, 440 p.p.m., while the lithium concentration was average, 42 p.p.m. (NaloviE, 1969). Saline alkali soils and solonchaks of the U.S.S.R. have average lithium contents: 23 p.p.m. Rubidium contents range from values of 19 t o 67 p.p.m. (Vinogradov, 1959). Tropical h urnid regions The upper and lower limits of lithium, rubidium and caesium contents of the soils of these regions are widely variable, ranging from values of less than 1.8 to 400 p.p.m. of lithium, less than 3 to 100 p.p.m. of rubidium, and from 3 to 300 p.p.m. of caesium. The lower limits indicated are related t o the limit of sensitivity of the spectrographic method employed. Eutrophic brown soils:In New Caledonia, these soils on limestonecemented flysch contain 1 7 p.p.m. of lithium and their rubidium content is low: only 3 p.p.m. However, in New Hebrides, these soils, on basaltic slags, contain high concentrations of lithium: 250-350 p.p.m., and relatively low concentrations of rubidium: 20-25 p.p.m. (Tercinier, 1964, 1966). Gray fermginous soils:In the Central African Republic, these soils, on granite and charnockite, contain low amounts of lithium: 3-9 p.p.m., and of rubidium: less than 3 p.p.m. On gneiss, amphibolite and migmatite these soils also have low lithium contents: 3-20 p.p.m., and very diverse contents for rubidium and

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caesium: from less than 3 t o 300 p.p.m. for rubidium and from 3 t o 150 p.p.m. for caesium (Boulvert, 1966). In Chad, gray ferruginous deep pseudogley soils on sandy and sandy clay sediments contain average quantities of lithium: 15-30 p.p.m., and are very rich in rubidium: 200-1,000 p.p.m. These soils are poor in caesium: 3 p.p.m. (Pias, 1968; Vizier, 1965). In Madagascar, gray fermginous soils are generally rich in these elements, with contents varying in relation to the parent rock: these soils, on sandstone, contain 30 p.p.m. of lithium and on schists, 140 p.p.m.; on basic rocks, limestone and sands, they contain from 85 t o 95 p.p.m. of lithium; rubidium contents range from 140 p.p.m. on sands t o 350 p.p.m. on basic rocks and 390 p.p.m. on sandstone. Caesium content reaches 60 p.p.m. in these types of soil formed on limestone (NaloviC, 1969). Ferrallitic soils :In the Central African Republic, these soils on different parent rocks contain mostly from 3 t o 30 p.p.m. of lithium. The lowest concentrations were found in these soils on granite: 2 . 7 4 p.p.m., while the highest concentrations were determined in soils on gneiss, with large variations: 3-300 p.p.m. In most soils, rubidium content is lower than or equal to 3 p.p.m., with the exception of ferrallitic soils formed on gneiss, where the rubidium content varies in the same range as lithium: 3-300 p.p.m. Caesium contents range from 10 to 30 p.p.m. (Boulvert, 1966). In Chad, ferrallitic soils on sandstone contain from 3 to 30 p.p.m. of lithium, as above. On the other hand, rubidium contents are higher: 100300 p.p.m. (Pias, 1968). Data obtained from the soils of Madagascar vary widely, in relation to the parent rock. Thus, a value of less than 1.8 p.p.m. of lithium was determined in these soils formed on volcanic ashes, and 70 p.p.m. in those formed on limestone; on gneiss and granite, these soils contain from 27 to 35 p.p.m. of lithium. Rubidium content is also relatively low in soils on volcanic ashes: 13 p.p.m., while the highest concentrations were determined in these soils on granite: 265 p.p.m. Caesium content is high in soils on limestone and basalt: 90 and 170 p.p.m. (Nalovic, 1969). All the ferrallitic soils studied in Polynesia, derived from basalt and andesitic basalt, have lithium content ranging from values of 3 to 30 p.p.m. These values vary in relation t o the degree of soil degradation and the induration in deep horizons:Very degraded ferrallitic soils: 3 p.p-m. Slightly degraded ferrallitic soils : 5-30 p.p-m. Indurated subsoil ferrallitic soils: 3-10 p.p.m. (Tercinier, 1963). Hydromorphic gley and pseudogley soils and alluvial soils :In the Central African Republic, these soils, on recent alluvions, have average concentrations of lithium: 25-30 p.p.m., but those of rubidium, 8 p.p.m., and caesium, 10 p.p.m., are low (Boulvert, 1966).

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In Chad, hydromorphic gley and pseudogley soils on sands and sandy clay sediments, contain 25-30 p.p.m. of lithium, 200 p.p.m. of rubidium and from 6 to 30 p.p.m. of caesium. On the other hand, halomorphic hydromorphic alluvial soils are rich in lithium: 30-100 p.p.m., and very rich in rubidium: 270-1,000 p.p.m. (Vizier, 1965; Pias, 1968). Hydromorphic and hydromorphic gley soils of Madagascar are also rich in lithium: 7 1 - 9 0 p.p.m.; rubidium: 90-180 p.p.m.; and caesium 220 p.p.m. (NaloviE, 1969). Slightly evolved erosion and deposit soils:In the Central African Republic, slightly evolved erosion soil contents vary, naturally, with the parent rock: these soils contain 2.7 p.p.m. of lithium on itabirite, and from 10 to 20 p.p.m. on amphibolite. A value of 300 p.p.m. of caesium was also determined (Boulvert, 1966). In Madagascar, slightly evolved alluvial soils are rich in lithium: 75-250 p.p.m., and rubidium: 280-480 p.p.m. (NaloviC, 1969). In the New Hebrides, slightly evolved deposit soils, on acid pumices covering basic slags, contain from 180 to 400 p.p.m. of lithium and only 25 p.p.m. of rubidium (Tercinier, 1964). All these results show that soil lithium and rubidium contents of the diverse climatic regions, although being extremely variable, fall between the upper and lower limits cited by Swaine (1955). These contents vary in relation t o the parent rock and, to a lesser degree, to some pedogenic processes, particularly in soils of tropical regions. The distribution of these elements between the different horizons of soils appears t o be linked t o the type of soil. Most often these elements accumulate in the upper horizons. Hydromorphy plays an important part in this distribution; this has been shown, particularly, in Madagascar (NaloviE, 1969).

ALKALINE EARTH ELEMENTS: BARIUM, STRONTIUM Barium and strontium contents of rocks vary according to the type of rock. Ultrabasic eruptive rocks are very poor in these elements: barium, 1 p.p.m.; strontium, 10 p.p.m. Basic eruptive rocks (basalt, gabbro.. .), although richer than ultrabasic eruptive rocks, are, however, less rich in barium, 270 p.p.m., than acid eruptive rocks (granite, charnockite.. .), metamorphic (gneiss and schists) or sedimentary rocks (clays). These rocks contain, on an average, 800 p.p.m. of barium. On the other hand, strontium contents are only slightly different: acid eruptive rocks contain, on an average, 300 p.p.m. while basic eruptive and sedimentary rocks contain from 440 to 450 p.p.m. Average values given by Vinogradov (1959) for neutral rocks are 650

100

p.p.m. for barium and 800 p.p.m. for strontium. For carbonated rocks, values are 10 p.p.m. for barium and 610 p.p.m. for strontium. These average values are similar to those of the lithosphere: 500 p.p.m. of barium and 400 p.p.m. of strontium (Vinogradov, 1959; Kovda et al., 1964). The following are some analytical data Concerning barium and strontium content of rocks. These data come from the U.S.S.R., as d o those previously cited:Amur region: sands, pebbles and sandy alluvions, 400-540 p.p.m. of barium and 100-200 p.p.m. of strontium; lacustrine alluvions formed for the most part of clayey loams, 600 p.p.m. of barium and 520 p.p.m. of strontium; flood plain deposits, 450 p.p.m. of barium and 870 p.p.m. of strontium. As for the granite, the barium content is average, but the strontium content is low: 100 p.p.m. (Kovda and Vasil’eyvskaya, 1958). Studies concerning sands of the lower Volga valley have demonstrated the influence of their origin on their barium and strontium contents: ancient alluvial and fluvio glacial sands, 20-100 p.p.m. of barium and 5 0 - 6 0 p.p.m. of strontium; ancient marine sands, 10-270 p.p.m. of barium and about 40 p.p.m. of strontium. Quaternary marine sands are distinctly richer, 170600 p.p.m. of barium and 160--1,000 p.p.m. of strontium (Vakulin and Mokiyenko, 1966).

TOTAL BARIUM AND STRONTIUM CONTENT O F SOILS

According t o Swaine (1955), barium soil contents range from values of 100 to 3,000 p.p.m. and strontium from 50 to 1,000 p.p.m. Vinogradov (1959) gives average contents for these two elements, near those of the lithosphere: 500 p.p.m. of barium and 350 p.p.m. of strontium.

Temperate and boreal regions The upper and lower limits of barium and strontium contents of the soils of these regions are 3,000 p.p.m. and 150 p.p.m. for barium and 800 and 40 p.p.m. for strontium. Mountain tundra soils of the Kola peninsula contain, on an average, 190 p.p.m. of barium and 380 p.p.m. of strontium (Dobrovol’skiy, 1963). In Scotland, podzols formed on granitic till contain 250 p.p.m. of barium and, on gneiss till, 3,000 p.p.m. These soils contain 800 p.p.m. on sandstone, and 1,500 p.p.m. on micaschists. Values of 1,500 p.p.m. of barium were found in brown podzolic soils on serpentinite till, and 2,000 p.p.m. on olivine gabbro till. In these same soils, a podzol, on sandstone till contains 40 p.p.m. of strontium and, on gneiss till, 700 p.p.m. A brown podzolic soil

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on olivine gabbro till contains 800 p.p.m. of strontium (Swaine and Mitchell, 1960). The average contents of podzolic gley soils of the Amur region are about 710 p.p.m. for barium and 440 p.p.m. for strontium (Kovda and Vasil’eyvskaya, 1958). Brown forest soils have, for the most part, average contents. In Scotland values of 600 p.p.m. of barium and 150 p.p.m. of strontium were determined in this type of soil on andesitic moraine (Swaine and Mitchell, 1960). In the Amur region, barium contents d o not go higher than 500 p.p.m. and strontium values attain 280 p.p.m. (Kovda and Vasil’eyvskaya, 1958). In northeastern China, contents are about the same for these soils on basalt: 570 p.p.m. of barium and 270 p.p.m. of strontium (Fanget al., 1963). On the contrary, in Madagascar, a black rendzina on gritty limestone contains much higher concentrations: 2,180 p.p.m. of barium and 625 p.p.m. of strontium (NaloviE, 1969).

Arid and semiarid regions Barium and strontium contents of the soils of these climatic regions are most often rather high. They range from values of 1 0 to 1,500 p.p.m. for barium and from 90 t o 3,000 p.p.m. for strontium; this latter element can attain, moreover, quite exceptional concentrations: 4,300 p.p.m. Chemozems of the Amur region have average contents of barium and strontium: 400 p.p.m. (Kovda and Vasil’eyvskaya, 1958). In Chad, brown isohumic soils on various sediments are richer, containing 1,000 p.p.m. of barium and 200 p.p.m. of strontium (Pias, 1968). Vertisols are also generally rich in these elements: in the Central African Republic, hydromorphic lithomorphic vertisols on amphibolite, and in Chad, topomorphic vertisols on sandy clay sediments, contain 300-1,500 and 900-1,400 p.p.m., respectively, of barium and 100--1,000 and 90-300 p.p.m., respectively, of strontium (Boulvert, 1966; Vizier, 1965). In Madagascar, in the same type of soil on alluvions, the range is narrower between the upper and lower limits: 630-750 p.p.m. of barium and 255380 p.p.m. of strontium (NaloviC, 1969). Equivalent values, 800 p.p.m. of barium and 240 p.p.m. of strontium, are found in a vertisol on limestone-cemented . flysch in New Caledonia (Tercinier, 1966). Subdesert soils of the Ustyurt region, derived from fine loam, contain about average contents: 100-300 p.p.m. However, these contents are widely variable and sometimes exceptionally high in strontium, attaining 4,300 p.p.m. (Dobrovol’skiy, 1961). Very saline alkali soils of Turkmenistan are also very rich in strontium: 700-3,000 p.p.m. These soils also contain high quantities of barium: 700900 p.p.m. (Grazhdan, 1959).

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In Madagascar, in a saline soil on alluvions, and in New Caledonia, in a solodized solonetz on limestone-cemented flysch, barium contents are the same as above: 700-900 p.p.m.; the strontium contents of these soils are much lower: only 90 p.p.m. (NaloviC, 1969; Tercinier, 1966). Tropical hum id regions

The upper limits of barium and strontium contents of tropical soil, 2,000- 3,000 p.p.m. of barium and 1,500-2,000 p.p.m. of strontium, are about the same as those of temperate zone soils and even, in some cases, those of arid zone soils. However, the lower limits are very low: 9-10 p.p.m. of barium and 3 p.p.m. of strontium. Eutrophic brown soils are most often rich in these two elements: in the New Hebrides on basic slags, and, in New Caledonia on limestone-cemented flysch, values, respectively, of 600-1,880 p.p.m. and 800 p.p.m. of barium were determined; strontium content was the same in both cases: 200-300 p.p.m. (Tercinier, 1964, 1966). Gray ferruginous soils have important variations in concentration, and the contents seem to depend on the type of parent rock. Thus, in the Central African Republic, contents are low, 27-100 p.p.m. of barium and 3-9 p.p.m. of strontium, for soils formed on acid eruptive rocks (granite and charnockite), and higher, but widely variable, for soils formed on rocks of metamorphic origin: values of 20-2,000 p.p.m. of barium and 3-80 p.p.m. of strontium were determined on gneiss (Boulvert, 1966). Similarly, in Madagascar, gray ferruginous soils on basic rocks are richer, 1,300 p.p.m. of barium and 350 p.p.m. of strontium, than those on schists, 300 p.p.m. of barium, or on sands, 3 p.p.m. of strontium (NaloviC, 1969). In Chad, gray ferruginous soils with deep pseudogley or concretions, on sandy clay material, contain only 60-150 p.p.m. of barium and 3-10 p.p.m. of strontium (Vizier, 1965). However, in other regions of the country, these same types of soil contain, respectively, 250-1,000 p.p.m. of barium and 20-200 p.p.m. of strontium (Pias, 1968). Ferrallitic soils show similar variations; however, contents are very rarely high. In the Central African Republic, very low contents were found in these soils formed on granite: 9-72 p.p.m. of barium and 2.7-9 p.p.m. of strontium; higher, but very diverse contents were determined in these soils on gneiss or micaschists: 30-720 p.p.m. of barium and 3-90 p.p.m. of strontium (Boulvert, 1966). In Madagascar, ferrallitic soils on volcanic ashes contain 25 p.p.m. of barium. These same soils, on gneiss, contain 1,050 p.p.m. and those on basalt and granite contain about 700 p.p.m. of barium. Strontium concentrations are highest on granite: 310 p.p.m., and lowest on limestone: 4 p.p.m. (NaloviC, 1969).

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In Polynesia, ferrallitic soils derived from basalt and andesitic basalt contain low concentrations of barium, varying in relation t o induration and degree of degradation of the soils:10-30 p.p.m. in soils with indurated subsoils 50-100 p.p.m. in slightly degraded soils 80-300 p.p.m. in strongly degraded soils (Tercinier, 1963). Hydromorphic gley and pseudogley soils are characterized by their extremely variable contents: in the Central African Republic, values of 1703,000 p.p.m. of barium and 25-300 p.p.m. of strontium were determined in hydromorphic gley soils on alluvions (Boulvert, 1966). In Chad, hydromorphic gley soils on clayey material, and halomorphic hydromorphic soils on clayey loam material, are rich in barium, containing from 85 t o 1,000 p.p.m. Values of 130-170 p.p.m. and 280-300 p.p.m. of strontium were found in these soils. On the other hand, hydromorphic deep pseudogley soils on sandy clay material contain only 100-200 p.p.m. of barium and 10-30 p.p.m. of strontium (Pias, 1968; Vizier, 1965). In Madagascar, contents are about the same in a hydromorphic gley soil on alluvions: 450 p.p.m. of barium and 44 p.p.m. of strontium (NaloviE, 1969). Barium and strontium contents of slightly evolved erosion soils vary naturally in relation to the parent rock. In the Central African Republic, these soils on itabirite contain only 18 p.p.m. of barium and 2.7 p.p.m. of strontium, while those on amphibolite contain from 80 t o 1,000 p.p.m. of barium and from 80 to 1,500 p.p.m. of strontium (Boulvert, 1966). On the whole, slightly evolved deposit soils are rich in barium and strontium:In Chad, values of 600 p.p.m. of barium and 1,000 p.p.m. of strontium were determined in a slightly evolved hydromorphic soil on gneiss (Pias, 1968). In Madagascar, on alluvions, contents are about 1,400-1,750 p.p.m. of barium and 95-145 p.p.m. of strontium (NaloviE, 1969). In New Caledonia, on debris of different rocks, or on limestone-cemented flysch, and in the New Hebrides, on acid pumices covering basic slags, contents range from 700 to 900 p.p.m. for barium and from 180 to 300 p.p.m. for strontium (Tercinier, 1966, 1964).

VARIATIONS OF THE BARIUM AND STRONTIUM CONTENT OF SOILS

The analytical results cited above show that, with the exception of some soils of tropical regions, soils contain substantial quantities of barium and strontium, no matter what their type and in what climatic region they developed. The values cited are well within the limits indicated by Swaine (1955).

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The concentrations of these elements depend primarily on the concentrations in the rocks on which they were formed: podzols and podzolic soils of Scotland, gray ferruginous and ferrallitic soils are good examples. Contents can also vary in relation to other factors: fundamental factors of soil evolution (particularly climatic factors such as rainfall and temperature), degree of evolution (for example, intensity of leaching and lixiviation) or secondary factors of soil evolution (erosion and degradation). All these factors explain, in particular, the widely variable concentrations found in the same type of soil formed on the same rock (for example, the gray ferruginous or ferrallitic soils of the Central African Republic). The distribution of these elements between different soil horizons depends, essentially, on the type of soil. Thus, in Scotland, there is an accumulation of barium and strontium in the lower horizons of the soils of the podzolic type on granite, sandstone and schists. On the other hand, in arid and semiarid regions and even in some soils of tropical regions, it is observed that it is most often on the surface that there is an enrichment of barium (soils of Madagascar, Nalovic, 1969). Barium accumulates there as a very slightly soluble sulphate; strontium, being more soluble, is carried away in depth by lixiviation. It is also noticed that subdesert soils and saline alkali soils are rich in strontium, marine deposits being the origin of this enrichment (Vinogradov, 1959). Moreover, the distribution of strontium in rocks follows that of calcium; calcareous soils are often rich in strontium. In arid, semiarid and tropical regions, the soils richest in alkaline earth elements are vertisols, hydromorphic soils or more or less hydromorphic alluvial soils. Hydromorphy conditions seem t o favour the fixing and accumulation of these elements.

BISMUTH According to Vinogradov (1959), bismuth contents of different types of rocks are very low: from 0.007 p.p.m. in basalt t o 0.01 p.p.m. in granite, clay and schists. Swaine (1955) and Kovda et al. (1964), give 0.02 p.p.m. as the average bismuth content of the lithosphere. Bibliographical data concerning bismuth contents of rocks and soils are lacking.

105 TOTAL BISMUTH CONTENT OF SOILS

Bismuth contents of soils (principally tropical and subtropical soils) of the different climatic and geographical zones were determined by arc spectrography. Bismuth is a difficult element t o analyze because the methods employed are not sensitive enough.

Temperate and boreal regions In Madagascar, the upper horizon of a black rendzina on gritty limestone contains less than 8 p.p.m. of bismuth (NaloviE, 1969).

Arid and semiarid regions In the Central African Republic, concentrations of bismuth in vertisols on amphibolite rarely attain 3 p.p.m. (Boulvert, 1966). In the same type of soil, in Madagascar on alluvions, or in New Caledonia on limestone-cemented flysch, contents are low and cannot be determined with exactitude (NaloviE, 1969; Tercinier, 1966).

Tropical hum id regions In the Central African Republic, on different parent rocks (charnockite, granite, amphibolite and gneiss) and in Chad, on sandy clay material, bismuth concentrations of gray tropical and ferrallitic soils are lower than 3 p.p.m. However, in a gray fermginous soil on limestone in Madagascar, a value of 10 p.p.m. was determined. Alluvial soils on alluvions, and slightly evolved erosion soils on itabirite or amphibolite in the Central African Republic as well as hydromorphic or alluvial soils on sandy clay material in Chad also have bismuth contents lower than 3 p.p.m. The highest concentration in the soils studied, 13 p.p.m., was found in he upper horizon of a slightly evolved fluvio-marine deposit soil (mangrove soil) in Madagascar (NaloviC, 1969).

GALLIUM Most rocks of the earth’s crust contain gallium. According t o Vinogradov (1959), basic eruptive rocks contain low quantities of gallium: 15-20 p.p.m.; contents are slightly higher, 20 p.p.m., in acid eruptive rocks (granite.. .) and highest, 30 p.p.m., in metamorphic (schists) and sedimentary (clays) rocks. On the other hand, sandstone and carbonated rocks contain the lowest quantities: 1 2 and 4 p.p.m., respectively (Turekian and Wedepohl, 1961).

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The average concentration of the lithosphere is about 15 p.p.m. (Swaine, 1955). Gallium is most often found in rocks in an alumino-silicated form, and its content varies in relation t o that of aluminium (Vinogradov, 1959). Gallium is easily determined by arc spectrography.

TOTAL GALLIUM CONTENT OF SOILS

Gallium content has been determined for the soils of the different climatic regions. Soil gallium content ranges from values of less than 2.6 to 100 p.p.m. Vinogradov (1959) cites 30 p.p.m. as the average concentration of gallium in soils. Temperate and boreal regions

Total gallium content of soils of these regions ranges from values of 10 to 70 p.p.m. In the U.S.S.R., a concentration of 40 p.p.m. of gallium was found in the peaty horizon of a tundra soil of the Kola Peninsula (Dobrovol’skiy, 1963). In the podzols of Scotland, contents vary in relation to the parent rock: 10-15 p.p.m. for podzols formed on granitic and sandstone till, and 40-70 p.p.m. for podzols derived from micaschists or gneiss till. Brown podzolic soils on serpentinite till or olivine gabbro contain 30 and 50 p-p-m. of gallium, respectively. Also in Scotland, a brown forest soil formed on an andesitic moraine contains 20 p.p.m. (Swaine and Mitchell, 1960). Rendzinas contain average quantities of gallium. In Madagascar, a value of 12 p.p.m. was determined in the upper horizon of a black rendzina on gritty limestone, and in Queensland, Australia, rendzinas contain, on an average, 22 p.p.m. of gallium (Nalovie, 1969; Oertel and Giles, 1963). Arid and semiarid regions

Soil gallium contents of these regions range from 3 to 60 p.p.m. The average concentration is about 20-30 p.p.m. Vertisols have widely variable contents :In New Caledonia, on limestonecemented flysch, gallium contents are low: 4 p.p.m. (Tercinier, 1966). In the Central African Republic, contents are average: 20 p.p.m., for hydromorphic lithomorphic vertisols on amphibolite (Boulvert, 1966) and slightly higher in Madagascar, on alluvions: 13-39 p.p.m., as well as in Queensland: 21-28 p.p.m. (Oertel and Giles, 1963).

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Similar values, 18-22 p.p.m., were determined in the brown isohumic soils of Queensland (Oertel and Giles, 1963). Subdesert soils of the Ustyurt region of the U.S.S.R., formed on fine loam deposits, contain about 16 p.p.m. of gallium (Dobrovol’skiy, 1961). Saline soils (saline soils, saline alkali soils and solonetses) are very often rich in gallium. Thus, in Turkmenistan, saline alkali soils are rich: 10-60 p.p.m. (Grazhdan, 1959). In Madagascar, a value of 35 p.p.m. was found in a saline soil on alluvions (NaloviE, 1969). In Queensland, solod contents range from 13 t o 24 p.p.m. (Oertel and Giles, 1963). However, the concentration of a solod on limestonecemented flysch in New Caledonia is only 3 p.p.m. (Tercinier, 1966). Also in New Caledonia, fersiallitic soils on limestone-cemented flysch are poor in gallium, containing from 3 to 4 p.p.m. (Tercinier, 1966). Mediterranean red soils of Queensland contain from 20 to 24 p.p.m. of gallium (Oertel and Giles, 1963). Tropical h urn id regions The range between the lower and upper limits of the total gallium contents of tropical zone soils is rather wide: from less than 2.6 p.p.m. to 100 p.p.m. However, the average content, 20-30 p.p.m., is the same as for the soils of other climatic zones. This is the case for eutrophic brown soils: values varying from 20 to 30 p-p-m. were found in Ghana on hornblendite and schists, and in the New Hebrides on basaltic slags (Burridge and Ahn, 1965; Tercinier, 1964). Gray ferruginous soils have rather variable contents :In Chad, these soils formed on sandy clay material are relatively poor in gallium: not more than 3 p.p.m. (Vizier, 1965). In the Central African Republic, for the same parent rock, contents are low or average: values of 3 p.p.m. as well as 10-30 p.p.m. have been determined on gneiss (Boulvert, 1966). In Queensland, these soils contain not more than 7 p.p.m. (Oertel and Giles, 1963). In Madagascar, contents vary in relation to the parent rock: contents are low on basic crystalline rocks (less than 2.6 p.p.m.), slightly higher on sandstone and sand and on some limestones (5-10 p.p.m.), and reach 18-19 p.p.m. o n limestone or schists (Nalovii?, 1969). Ferrallitic soils also have widely variable contents :In the Central African Republic, these soils formed on granite or schists are poor in this element: 2.7-9 p.p.m. Very different concentrations can also be found on the same parent rock: values of 4-9 p.p.m. were found in

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soils formed on amphibolite on the one hand, and 60 p.p.m. on the other; on gneiss, 9-50 p-p.m. of gallium were determined (Boulvert, 1966). In Ghana, more or less desaturated ferrallitic soils are richer in gallium when they are derived from basic crystalline rocks or from phyllite, 20 and 40 p.p.m., than when they are derived from granite: 10 p.p.m. (Burrridge and Ahn, 1965). The same phenomenon was observed in the ferrallitic soils of Madagascar: on granite 2.6 p.p.m., on volcanic ashes or basalt or limestone 6-9 p.p.m., and on cipolin 17 p.p.m. (NaloviE, 1969). Likewise, in Australia, Queensland, humiferous ferrallitic soils are a little richer (19-30 p.p.m.) than soils of the same type, but leached (20-22 p.p.m.); krasnozems are the richest: 28-41 p.p.m. (Oertel and Giles, 1963). In Polynesia, concentrations of gallium in ferrallitic soils formed on basalt and andesitic basalt are widely variable: values of 8 and 100 p.p.m. were found in the upper horizons of these soils; when the soils are degraded, gallium contents vary in relation t o the degree of degradation: non-degraded soils, 1 7 p.p.m. and highly degraded soils 7 p.p.m. (Tercinier, 1963). Hydromorphic gley or pseudogley soils :In Chad, these soils formed on sandy clay material are very poor in this element, containing less than 3 p.p.m. (Vizier, 1965). On the contrary, in the Central African Republic, hydromorphic pseudogley soils on alluvions have average contents: 10-20 p.p.m., as does a black soil with temporary hydromorphy, in Dahomey: 10 p.p.m. (Boulvert, 1966; Pinta and Ollat, 1961). Hydromorphic soils and hydromorphic gley soils on alluvions, in Madagascar, are richer, containing 26-36 p.p.m. (NaloviE, 1969). Slightly evolved deposit o r erosion soils:Gallium contents are low, 4.5 and 8 p.p.m., in slightly evolved erosion soils on itabirite or amphibolite of the Central African Republic (Boulvert, 1966). In Polynesia and the New Hebrides, contents are average in slightly evolved deposit soils formed on alluvions of volcanic origin: 12-27 p.p.m., or on acid pumices covering basic slags: 20-30 p.p.m. In Madagascar, contents are higher in a flood terrace soil, 3 7 p.p.m., and in an alluvial bank soil, 47 p.p.m. The highest concentration, 78 p.p.m., was determined in a mangrove soil (Nalovie, 1969).

VARIATIONS OF THE GALLIUM CONTENT O F SOILS

As has been shown above, most soils of the different climatic regions have average gallium contents, corresponding t o those cited by Vinogradov (1959). These contents vary, most often, in relation t o the parent rock. Soils formed from metamorphic rocks contain more gallium than those formed

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from other rock types. This is true for the podzols of Scotland on micaschists and gneiss. Conversely, gray fermginous and hydromorphic pseudogley soils of Chad, on sandy clay material, are very poor in this element. Secondary pedogenic factors can also intervene, particularly in tropical regions: leaching, lixiviation, degree of degradation and soil induration (ferrallitic soils of Polynesia and Australia, Tercinier, 1963; Oertel and Giles, 1963). In temperate and boreal regions, the distribution of gallium is essentially uniform between soil horizons, but content tends to decrease slightly with increasing depth, for example, brown podzolic soils and podzols on serpentinite, sandstone or gneiss in Scotland (Swaine and Mitchell, 1960) and black rendzina on gritty limestone in Madagascar (NaloviE, 1969). On the contrary, in arid, semiarid and tropical regions, soil gallium content increases with soil depth. Conten varies in the same way as that of clay, but not in the same proportion. The accumulation of gallium occurs in the most clayey horizons, as has been shown for the soils of Dahomey (Pinta and Ollat, 1961), and most of the soils of Madagascar (NaloviC, 1969).

GERMANIUM According to Vinogradov (1959), basic eruptive rocks contain, on an average, 1.5 p.p.m. of germanium. Acid eruptive rocks contain 1.4 p.p.m. and metamorphic and sedimentary rocks, 2 p.p.m. Sandstone and carbonated rocks have much lower contents: 0.8 and 0.2 p.p.m., respectively (Turekian and Wedepohl, 1961). Various authors cite a value of 7 p.p.m. as the average concentration of germanium in the lithosphere (Swaine, 1955: Kovda et al., 1964).

TOTAL GERMANIUM CONTENT OF SOILS

Data concerning soil germanium contents are extremely rare. Vinogradov (1959) cites a value of about 1 p.p.m. as the germanium content of the soils of the U.S.S.R. Swaine (1955) cites a value of 10 p.p.m. in some soils of Scotland. The only analytical data available are from various soils of arid, semiarid and tropical regions studied by the Spectrography Laboratory. Germanium is a difficult element to determine because of the lack of sensitivity of the spectrographic method generally used. Values are most often low and the data which follow are only estimations.

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Arid and semiarid regions In the Central African Republic, vertisols on amphibolite contain less than 3 p.p.m. (Boulvert, 1966). In Madagascar, vertisols and saline soils on alluvions contain up t o 9 p.p.m. (Nalovie, 1969).

Tropical humid regions In the Central African Republic, Chad and Dahomey, all the soils studied, gray ferruginous and ferrallitic soils, are also very poor in germanium, containing less than 3 p.p.m. (Boulvert, 1966; Vizier, 1965; Pinta and Ollat, 1961). The highest concentrations have been determined in Madagascar in a gray ferruginous soil formed on schists: 9 p.p.m., and ferrallitic soils formed on granite or cipolin: 14 and 17 p.p.m., respectively (NaloviE: 1969). The soils of New Caledonia (ferrallitic soils, eutrophic brown soils, and slightly evolved deposit soils) on basaltic slaggy tuffs and coralline limestone contain less than 2 p.p.m. of germanium (Tercinier, 1966).

SILVER Rocks generally contain low concentrations of silver. Basic eruptive rocks (basalt), metamorphic rocks (schists) and sedimentary rocks (clays) contain, on an average, 0.1 p.p.m. of silver. In acid eruptive rocks (granite) a value of 0.05 p.p.m. was determined (Vinogradov, 1959). According t o Kovda et al. (1964), the average silver content of the lithosphere is about 0.1 p.p.m.

TOTAL SILVER CONTENT OF SOILS

Soils are also poor in silver. Swaine (1955) gives a value of less than 1 p.p.m. for the average soil silver content. However, some rare soils of Scotland and the U.S.A. contain 2-5 p.p.m. and even up t o 30 p.p.m. of silver. Data concerning soil silver contents of the diverse climatic regions are rare. Analytical results cited below, concerning the soils of arid, semiarid and tropical zones, were obtained from analyses performed by the Spectrography Laboratory.

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Temperate and boreal regions The average silver content of the upper horizon of well-drained podzols of New Brunswick is about 3.8 p.p.m. on sulphide rich bed rocks, and 1.6 p.p.m. on other sediments: in the latter case, the extreme values of about fifty profiles are equal to 0.2 and 7.8 p.p.m. (Presant and Tupper, 1965). In Madagascar, the upper part of a black rendzina on gritty limestone contains less than 2.3 p.p.m. (Naloviti, 1969).

Arid and semiarid regions A value of less than 3 p.p.m. of silver was determined in the hydromorphic lithomorphic vertisols of the Central African Republic and in those of Madagascar, on alluvions (Boulvert, 1966;Nalovi&,1969).

Tropical hum id regions Tropical soils are also very poor in silver. Gray ferruginous and ferrallitic soils:In the Central African Republic and Dahomey, these soils on different parent rocks (charnockite, gneiss, amphibolite, etc.) contain less than 1 p.p.m. of silver (Boulvert, 1966;Pinta and Ollat, 1961). In Chad, on sandy clay material, contents range from less than 1 p.p.m. to 3 p.p.m. (Vizier, 1965). In Madagascar, concentrations are lower than 2 p.p.m. in these types of soil on granite, gneiss, limestone and sand, but they attain 5 p.p.m. in the upper horizon of a ferrallitic soil on basalt (Naloviz, 1969). In Polynesia, contents are higher: ferrallitic soils with an indurated subsoil and degraded ferrallitic soils on andesitic basalt contain 3-7 p.p.m. of silver. The highest concentration, 24 p.p.m., was found in the upper horizon of a non-degraded ferrallitic soil on basaltic debris (Tercinier, 1963). Hydromorphic soils:In Chad, in the upper horizons of a shallow hydromorphic surface gley soil and a hydromorphic deep pseudogley soil, concentrations are lower than 3 p.p.m.; in the lower horizons of these same soils concentrations are equal to 3 p.p.m. (Vizier, 1965). Slightly evolved deposit or erosion soils:In the Central African Republic, a slightly evolved erosion soil on itabirite contains less than 3 p.p.m. of silver; however, in Madagascar, the upper horizons of slightly evolved deposit soils are richer: 5-9 p.p.m. of silver (Naloviti,

1969). Except for a few cases, all the soils analyzed show low concentrations of silver.

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TIN Tin contents of rocks vary according t o the type of rock. They are lower, 1.5 p.pm., in basic eruptive rocks (basalt, gabbro.. .) than in acid eruptive rocks, such as granite, 3 p.p.m., and than in metamorphic and sedimentary rocks (schists and clays), 10 p.p.m. (Vinogradov, 1959). The average concentration of the lithosphere is about 40 p.p.m. (Swaine, 1955; Kovda e t al., 1964).

TOTAL TIN CONTENT OF SOILS

Tin is rarely determined in soils, and data are rare. According t o Swaine (1955), soils contain up t o 10 p.p.m. of tin.

Temperate and boreal regions In New Brunswick, Canada, an average value of 7.1 p.p.m. of tin was found in the upper horizons of podzols formed on sulphide rich bed rocks; in soils of the same type, formed on other sediments, the average content was about 2.3 p.p.m., the upper and lower limits being 9.1 and 0 p.p.m. (Presant and Tupper, 1965). In northeastern China, a value near 6 p.p.m. was determined in brown forest soils on basalt (Fang e t al., 1963). On the contrary, in Madagascar, the upper horizon of a black rendzina on gritty limestone contains less than 2.4 p.p.m. (NaloviE, 1969). The maximum content was found in Poland in soils close to mining deposits: 50 p.p.m. (Sarosiek and Klys, 1962).

Arid and semiarid regions The analytical data cited below are from analyses performed by the Spectrography Laboratory of the “Services Scientifiques Centraux de 1’0.R.S .T.O.M .” Soil tin contents range from less than 3 p.p.m. t o 50 p.p.m. In New Caledonia, fersiallitic soils on limestone-cemented flysch contain from 7 t o 8 p.p.m. (Tercinier, 1966). Vertisols have widely variable tin contents. Thus, in the Central African Republic, hydromorphic lithomorphic vertisols on amphibolite contain from less than 3 t o 50 p.p.m. (Boulvert, 1966). In Chad, topomorphic vertisols on sandy clay sediments contain, on an average, 3 p.p.m. of tin (Pias, 1968). In Madagascar, vertisols on alluvions have tin contents of less than 3 p.p.m. and, in New Caledonia, topomorphic vertisols on limestone-cemented flysch contain 4 p.p.m. (NaloviE, 1969; Tercinier, 1966).

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Saline soils (saline soils and solonetses) have about the same tin concentrations: less than 3 p.p.m. in the saline soils on alluvions, in Madagascar, and 7 p.p.m. in a solodized solonetz on limestone-cemented flysch, in New Caledonia (NaloviC, 1969; Tercinier, 1966).

Tropical hum id regions In the soils studied, tin contents range from less than 1p.p.m. to 60 p.p.m. With few exceptions, the gray femginous soils and ferrallitic soils studied contain from less than 3 to 1 0 p.p.m. of tin. In the Central African Republic, these soils formed on different parent rocks (gneiss, amphibolite, charnockite, granite, etc.) contain, for the most part, 3 p.p.m. or less. An exceptional value of 60 p.p.m. was found in the lower horizon of a gray ferruginous soil on amphibolite (Boulvert, 1966). It is the same for these soils in Chad, on sandy clay material (Pias, 1968; Vizier, 1965). In Dahomey, concentrations are slightly higher: 3 p.p.m. in a gray femginous and “terre de barre” soil and 16 p.p.m. in a slightly ferrallitic clayey soil (Pinta and Ollat, 1961). In Madagascar, gray ferruginous and ferrallitic soils, formed on granite, limestone and volcanic ashes, are very poor in tin: less than 2.7 p.p.m., with the exception, however, of a ferrallitic soil on granite and another on cipolin, in which values of 2.8 and 6 p.p.m. were determined (Nalovie, 1969). Contents are also very low in more or less degraded ferrallitic soils with indurated subsoil, less than 1 p.p.m., formed on basalt and andesitic basalt, in Polynesia (Tercinier, 1963). Hydromorphic and alluvial soils:In the Central African Republic, hydromorphic pseudogley soils on alluvions, contain up t o 3 p.p.m. of tin (Boulvert, 1966). In Chad, in the same type of soil on gneiss or sandy clay material, and in New Caledonia on limestone-cemented flysch, concentrations are about 9-10 p.p.m. (Pias, 1968; Vizier, 1965; Tercinier, 1966). On the other hand, in Dahomey, a value of 27 p.p.m. was determined in the upper horizon of a tropical black soil with temporary hydromorphy (Pinta and Ollat, 1961). Slightly evolved deposit soils:These soils also have widely variable concentrations: in New Caledonia, on various types of rock debris, they contain less than 3 p.p.m. of tin, on limestonecemented flysch they have tin values of 4 and 7 p.p.m. and, in Madagascar contents reach 22 p.p.m. in the upper horizon of a mangrove soil (Tercinier, 1966; NaloviC, 1969). On the whole, the tin contents of the various soil types in the different climatic zones, that have been analyzed by the Spectrography Laboratory, are very low and are close t o the contents cited by Swaine (1955).

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The distribution of tin between the different horizons of soil profiles generally follows that of organic matter and clay. An accumulation of this element is noticed in the surface horizon, particularly in soils with high organic matter contents and in soils with temporary or permanent hydromoqhy. This has been shown in Madagascar, in a mangrove soil, and in Dahomey, in a black tropical soil (NaloviE, 1969; Pinta and Ollat, 1961). Besides, in some tropical soils, in which the organic layer is not very thick, tin accumulates at depth, in the clayey horizon. This is the case for ferrallitic soils of Dahomey and Chad (Pinta and Ollat, 1961; Pias, 1968).

See also the following works published since 1968: POLAND: Boratyfiski, K., Roszyk, E. and Zietecka, M., 1972; Dobnaiiski, B., Glifiski, J., Cao Thai, V., 1971. U.S.S.R.: Andrianova, G.A., 1971 ; Araratyan, L.A., 1971 ; Do-Van-Ay, Borovik-Romanova, T.F., Koval’skii, V.V. and Makhova, N.N., 1 9 7 2 ; Gyul’akhmedov, A.N. and Mugalinskaya, E.A., 1970. U.S.A.: Bradford, G.R., Bair, F.L. and Hunsaker, V., 1971. CAMEROUN: NaloviE, L. and Pinta, M., 1972. NEW ZEALAND: Wells, N. and Whitton, J.S., 1972.

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CONCLUSION Trace elements can be found in most rocks of the earth’s crust and in practically all the soils of the diverse climatic regions of the globe. The concentrations of these elements in rocks depend upon the type of rock and the trace element considered. Ultrabasic eruptive rocks (dunite, peridotite, etc.) and basic rocks (basalt, gabbro, etc.) are rich in cobalt, chromium, copper, nickel, vanadium and zinc and relatively poor in lithium, rubidium, caesium, barium and strontium. Acid eruptive rocks (granite, rhyolite, etc.), on the contrary, are rich in alkaline and alkaline earth elements, boron and tin and poor in chromium, cobalt, copper and nickel. Contents of the trace elements mentioned above in metamorphic rocks (gneiss and schisk) and some sedimentary rocks (clays), fall between those of basic eruptive and acid eruptive rocks. Moreover, these rocks are richer in iodine, molybdenum and lead, as are sandstones and carbonated rocks. These two latter types of rocks are generally poorer in trace elements than crystalline rocks. Boron and, especially, iodine contents of various sedimentary rocks of marine origin attain 100 p.p.m. and sometimes even 1,000 p.p.m. Soil contents of trace elements are, on an average, about the same as those of the parent rocks on which the soils were formed. Therefore, for a given type of soil, contents vary widely, according to the nature of this parent rock. In Scotland, for example, podzols on serpentinite have much higher cobalt and nickel contents than those formed on granite and schists. Similarly, in Ghana, cobalt, copper, nickel and vanadium contents of moderately desaturated ferrallitic soils vary according to the parent rocks, soils on granite being poorer in these elements. However, the range of these concentrations is generally wider in soils than in rocks. For example, the upper and lower limits for cobalt, chromium and zinc are, respectively: 200 p.p.m. and traces, 3,000-4,000 p.p.m. and traces, and 900 p.p.m. and traces. For some elements, such as boron, iodine, molybdenum and lead, soil contents are much higher than those of the parent rocks and may seem to have no relation to them. Thus, molybdenum contents range from traces t o 20-25 p.p.m., for example. Trace element contents and distribution can clearly depend upon processes which led to the formation of the soil: ferrallitisation, ferruginisation, podzolization, accumulation, etc., which are themselves functions of various climatic, biological and other factors. In soils, there is a positive relationship between trace element content and that of fine mineral elements (clay and clay + silt) and, even more, that of humus. This relationship may be demonstrated for most elements, even those which can only be found in very low quantities, such as iodine, molyb-

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denum and selenium. Thus iodine contents are highest in very humiferous and heavy-textured soils. This also applies to molybdenum and selenium. Therefore the distribution of elements between different horizons of a profile is related, in most cases, to the humus and clay content. There is generally an accumulation, which seems t o be of biogenetic origin, in the upper horizons rich in organic matter: trace elements contained in the debris left by vegetation in the soil or on its surface are released when the vegetation decays. In some tropical soils, where the humiferous horizons are not very thick, trace element concentrations are the highest in the lower clayey horizons (soils of Dahomey). Sandy soils are very often deficient in elements all along their profile. Trace elements are found in soils in various forms and as mineral or organic compounds whose solubility depends on soil pH. Thus, compounds of cobalt, copper, nickel, manganese, etc. are soluble in an acid medium (pH lower than 6) while, on the contrary, molybdenum compounds are soluble in an alkaline medium. Generally, heavy rainfall increases soil acidity (podzols and ferrallitic soils) and acid soils are poorer in cobalt, copper, nickel, manganese, etc. which are easily lixiviated by very abundant percolation waters. The redox potential also plays a part in the mobility of trace elements. This potential depends on the presence, position and, if it occurs, movement of groundwater, as well as the possible more or less temporary water-logging of certain soil horizons. Finally, this potential also depends on soil porosity, as well as on the general oxidation conditions of the soil and the possible presence of certain reducing agents. Seasonal variations have been observed in the soil contents of certain elements, such as nickel and cobalt, which appear to be linked to that of the ratio ferrous-Fe, ferric-Fe, an expression of the pattern of development of the redox potential. Therefore, trace element concentrations are highest in soils rich in humus, fine-textured and having a neutral or alkaline pH, for example, the chernozems and vertisols of semiarid regions. In a given region, trace element concentrations of chernozems are often higher than those determined in other types of soil, and the distribution of these elements is uniform between the different horizons. On the other hand, contents are often very low in podzols, podzolic and leached soils, and the accumulation of trace elements occurs in the illuvial B horizons. On the contrary, eluvial upper horizons are poor in trace elements. In other types of soil, such as brown forest soils, rendzinas of temperate regions, brown isohumic soils, fersiallitic soils, saline soils of semiarid regions, gray ferruginous soils and ferrallitic soils of tropical regions, hydromorphic and alluvial soils, slightly evolved soils, etc., contents depend on the extent of the influence of one or other of the factors mentioned above. Thus, there is an accumulation of cobalt, copper, manganese and nickel in the gley

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horizons of the poorly drained hydromorphic soils of Scotland. Peaty soils are rich in molybdenum and brown forest soils generally contain sufficient quantities of all the elements. Boron, cobalt, copper, molybdenum and zinc contents are high in solonetses and richly saline alkali soils. Collected data seem t o show that trace element contents of tropical soils may also depend on their degree of evolution as, for example, the intensity of the leaching phenomena that are produced. This is particularly true for gray ferruginous and ferrallitic soils, whose trace element concentrations are often widely variable for a given parent rock. “Total” trace elements constitute, in a way, the soil reserves of these elements, but it is also interesting to know the contents of trace elements “available” to plants. “Plant available” contents depend not only on total element contents, but also on soil pH and rH, as well as on soil humus and organic matter contents. Thus, peaty soils, very rich in total copper are nevertheless deficient in “plant available” copper because the organic compounds formed with this metal are generally insoluble in the existing physico-chemical conditions of these soils. To sum up, trace element contents of soils are the result of the respective influence of the parent rocks and various pedogenic factors. The concentrations of plant-available elements give rise to the phenomena of deficiency or toxicity of soils. Deficiency generally occurs in podzols, podzolic soils, peaty soils, hydromorphic gley soils, acid pH soils subjected t o intensive leaching, sandy soils and soils on acid eruptive rocks. Deficiency is also found in alkaline pH soils where mineral and organic compounds of these elements are only very slightly soluble. On the other hand, cultivation conditions such as intensive liming in the case of boron and manganese, or the supplying of phosphorus fertilizers in the case of zinc, may also cause deficiency. These deficiencies are generally corrected with the aid of fertilizers containing the deficient elements and by controlled liming. Toxicity is often caused in the same way: parent rocks rich in trace elements and a soil with an acid pH, as in the case of manganese, for example. On the contrary, in the case of molybdenum, toxicity generally occurs in heavy-textured and more or less hydromorphic alkaline soils derived from calcareous rocks. Some toxicities are due to man’s interference, either directly, as in the case of anticryptogamic treatments with copper sulphate (southwestern France), or indirectly, as the result of a very strong cultivation acidification (manganese toxicity in the Niari Valley of the Congo). It is impossible to judge the fertility of soils without a sufficient knowledge of total and plant-available soil trace element contents and their distribution in profiles, which is partially influenced by the principal pedogenic factors.


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REFERENCES UP TO 1968 Agrawal, H.P. and Motiramani, D.P., 1 9 6 6 . Copper status in soils of Madhya Pradesh. J. Indian SOC.Soil. Sci., 14(3): 161-171. Alban, L.A. and Kubota, J., 1 9 6 0 . A study of extractable soil cobalt of the southeastern United States. Soil. Sci. SOC.Am. Proc., 24(3): 183-185. Anderson, M.S., Lakin, H.W. and Beeson, K.C., 1 9 6 1 . Selenium in Agriculture. U.S.D.A. Agric. Handb., No. 2 0 0 , 6 5 pp. Anjaneyulu, B.S.R., 1 9 6 4 . Availability of manganese in some Indian soils growing sugarcane. J. Indian SOC.Soil. Sci., 12(4): 269-273. Archer, F.C., 1963. Trace elements in some Welsh upland soils. J. Soil. Sci., 1 4 : 144-148. Aslanyan, G S h . , 1 9 6 1 . Effect of boron fertilizer o n yield and quality of potato tubers. Agrobiologiya, 3: 452-454 (in Russian). Asmus, F., 1 9 6 1 . Zur Kupfer- und Kobaltversorgung einiger Grundlandboden. Rocz. Glebozn., 1 0 : 263-268. Asratyan, G.S., Stepanyan, M.S. and Shmavonyan, D.M., 1965. Iodine content of soils and occurrence of endemic goitre in t h e Radzan region of the Armenian SSR. Izv. Akad. Naukarmyan SSR Biol. Nauk., 18(10): 23-28 (in Russian). Atlavina, S.A., 1 9 6 5 . Some regularities in t h e distribution of zinc, copper and manganese in meadow irrigated soils of t h e middle reaches of the Amu-Dar. Izv. Akad. Nauk. Turkmen SSR, Biol. Nauk., 5: 53-59 (in Russian). Aubert, G., 1 9 5 6 . Les micro Blements dans les sols. Comm. SOC. GBochim. Paris XII, 1 9 5 6 . Bull. PBdo. ORSTOM, 1 9 5 7 , 7 ( 1 ) : 4-5. Aubert, G., 1 9 6 5 . Classification des sols. Tableaux des classes, sous-classes, groupes e t sous-groupes de sols, utilisBs par la section de PBdologie de I’ORSTOM. Cah. PBdol. ORSTOM, I I I , 3 : 269-288. Badhe, N.N. and Zende, G.K., 1962. Cobalt status of Konkan soils in relation to pH, organic carbon, lime and iron. Indian J. Agron., 6: 304-310. Bgjescu, I., 1 9 6 4 . Contribution to t h e study of exchangeable and active manganese in soil of Oltenia. Anal. Inst. Cent. Cer. Agric. Sect. Pedol., 32: 211-219 (in Roumanian). BHjescu, N. and BHjescu, I., 1960. The copper, zinc, nickel and cobalt content of soils in the eastern part of the Olt region. Biol. Stunje Agric. Bucuresti, pp. 301-305 (in Roumanian). BHjescu, I. and Chiriac, A., 1962. Some aspects of t h e distribution of copper, cobalt, zinc and nickel in soils of the Dobrudja. Anal. Inst. Cent. Cerc. Agric., 3 0 A : 79-87 (in Roumanian). Bgjescu, I. and Salzman, S., 1 9 6 5 . Boron in some soils and running waters in the south of Rumania. Anal. Inst. Cent. Cerc. Agric., 3 3 : 111-120 (in Roumanian). Balks, R., 1 9 6 1 . Untersuchungen uber den Bleigehalt des Bodens. Kalibriefe Fachgeb., 1 , 1 1 , Folge, pp. 1-7. Banfi, G., 1960. The influence of zinc o n the growth of certain vegetable species. Trans. 7th Int. Congr. Soil. Sci., 3 : 554-562. Barufke, W., 1 9 6 2 . Uber die Bedeutung des Kobalts als Spurenelement auf brandenburgischen Grunlandbodei. Wiss. Z. Humboldt. Univ. Berlin, Math. Naturwiss. Reihe, 11: 135-144. Beer, K., 1966. Untersuchh ,gen uber Vorkommen und Bindungszustand des Mangans in typischen thuringer Boden. Chem. Erde, 25(4): 282-299. Beer, K., Grundler, C. and Prausse, A., 1 9 6 6 . Einfluss von Kalkung und Dungung auf die Dynamik der Manganfraktionen in thuringer Buntsandsteinverwitterungsboden und auf die Manganaufnahme von Solanurn tuberosurn L. Albrecht-Thaer-Arch., 10: 906926.

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141 Prasad, R.N. and Pagel, H., 1973. Vergleichende Untersuchungen iiber den Gehalt an “verfiigbarem” Bor in wichtigen Boden der ariden und humiden Tropen. Arch. Acker Pflanzenbau Bodenkunde, 17(4): 271-281. Rai, M.M., Shitoley, D.B., Pal, A.R., Vakil, P. and Gupta, S.K., 1970. Available micronutrient status of deep black soils of Madhya Pradesh. J. Indian SOC.Soil Sci., 18(4): 383-389. Rai, M.M., Digue, J.M. and Pal, A.R., 1972a.Availability of copper in deep black soils of Madhya Pradesh. J. Indian SOC.Soil Sci., 20(2): 135-142. Rai, M.M., Pal, A.R. and Shitoley, D.B., 1972b. Available molybdenum status of deep black soils of Madhya Pradesh. J. Indian SOC.Soil Sci., 20(1): 53-58. Rai, M.M., Pal, A.R., Chimania, B.P., Shitoley, D.B. and Vakil, P., 1972c. Available micronutrient status of shallow black soils of Madhya Pradesh. J. Indian SOC.Soil Sci., 20(2): 129-134. Randhawa, N.S., 1971. Present status of micronutrient research in India. World Soil Resources Reports, 41 : 91-95. Rao, P.S. and Hadimani, A.S., 1971. Manganese status of some soils in northern districts of Mysore state. Mysore. J. Agric. Sci., 5(3): 243-251. Regus, J.R., 1969. Cobalt and copper contents of some tropical soils and grasses from Puerto Rico. J. Agric. Univ. P. Rico, 53: 348-356. Reid, A.S.J. and Webster, G.R., 1969.The manganese status of some Alberta soils. Can. J. Soil Sci., 49(1): 143-150. Rudneva, E.N., Verigina, K.V. and Dobritskaya, Yu.I., 1972. Content of trace elements in some soils and parent material of Karelia. Pochvovedenie, 10: 26-38 (in Russian). Sadowski, S. and Dunat, S., 1968.Available molybdenum contents of some soils of Kozle and Prudnik regions. Roczn. Gleboz., 19(2): 267-280 (in Polish). San’ko, P.M., Klebanovich, V.F. and Sinitsa, L.A., 1971. Content of zinc in soils of Belorussian SSR. Agrokhimiya, 12:96-105 (in Russian). San’ko, P.M., Lozovskii, L.I. and Sinitsa, L.A., 1973a. Iodine in soils of White Russia. Agrokhimiya, 7: 111-118 (in Russian). San’ko, P.M., Lozovskii, L.I. and Sinitsa, L.A., 1973b. Iodine in grasses and soils of meadows, ground water and lacustrine silts of White Russia. Agrokhimiya, 10: 110118 (in Russian). Sapetti, C. and Arduino, E., 1973. Inquinamenti da piombo nei pressi dell’ autostrada Torino-Milano. Agrochimica, 17(6): 540-545. SaviE, B, and JekiE, M., 1968.Contribution of the study of the manganese, copper and zinc content of smonitza in Macedonia. Arh. Poljopr. Nauke Tch., 21: 122-128 (in Croatian). Schnorr, H. and Bergmann, W., 1968. Uberblick iiber die Mikronahrstoffversorgung der Boden der Bezirke Rostock, Schwerin und Neubrandenburg. 2 Mitteilung: die Bor und Molybdanversorgung. Albrecht Thaer-Arch., 12(12): 1113-1118. Shanker, H. and Dwivedi, K.N., 1972.Zinc status of some soils of Uttar Pradesh. Indian J. Agric. Res., 6(3):196-200. Sharma, B.M. and Deb, D.L., 1974. Copper status of soils of Union territory of Delhi, with special references to cropping sequence. J. Indian SOC.Soil Sci., 22(2): 145-150. Sharma, O.P. and Shinde, D.A., 1968. Manganese status of black soils of Indore districts. J. Indian SOC.Soil Sci., 16(1):65-69. Sharma, R.C. and Shucka, U.C., 1972. Boron status of Bhuna soils of Hissar district, Haryana. Indian J. Agric. Res., 6(4): 285-288. Sharova, A.S., Sklyarov, G.A. and Artem’eva, K.A., 1970.Molybdenum content of forest soils of the northern subzone of the taiga of the European North of the USSR. Agrokhimiya, 8: 94-98 (in Russian). Shirokov, V.V. and Panasin, V.I., 1972.Content of mobile copper, zinc, cobalt, boron, manganese and molybdenum in the main soil groups of polders in Kaliningrad oblast. Sov. Soil Sci., 3: 341-344.

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Sillanpaa, M., 1 9 7 2 . Trace elements in soils and agriculture. Soil Bull., F.A.O., 1 7 , 6 7 pp. Silva Teixeira, A.J. da, Menezes de Sequeira, E. and Lucas, M.D., 1 9 7 1 . Soil micronutrient map of Portugal. Agron. Lusit., 31(4): 293-304. Singh, D., Denge, R.S. and Dixit, R.C., 1 9 7 1 . Copper status of medium blacksoils(1ndore District) Jawaharlal Nehru Krishi Vishwa Vidyalaya. Res. J., 5(2): 14-17. Singh, L. and Singh, S., 1 9 7 3 . Distribution of cobalt in kankan and soils of Vindhyan region of Mirzapur (India). Proc. Indian Nat. Sci. Acad., part B, 3 9 ( 1 ) : 136-141. Singh, M., 1970. Distribution of manganese in tropical and brown sierozem and desert soils of erstwhile Punjab (India). Agrochimica, 1 4 : 565-576. Singh, M., 1971. Availability of manganese in submerged paddy soils as affected by pH, anions, iron, organic matter. Riso, 2 : 165-170. Singh, M. and Pathak, A.M., 1 9 6 9 . Manganese in relation t o climate and soil character. Agrochimica, 1 4 : 213-222. Singh, R. and Singhal, J.P., 1 9 7 0 . Distribution of trace elements in Aligarh soils. Agrokem. Talajt., 1 9 : 69-77 (in Hungarian). Singh, S. and Jain, R.K., 1 9 7 1 . Forms of copper in t h e soils of Narsinghpur, district of Madhya Pradesh. Indian J . Agric. Res., 5(4): 271-274. Singh, S. and Singh, L,, 1 9 6 9 . Manganese status of some soils of Vindhyan region of Mirzapur (U.P.). Indian J. Agric. Chem., 2 : 74-82. Singh, S. and Singh, R.S., 1 9 7 2 . Studies o n water soluble boron in magnesium rich saline alkali soils of south west of Bihar. J. Indian SOC.Soil Sci., 20(2): 143-149. Singh, S. and Singh, S.B., 1 9 7 1 . Boron status in t h e soils of Mariahu Tehsil. Allahabad Fmr., 4 5 ( 4 ) : 373-376. Sinitskaya, G.I., 1 9 6 9 . Iodine content in t h e Zeya-Bureya plain soils. Uchen. Zap. Dal’nev. Gosud. Univ., 27: 72-88 (in Russian). Six, L., 1 9 7 0 . Investigations o n zinc content in profiles of alluvia of the Rdba river. AgrokBm. Talajt., 1 9 : 311-322 (in Hungarian). Six, L., 1971a. Investigations o n t h e zinc content of some soil profiles formed o n Danube alluvia of t h e little Hungarian plain. AgrokBm. Talajt., 20(1/2): 107-118 (in Hungarian). Six, L., 1 9 7 1 b . Investigations o n the zinc content of some profiles in the Marcal Valley. Mosonmagy. Mezog. Kar. Kozl., 1 4 (3): 29-51 (in Hungarian). Six, L. and Lukdcsy, D., 1971. Investigations of the total zinc content of soils in t h e Hansag. Mosonmagy. Mezog. Kar. Kozl., 1 4 ( 3 ) : 53-73 (in Hungarian). Six, L. and Nagy, L., 1 9 7 2 . Investigations of t h e mobile zinc in chernozems in t h e Saponya district of the Mezofold. Mosonmagy. Mezog. Kar. Kozl., 1 5 ( 3 ) : 77-96 (in Hungarian). Sri Vasta, A.R., Dubey, R.R. and Sinha, H., 1970. Manganese status of Bihar soils. Indian J. Agric. Chem., 3: 42-48. Stanton, D.A., Du, T. and Burger, R., 1 9 7 0 . Studies o n zinc in selected Orange Free State soils. IV - Factors affecting t h e availability of zinc. Agrochemophysica, 2(2): 33-40. Staszewski, T. and Kociaikowski, Z., 1974. Some microelements in black earths of szamotuly glacial basin. Roczn. Gleboz., 25(2): 113-114 (in Polish). Stoilov, G. and Atanasov, I., 1 9 7 1 . Distribution of manganese, iron, cobalt and copper in mechanical fractions of chernozem smonitza. Izv. Timiryazev. se1’-Khoz. Akad., 3 : 141-148 (in Russian). Stoyanov, D. and Stefanova, V., 1969. Water soluble selenium in certain soil types in Bulgaria. Pochv. Agrokhim., 4(2): 3-5 (in Bulgarian). Sviridov, A.S., Kazakova, Ye.G., Sviridova, E.V. and Belosokhova, N.F., 1 9 6 9 . Content o f available minor elements in the chernozems of Tambov oblast. Sov. Soil Sci., 5: 557561. Takkar, P.N., 1970. Distribution of iron and manganese in meadow forest non calcic brown and gray brown podzolic soils of the Himachal Pradesh (India). Geoderma, 3: 215-222.

143

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144 BORON 1 ;OIL TYPE

31L CLASSIFIATION SYSTEM ;h APPROXdATION J.S.D.A.)

phagnum peats and organic soih andy and clay soils

dmaquept

Netherlands

iumus sandy soils

ydraquent

France Gascony

:aleareow soils (9 t o 18%) ich in clays (29 t o 43%)

LOCATION

'ARENT ROCK 4ND PARENT IOCK CONTENT u.u.m.)

Finland

:OTAL BORON >ONTENT P.u.m.)

IORIZON

Denmark

11 soil

rpic eutrochrept

niocene sandstones

n subsoil

ion calcareous soil! ( 0 t o 0.8%) pH rich in clays study of boron in element

France Italy

Switzerland

Germany

various limestones: 8 red muschelkalk: 80 paleozoic schists: 80-100

I

IS

in relation to g(

:hemistry of this

146 BORON 1 ~~

AVAILABLE T O PLANTS BORON CONTENT (p.p.m.)

IORON 7ARIATIONS

IEFICIENCY )R TOXICITY

FFECTS O F ‘ERTILIZERS

~

LEFERENCES

Curki, M., 1062

iming reduces boron availability, effect is greater o n a sandy soil than o n a loam soil: five soil types show considerable variations in fixation and leaching of boron

.o risk of boron toxicity when small borax applications are made t o soils al short intervals

ensen. J.. 1964

ffect of liming o n boron availability depends on organic matter content and PH

0.31-0.91

vailable boron decreases with increasing pH

.ehr, J.J. and Henkens. C.H., 1962

n alkaline or calcareous soils the limit of def ciency in vine i! 0.75

pplication of borax has a favourable effect o n formatioi and growth of fruii

)ecau. J . et al.. 1962

0.084.51

eficiency in vine produces “millerandago” disease in grape

Caurice, R

1961

‘eatment with 10-40 glplant borax has a favourable effect o n grapes

:ifem, R.,

961

roadcasting of 30 kgl ha borax is n o t toxic for clover o n soils well provided with P. K , Ca. Bapplication of the same amount as a spray depresses growth and decreases yield

.immerman. W.,1961

teide. F. and Thiele, A.. 1958

146 BORON 2 LOCATION

'ARENT ROCK \ND PARENT 3OCK CONTENT p.p.m.)

Germany Thuringia

limestone and loess soils 3untsandstein soils on these and highly parent weathered slate materials

SOIL TYPE

SOIL CLASSIFICATION SYSTEM 7th APPROXIMATION (U.S.D.A.)

Germany Thuringia

Studies o n boron in several hundred soil

Germany Thuringia

arable soils

Germany Mittelgebirge

divine nephelinite liabase, granodiori neiss. phyllite, quartz lorphyry

Germany East ern Bavaria

podzols podzols brown earths

heavy soils: parabraunerde pararendzinas pseudo-gley soils

Austria pre-alpine region

Czechoslovaki; Beskydy mountains

Yugoslavia Serbia

Poland

lates

loamy soils

andstone

acidic sandy soils

POTAL BORON :ONTENT P.P.m.)

HORIZON

i

spodosols ochrept

A. B, C

ochrept eutrochrep t aquents

loron amounts are always lower than those o f parent materials

chernozems slightly leached an degraded chernozems meadow chernozems carbonate chernozems podzols acid bog soils saline soils solonets soils

ustolls

podzolic sandy soils

~podosols

argiustolls

16.8-38.6 18 and 16.9-29.8

aquic argiustolls

18

trgiustolls

12.3

~podosols umbraquept natric salorthid natrargid

:0.9 1.3-25.3 ,5.3 .0.5-66.8

iccumulation in B horizons loron is leached from B horizon

biological accumulation o f boron in the upper horizons

147

BORON 2 AVAILABLE TO PLANTS BORON CONTENT (p.p.m.)

BORON VARIATIONS

water-soluble boron: tends to be high water-soluble boron: low

,oron contents increase with increas ing amounts of clay + silt

]E4

1.2

DEFICIENCY l R TOXICITY

EFFECTS O F FERTILIZERS

REFERENCES

M a i n , B. and Sasum, K.. 1962

Bergmann, W. e t al., 1962 hot water soluble boron: 0.4-0.87

,oron content varies with PH, clay content and soil parent material. Boron val ues are subject to marked seasonal variations

Buchel, L. and Bergmann, W.,1966

)oron contents vary according t o parent rock

LentWhig. S. and Fielder, H.J., 1966

hydrochloric acid extracts

Rid. H. and Schiecke, I., 1965

majority of soils contain 0.36 to 0.10 of h o t water soluble boron

SchiIler. H., 1961

ficiencies in boron

water soluble boron represents 2.98%

2.3% 3.15% 2.45%

Beneg. S., 1964

>ositivecorrelation between humus content and soluble boron. Boron is higher in humus horizon. bu. does not change sig nificantly with depth. in podzols

Kosanovic', V. and Halasi, R., 1962

1.89

vater soluble boron was increased from 0.084.13 to 0.120.15 by mineral fertilizers and from 0.08-0.13 t o 0.204 3 by farm yard manure

farm yard manure has a higher effect than mineral fertilizers o n water soluble boron

lobrzadski, B.. 1960


'ARENT ROCK i N D PARENT LOCK C O N T E N T p.P.m.)

OIL T Y P E

iOIL CLASSIFI:ATION SYSTEM ' t h APPROXMATION

'OTAL BORON :ONTENT

HORIZON

P.p.m.)

U.S.D.A.) Poland

ght podzolized soils

Poland Lublin

lkaline humus rendzina soils rown soils

Poland

endzina rown soils lack earths odzolic soils ok lessivds

Pc nd Lodz boulder clays

cultivated horizons

endolls Bchrept

rganic soils lluvial soils

endoll Bchrept lStOll.9 podosols llfisols or ultisols iistosols luvent

odzolic soils r o w n earths lack earths endzinas eat bog soils

podosols Bchrept 1stolls endolls iistosol

he same soils

Hungary

5 chernozem profiles

cultivated horizons subsoil

i

5-73

top layer

0-20 cm

deeper layers

Istolls

149

BORON 3 AVAILABLE TO PLANTS BORON CONTENT (p.p.m.)

lORON IARIATIONS


available boron in t h e cultivated layer of sandy podzols was 6.4 to 8.5% of total boron

ivailable and total boron contents increase with increasing humus content of cultivated layer

ZFFECTS O F ?ERTILIZERS

EFERENCES

farm yard manure has a higher effect than mineral fertilizers o n total ant water soluble boron contents

'obrzaxhki. B.. 1963

~~

0.15-1 0.07-0.8

1

h o t water soluble boron

The ratio acid soluble to water soluble boron varies from 1 to 3.2, i t is lowest in acid soils and highest in soils of pH > 6.8

.he amount of boron depends chiefly on mechanical composition and on humus content. The amounts of total and soluble boron decrease in deeper soil layers

lyszka. A., 1960

no boron deficienc slightly acid soils when the level of h o t water soluble boron is above 0.3 p.p.m. and on neutral and alkaline soils when the level is above 0.6 p.p.m. in arable layer

1

wiecicki, C.. 1964 water soluble boron: 0.05-0.69 hydrochloric acid soluble boron: 1.6-24

0.05 to 1.02

0.04 to 0.56

water solut boron. representing 0.6 to 3.5% of total boron and 1.2 t o 55% of hydrochloric acid soluble boron water soluble boron representing 0.1 to 3.3% of total boron and 0.5 t o 38% of hydrochloric acid soluble boron

water soluble boron content is good

leeper layers of peatbog soils are richer in water soluble boron: 2.85 p.p.m.

usierowicz. A. and Swiecicki. C.. 1963

Boron concentration tends t o decrease with depth, reflecti changes in humusclay complex b u t is unrelated t o pH and CaCo, levels of the soils

ciics. L. and Elek, E., 1962

1 60 BORON 4 LOCATION

'ARENT ROCK 9ND PARENT tOCK CONTENT P.P.m.)

SOIL TYPE

SOIL CLASSIFICATION SYSTEM 7 t h APPROXIMATION (U.S.D.A.)

rOTAL BORON :ONTENT P.P.m.)

Bulgaria North

iedirnentan residual parent material of cretaceous age: Pliocene clay

rhernozema gray forest soils solonchacks salinized virgin soils

ustoll alfisol or ultisol

!8-53 13

natric salorthid hapludent

.60

are rich in boro

soils :arbonate chernozems eached and podzolized chernozems

Rumania South

argiustoll

2alcareous chernozems podzolic soils jolonets solonchacks

U.S.S.R. Latvia ieavy boulder clays

U.S.S. R. Estonia

calcic argiustoll

iiberian limestones

sod podzolic and gleyed sandy soils of coastal areas 3odzolic meadow soils peaty lowland soils

calciustolls alfisol or ultisol

ow

salorthid

iigh

psamment

i

humaquod

15-35

histosol

i ch

spodosols

L.5-25 1.3-6.5

soils on these parent rocks podzolized soils

U.S.S.R.

Investigations and bibliographical references on boron in soils or U.S.S.R.

U.S.S.R.

Investigations and bibliographical references on boron in soils of U.S.S.R.

U.S.S. R.

U.S.S.R. Karelia

I

I

ihungite

acustrine glacial clays noraines

soils on that mineral dernopodzolic soils

sandy loams and leached and podzolized soil

alfic haplorthod

alfic haplorthod

HORIZON

I

161 BORON 4 AVAILABLE TO PLANTS ONTENT

DEFICIENCY OR TOXIClTY

ARIATIONS

0.9

REFERENCES

Palaveyev, T., 1958

0.7-1 0.3-0.5

2.2

:FFECTS OF 'ERTILIZERS

depth in leached chernozems and gray forest soils is due chiefly to t h e intensity of leaching process. The higher contents of water soluble boron of salinized soils are caused by the supply of ground waters fr salinized Pliocene deposits

I

water soluble boron

0.7-1

~~

0.5-0.7

water soluble

Dron content decreases from steppe soils t o forest soils. Positive correlation with pH, humus ant clay contents

water soluble boron

oron contents depend o n soil texture; peaty lowlands soil have rich supplies of mobile and total boron in upper laye total boron is uNf o m l y distributed in the profiles

EFICIENCY )R TOXICITY

~~

:FFECTS O F ‘ERTILIZERS

REFERENCES

~~

3.1 0.3-0.5 0.7-1.1 0.6-1.2 0.4-0.6

e

0”

fi

P

s

0.9

-s B

1.1-1.6

0.7 1.3 1.6

3-7 3-8

c. O

rJz

1.3 5-8,

I

Kick, H..1963

;oilsare rich in organic matter

1

3-4 2.6-6

2.5-3

2

2 ’3 ) I

3 0.6-1.2 5-24 .

fertilizers are

watersoluble boron

USefUl

J

0.12-0.31 0.19-0.38

Ravikovitch. S. e t al., 1961

ieficiency limit is reached in sandy soils; toxicity limit is reached in alluvial soils

1.6’ 1.1

Ieficiency limit is reached for all the soils

watersoluble boron

Giles, J.B.. 1964

>oroncontent does n o t vary in acid substrata ,oron content remains constant within the profile

Peyve. Ya.V., 1963

:ontent is good. no deficiency or toxicity is observed

Tercinier, G., 1966


PARENT ROCK AND PARENT ROCK CONTENT (p.p.m.)

SOIL TYPE


rOTAL BORON >ONTENT p.p.m.)

Polynesia Moorea Island

volcanic alluvions

more or less humiferous hydromorphic

haplumbrept

!-3

humic haplaquept

I

plunthaquox

!-3

oxisols

!-3

hapludent o r haplustent

.-2

HORIZON

soils basalts, andesitic basalts

basaltic debris India

semi-peaty hydromorphic soil indurated ferrallitic soils more or less degraded ferrallitic soils stony gray-brown young soils

surface horizon

goradu soil (yellowish brown alluvial sandy loam) with only 0.679 organic matter

150 cm

India

on boron in different Investigations soil types

India F’unjab

normal soils

India Gujarat

India G u jara t

alluvium (old and new) derived from trap and limestone Pleistocene and recent sediments derived from granites. metamorphic crystalline and basalts iecan trap basalt

upper horizon

saline-alkali soils

iatric salorthid

goradu soils (yellowish brown alluvial sandy loam) medium black soil black cotton soil

.ertic eutrochrept rertisol

black soil

rertisol

alluvial soil deltaic alluvial soil

luvent luvent

medium black soil

.ertic eutrochrept

surface horizon subsurface horizon surface horizon subsurface horizon

163 BORON 10 AVAILABLE TO PLANTS BORON CONTENT (p.p.m.)

ORON 'ARIATIONS


REFERENCES

Tercinier, G., 1963

oron content does n o t vary within the profile; very slight increase of boron content in very humiferous horizons

LO toxicity

is observed

0.3

CFFECTS OF ?ERTILIZERS

Gandhi, S.C. and Mehta, B.V., 1960

0.5

Datta, N.P.. 1964

3-11.8 0.3-4.8

boron in saturatio extracts

Kanwar, J.S. and Singh, S . S . . 1961

Mehta, B.V. e t al., 1964

Xaychaudhuri. S.P. and Datta Biswas, N.R.. 1964

0.5-0.7

0.77

possibility of boron deficiency exists in the semihumid areas. and a possibility of toxicity exists when boron content: are higher than 1.5

oils are capable of satisfying the needs of plants having low requirement

0.2-1.5

0.47-0.86 0.77-0.80

ositive correlation between pH and watersoluble boron in b o t h types of soils; water-soluble bora increases with decreasing rainfall. in normal soils; watersoluble boro decreases with increasing depth in b o t h types of soil

watersoluble boron

164

--

BORON 11 LOCATION


India Different RGL~OM

decan trap augite, basalt igneous rocks, alluvium (old and new) derived from trap and limestone gneiss, granite and crystalline gneiss granites and crystalline gneiss alluviumargillace-

SOIL TYPE

black soils

rertisols

25-57

red loams

rerochrept

8-34

laterite

1quox

25

luvent

15-42

irthox and vertisols

27-50

llfisols or ultisol

45

fluvent

67

alluvial soils ous (acid and coastal alluvium alkaline) arenaceous alluvium-calcareoru shales, slates, quartzite, limemixed red and stone, granitoid black soils gneiss. calcareous shales. lime stone, coastal alluvium grey sandstone 3odzolic soil and drab shales alluvium huuvi.l soil India Rajasthan (West)

India Bihar

Ceylon

SOIL CLASSIFITOTAL BORON >ATION SYSTEM CONTENT rth [email protected].) MATION U.S.D.A.)

4.1-42.1 (average 19) 7 soils have more than 30 17 soils range from 20 to 30 28 soils range from 10 t o 20 10 soils have less than 10

$2 typical soil

samples from a n d zone

alluvium

5 soils handy loam .oamy sand :lay loam loam

Investigations o n I!

1

inceptisols

on toxicity

18 19 40 40-83

HORIZON

166 BORON 11 AVAILABLE T O PLANTS BORON CONTENT @.P.m.)

BORON VARIATIONS


SFFECTS O F 'ERTILIZERS

REFERENCES

Raychaudhuri, S.P. and Datta Biawas. N.R., 1964

water soluble boron: total boron contents deficiency limit: are significantly 0.89-10.2 (averse 0.35 3.22). AU a o h have correlated with toxicity limit: l.! more tbur 0.36 of the amount of calwatenolubb boron. cium carbonate 52 s o h have more and finer soil fracthan 1.6 of watertions; available aoluble boron. boron b not signif, watersoluble boron icantly correlated represents 3.09 tc with calcium car81.1% of t o w bonate and finer boron soil fractions, it ia correlated with pH

Moghe. V.B. and Mathur. Q.M..1966

I

I

Jha. K.K., 1964

Tea Reaenrch Institute Report 1960

166 CHROMIUM 1 SOIL CLASSIFICATION SYSTEM 7th APPROXIMATION (U.S.D.A.)

LOCATION


SOIL TYPE

Wales

rhyolite mixed drifts dolerite pumice tuffs mixed drifts

1

serpentine till olivine gabbro till

brown podzolic soil freely drained x o w n podzolic soil imperfectly drained brown forest soil freely drained peaty gleyed podzol with iron pan ?odzol freely drained podzol freely drained non calcareous gley soil poorly drained peaty podzol with iron pan

Scotland

andesitic moraine granitic till granitic gneiss till quartz micaschist till Silurian slate till sandstone till

soils o n those parent materials

haplorthod haplorthod ochrept femod spodosol spodosol aquept placaquod

France

19 different soil profiles: vineyards, orchards ..

France

Studies and bibliographical references on chromium in soils


..

olivine, nephelinite. diabase, granodiorite. gneiss, phyllite. quartz porphyry

Yugoslavia Treskavica

Czechoslovakia

serpentine

mown earths

ochrept

podzols

spodosols

grassland soils

aquepkq

4 8 profiles of different soil types: 10% of soils contain chromium and they all originate from serpentine

gray forest soils and soils transitional between dernopodzolic and gray forest soils

U.S.S.R. Meschov plain U.S.S.R. Lower Volga

ancient alluvial sands ancient marine sands fluvioglacial sands quaternary marine sands

U.S.S.R. Bielorussia

fluvioglacial and ancient alluvial sands: 26.3 morainic clay loams: 61.5 loessial and loess-like loam: 58 lacustrine glacial clay: 115

alfisols

I

soils o n those parent materials

sod podzolic soils of different textures: sandy, loamy, clayey soils

alfic haplorthod or alfisols

167 CHROMIUM 1 TOTAL CHROMIUM CONTENT (p.p.m.) 15-20 300 250-400 250-300 25-30 3500-2000 300-100-200-300

80 7-50 150-200 150-200 200-250

IORIZON

AVAILABLE TO PLANTS CHROMIUM CONTENT (p.p.m.:

CHROMIUM VARIATIONS

iEFERENCES

< 0.03

no great variations of chromium content with increasing depth

4rcher. F.C.. 1963

soluble chromium content depends o n t h e content of parent rock gleyed horizons are rich in chromium

Iwaine, D.J. and Mitchell, R.L., 1960

different horizons 3.2-0.3

J

leyed B and C horizons

9.31-1.10

different horizons

D.03-0.17

pH 2.5 2.5% acetic acidsoluble chromium

10-30 1.004-0.28.1N ammonium

2.5-26.8

3ertrand. D. and Vinchon. C.. 1964

acetate soluble chromiun

irosman, R., 1966

high

umus horizon

high content ( 1 soil contains 3 3 0 P.P.m.) 100

chromium contents in different soil types depend o n parent rocks, and are proportional t o the contents of Fez03

.entschig, S. and Fielder, H.J.. 1966

chromium content increases with increasing thickness of the humus horizon

; a d . B.. 1964

:hromium content depends on parent rock content and o n soil forming process

:melhaus, V. and Valek, B., 1964

.20 cm horizon

'yuryukanov. A.N. and Vasil'evskaya. V.D.. 1964

traces traces-63 traces 50-123

:cumulation of chromiun in humic horizon

:he chromium distribution within the profile depends o n humus content, soil forming proces and relief

rakulin, A.A. and Mokiyenko, V.F.,

.he chromium content depends o n parent rock, soil texture, degree of podzolization and biological accumution

,upinovich, I.S.. 1965

1966

168 CHROMIUM 2 LOCATION

PARENTROCKAND PARENTROCKCONTENT @a.m.)

SOIL TYPE


U.S.S.R. UStYurt

fine clay loam deposit of quaternary age

gray brown r o b

xerochrept or ustochrept

sandy structureless takyr soils

salorthid

U.S.S.R. Turkmenistan Tedzhen Delta U.S.S.R. Amur Basin

granite: 35 lacustrine auuvions: 300 sand with gravels: 140 tertiary sandy alluvions: 79 stratified plain deposits: 150

brown forest soil brown podzolic soil gley podzolic soil thick meadow soil flood plain meadow soil chemozems

ochrept hapludalf aquult aquept aquept ustou

Dahomey

tertiuy sandy clay sediments

slightly ferrallitic clay soil slightly ferrallitic clay soil tropical fermginous soil slightly ferrallitic “terre de barre” soil tropical black soil

haplorthox haplorthox ustult or tropept eutrorthox

Ghana phy Uite granite G1 pegmatite sandy parent material B2 hornblende schists B2 basic material lvory Coast

amphibolite granite schists amphibolite schists charnockite

Central African Republic

quartz, micaschists. migmatite. amphibolite. granite. gneiss, charnockite amphibolite, granite. gneiss, migmatite amphibolite, itabirite quartz young alluvions

vertisol

19 forest soil profiles slightly desaturated ferrallitic soils

eutrorthox

lithosol desaturated ferrallitic soil tropical eutrophic brown soil slightly desaturated soil

eutisol eutrorthox eutropept eutrorthox

femsol brown earth red soil more or less leached ferrallitic soils hydromorphic with depth pseudogley soils ferrallitic soils red femsol black humiferous erosion ranker very leached ferrallitic soil

ochrult eutrochrept orthox ultisols aquept

slightly ferrallitic soils

oxisols

hydromorphic leached gray ferruginous soils slightly evolved erosion soils red ferruginous intergrade femsol mineral hydromorphic pseudogley soil

haplustalf

oxisols ochrult haplumbrept pale udult or pale ustult

hapludent ochrult aquept

169 CHROMIUM 2 TOTAL CHROMIUM CONTENT

HORIZON

4VAILABLE TO PLANTS 2HROMIUM CONTENT :P.P.m.)

CHROhlIUM VARIATIONS

REFERENCES

(p.p.m.)

0-44

)-60 water-soluble chromium water-soluble high contents chromium accuof chromiun mulates in humus in surface horizon horizons

Grazhdan, P.E., 1959

70-100

100 230 130 170 130 400 90-160 35-210 60-108 35-120

1

100 300 200 150 (average) 30-80 50-300 100 20 10-50 10-60 10-60 25 60 25

accumulation in humus horizon

Kovda. V.A. and Vasil’eyvskaya, V.D., 1958

:hromium content generally increases with increasing depth and clay content. In the slightly ferrallitic clay soils chromiu m accumulates in the 40-100cm horizon

Pinta, M. and Ollat, C., 1961

:hromium content increases with increasing depth

Bumdge, J.C. and Ahn, P.M., 1965

(ery slight variations of chromium content within the profile: chromium content increases slightly with increasing depth

Riandey, C.. 1964

A 1 horizon

103-160

100-250 20-80 30-50 10-50 100-200 30

Dobrovol’skiy, V.V., 1961

different horizons

1

upper horizons

different horizons

Boulvert, Y..1966

170

CHROMIUM 3 LOCATION


SOIL TYPE

SOIL CLASSIFICA. TION SYSTEM 7 t h APPROXIMATION ( U S . D. A. )


gneiss. amphibolite, charnockite, migmatite gneiss

slightly ferrallitic soils

inceptisols o r oxisols

very slightly leached red ochreous soil gray f e m g i n o u s soils

oxic haplustalf or alfic eutropept tropept or ultisol o r alfisol haplaquept aquert

charnockite, gneiss, amphibolite, young alluvions amphibolite

Chad

hydromorphic pseudo gley soil hydromorphic. lithomorphic vertisols slightly evolved erosion soils saline soils, unleached alkali soils

clayey sediments arkose. arkosic sandstone argillite sandy and clayey sediments sandy sediments clayey loam sediments sandy clayey sediments clayey sediments

Chad

gneiss amphibolite

sandy clay material

1 c

Madagascar

sand and sandy loams sandy clay alluvium sandy clay alluvium schists sandstone granite cipolin gneiss gritty limestone

Madagascar

alluvium limestone, basalts, volcanic ashes granite marl. basalts metamorphic acid rock sandstone material, sand

humic gley soils ferrallitic soils gray ferruginous soils subarid isohumic soils gray ferruginous pseudogley soils halomorphic hydromorphic alluvial soils topomorphic vertisols hydromorphic gley soils

hapludent salorthid, natric salothid umbraquept oxisols tropept o r ustalf or ustult ustochrept ochraquult aquic tropofluvent aquert haplaquept

slightly evolved hydromorphic deposit soil hydromorphic gray ferruginous with deep pseudogley soils gray ferruginous soils hydromorphic slightly humiferous gley soils

aquic hapludent

slightly evolved flood terrace soil slightly evolved alluvial bank soil “mangrove” soil vertisol gray ferruginous soil

hapludent fluvent hydraquent vertisol tropept or ustult or ustalf

gray ferruginous soil ferrallitic red soil reddish-brown humiferous ferrallitic soil leached slightly ferrallitic red soil black rendzina hydromorphic soils hydromorphic gley soils saline soil ferrallitic soils ferrallitic soil vertisols slightly ferrallitic soil gray ferruginous soils

tropept

}

or ultisol or alfisol

haplaquept

orthox haplohumox rhodudult rendol aquent o r aquept salorthid oxisol vertisol oxisol tropept o r ultisol or alfisol

171 CHROMIUM 3 TOTAL CHROMIUM CONTENT (p.p.m.)

60-175 100 80-200 100-500 100 300-1000 100-200 25-80 100-280 100-150 4-80 100-200 100-300

180-300 60 30 60-80 50 110 190 520 190 95 78 185 165

130 95

1

210-220

190-430 70 200-540 185 80-165

HORIZON

I

I I

AVAILABLE T O P L A N T S CHROMIUM C O N T E N T (P.P.m. )

ZHROMIUM VARIATIONS

REFERENCES

Boulvert. Y.. 1966

different horizons

upper horizon

rery slight variations Pias. J.. 1968 of chromium content through the profiles. The chromium content increases slightly with increasing depth

Vizier, J.F.. 1965 rery slight variations of chromium content through the profiles. The chromium content increases slightly with increasing dei h

upper horizon

:hromium content Nalovi;. Lj.. 1969 varies very slightly through the profile and decreases very slightly with increasing depth

hromium content Naloviz. Lj.. 1969 varies slightly through the profile, it depends on parent rock, soil type, and clay content. Organic matter content has no effect on that of chromium

172 CHROMIUM 4 LOCATION

China (North Eastern Inner Mongolia

'ARENT ROCK AND 'ARENT ROCK CONTENT P.P.m.1

malts

SOIL TYPE

111 soil profiles brown forest soils

SOIL CLASSIFICATION SYSTEM 7th APPROXIMATION (U.S.D.A.) ochrept

different soil types

India New Hebrides

icid pumices and obsidian on basic slags basaltic slags

slightly evolved deposit soils reddish-brown soils eutrophic brown soils reddish-brown soils

orthent ochrept eutropept ochrept

New Caledonia

iuartz, weathering products of very different rocks imestone-cemented flysch

fluviomarine. slightly evolved humiferous soil slightly evolved deposit soils eutrophic brown soils and mediterranean reddish-brown soils solodized solonets topomorphic vertisol

haplumbrept

New Caledonia

ilaggy basaltic tuffs..dolerite

Jasaltic sediments :alcareous sand and coralline limestone :oralline limestone, volcanic pumices Polynesia Moorea Island

rolcanic alluvium msalts, andesitic basalts incient basaltic debris Jasaltic debris

orthent eutropept and xerochrept natrargid aquert

reddish-brown soils. brown soils more or less degraded ferrallitic soils erosion soils, slightly evolved deposit soils rendzina-like soils peat soils, gray alluvial soil

ochrept oxisols

more o r less humiferous hydromorphic humocarbonated soils

aquic lithic rendoll

more or less humiferous hydromorphic alluvial soils semi-peaty hydromorphic soil indurated ferrallitic soils more or less degraded ferrallitic soils undegraded ferrallitic soil stony gray brown young soils

aquic haplumbrept

orthent rendollic eutrochrept histosol, fluvent

hydraquent plinthaquox oxisols oxisol haplumbrept

178 CHROMIUM 4 TOTAL CHROMIUM CONTENT (p.p.m.)

H0 R I 20 N

average: 103 concentration of chromium are higher than tho- recorded for soila of Europe and North America

Pecumulation in A horizon

AVAILABLE TO PLANTS CHROMIUM CONTENT @.p.m.)

JHROMIUM VARIATIONS

Fang, C.L. et al.. 1963

Sinha, R.C.P. and Baneriee. B.K., 1965

104-176

1

upper horizon

70-90

J

4000 900-2700 900-2500

900 2400

I

80-2400

140-220

tracee4 1000-2000 140 115-260 130-630 230 550-2000

REFERENCES

I

upper horizon

1

zhromium concentrations vary slightly through the proffles

Tercinier, G.. 1964

there is a positive correlation between humus and chromium concentrations

Tercinier. G.. 1964

Tercinier, G.. 1964

upper horizon

upper horizon

there is a positive cor- Tercinier, G., 1963 relation between chromium and humus contents; chromium content varies slightly through the profile

174

COBALT 1 ~~

LOCATION

'ARENT ROCK \ND PARENT t O C K CONTENT p.P.m.)

;OIL T Y P E

samples lays and fine mineral soils mganogenic soils. raw peat soils. mould mud soils ake-mud soils ;erpentine till )livine gabbro till

indesitic moraine granitic till

granitic gneiss till xuartz micaschist till ~ilurianslate till sandstone till Wales

Germany Black Forest

Germany Bavaria (East)

'OTAL C O B A L T 'ONTENT ?.P.m.)

Jrthent iistosol

igh content

IORIZON

176 surface layer

Finland

Scotland

;OIL CLASSIFI:ATION SYSTEM l t h APPROX,MATION U.S.D.A.)

rhyolite mixed drifts dolerite pumice tuff mixed drifts

27 different

groups of parent rocks paragneiss: high content orthogneiss: low content granites: 1.5-6.5

brown podzolic soil, freely drained mown podzolic soil with gleyed B and C horizons. imperfectly drained mown forest soil, freely drained beaty gleyed pod zol with iron pan poorly drained )odzol freely drained bodzol freely drained i o n calcareous gley soil. poorly draine Jeaty podzol wit iron pan

7

1

low content

laplorthod

0-200

haplorthod

0

:leyed B and C horizons

xhrept

0-20

: 1-3

1

ferrod o r sideraquod spodosol

0-20

spodosol

!5-40

haplaquept

0-30

placaquod

:3-4

I

i

different horizons

3

LO

soils o n these parent rocks

!O-30 !O-25

top -50 cm layer

8-15

1

soils o n these parent rocks :5

heavy soils: para braunerde. pararendzina! pseudogley soils

ochrept typic eutrochrept haplaquept

Investigations on

176

COBALT 1 AVAILABLE TO PLANTS COBALT CONTENT (p.p.m.)

COBALT VARIATIONS

3EFICIENCY 3R TOXICITY

CFFECTS O F FERTILIZERS

REFERENCES

Malcitie, 0..1962

cobalt content in mineral soils increases from coarse t o fine soils being twice as great in fine clays as in fine sands; it increases with p H

Swaine, D.J. and Mitchell, R.L., 1960 acetic acidsoluble cobalt pH 2.5

on rhyolite cobalt con t e n t is lower t h a n on other parent materials; cobalt content decreases with increasing depth

Archer, F.C.. 1963

leficiency in cattle when forage contains less than 0.06 of cobalt

Riehm, H. e t al., 1960

< 0.07 cobalt concentration#

id composition of

Rid. H. and Schiecke. I., 1965

176 COBALT 2 LOCATION

'ARENT ROCK LNDPARENT LOCK CONTENT P.p.m.1

;OIL TYPE


'OTAL COBALT 'ONTENT p.p.m.)

IORIZON

~~

Germany Brandenberg District

ow moor soils iigh moor soils

Germany D.D.R.

viand soils


Spain Western Andalusia Guadalquivir Valley

Nlivine-nephelinite iabase ranodiorite neiss Nhyllite uartz porphyry Nurest tertiary chalks: 4-5 lore weathered chalks: 10-12 ranitic rocks: 8 ideozoic slates: 12-14

1

brown earths and podzols

} histosols

.3-1.25 .64-1.50

aquept or aquent

A, B and C horizons

ochrept and spodosols

.erorendzinas and serozems )lack earths

rendoll orthid vertisols

,ed loams ,ed bottomland

xerochrept fluvent

}

11.2

10.6

9.2 :6

SOilS

}

erra rossas and calcareous solonchaks )rown earths

xerochrept natric salorthid or natrargid ochrept

Yugolsavia Treskanca

passland soils

aquept or aquent

Poland Opat6vSandomiez Region

:hernozems x-own soils pseudopodzols

calciustoll ochrept spodosols

ccumulation ccumulation ccumulation

.op horizon 3lC horizon 3/C horizon

Poland Kielce Region

Yendzinas

rendoll

ccumulation

alc horizon

Poland Wielkopolska

duvial soils zhernozems podzols peat soils

fluvent calciustoll spodosol histosol

ranite

6.2

.2

177 COBALT 2 AVAILABLE TO PLANTS COBALT CONTENT @a.m.)

soluble cobalt

ZOBALT JARIATIONS


EFFECTS OF FERTILIZERS

REFERENCES

.otal and available cobalt contents are higher in mineral than in organic soils;with increasing total cobalt its solubility decreases; cobalt content increases with organic substances

m imgated soils

application of 8 kgl h a CoSO, increases the cobalt content of hay

Barufke. W.,1962

> 0.08

(rich) in 35% of soils 0.044.08 (medium) in 47% of soils < 0.04 (poor) in 33% of soils

plants often show toxicity

Asmus, F., 1961

:ontents of cobalt are related t o the parent-rocks and vary directly with content of Fe,O,

Lentschig, S. and Fielder, H.J.,1966

!xcept in black earths. cobalt content decreases with increasing depth. In the different horizons of a soil. cobalt content is related to pH

Gonzalez-Garcia. F. and Garcia Gomez. A.M., 1964

:obalt content increases with increasing thickness of humus horizon

SaviE, B.. 1964

Piotrowska. M., 1965

iccumulation and solubility are related t o clay mineral of montmorillonite group high content high content

1N hyc chloric acid-

Kabata-Pendias. A., 1965

Czekalski, A. and Kocialkowski. 2.. 1966



SOIL TYPE

Poland Holy-Cross Mountain Region

sandy soils

Czechoslovakia slates sandstone Beskydy Mountains

loamy soils acidic sandy soils

Czechoslovakia serpentine and other rocks

48 soil profiles

Hungary

1 5 chernozem

SOIL CLASSIFI:ATION SYSTEM f t h APPROXMATION U.S.D.A.)

?OTAL COBALT >ONTENT P.u.m.)

HORIZON

:obalt content is higher in loamy soils than in sandy soils

:alciustoll

profiles

Hungar, South-Eastern Transdanubia

brown forest soils alluvial grassland soils chernozems

whrept iquent

degraded chernozems brown forest soils podzols

:alciustoll or haplustoll Jchrept ipodosol

loess

zonal soils

:alciustoll or

eruptive rocks, schists

rendzinas and soils on these parent rocks skeletal soils

.endoll

chernozems red-brown and red forest soils podzols

:alciustoll Jchrept

Rumania Cluj Region

Rumania Dobrudja

i.2

argiustou

limestone Rumania OIt Region

:alciustoU

Jrthent

arable layer ipodosol

ow

179 COBALT 3 AVAILABLE TO PLANTS COBALT CONTEN? (p.p.m.)

ZOBALT VARIATIONS


EFFECTS OF 'ERTILIZERS

iEFERENCES

weathering and soil forming process result in a higher trace element content in the soils than in the parent material; solubilitir are higher in the upper soil horizons

Kabata-Pendias, A. and Galczynska, B., 1965

accumulation of cobalt in the B horizons of loamy soils on slates; leaching of cobalt from the B horizons of acidic sandy soil

Benex, S., 1 9 6 4

:obalt occurs only in no toxicity is encountered serpentine soils; cobalt content depends on parent. rock and soil type, and soilforming process influences its distribution

gmelhaus. V. and Valek. B., 1 9 6 4

:obalt concentration tends to decrease with depth, reflecting changes in humus clay comple but is unrelated t o pH and CaCo, level high levels of pH affect the availability of cobalt

Szucs, L. and Elek. E.. 1962

:obalt tends to accumi late in the B horizo especially in brown forest soils

Zzopf, J., 1 9 6 4

:obalt contents ere greater in degraded chernozems than in brown forest soils and insignificant in podzols

Yemes, M., 1959

:obalt concentration rendzinas and soils in skeletal soils on on eruptive roc are deficient in eruptive rocks varit greatly according cobalt to parent material

Bijescu, I. et al., 1 9 6 2

I

1 N nitric

Bsjescu, N. and Bgjescu, I.. 1960

180 COBALT 4 LOC AT1ON

'ARENT ROCK LND PARENT LOCK CONTENT P.P.m.)

Bulgaria

L'OTAL COBALT >ONTENT :P.P.m.)

SOIL TYPE

#OILCLASSIFI:ATION SYSTEM ' t h APPROXMATION U.S.D.A.)

:innamon forest soils neadow cinnamon soils :hernozemsmonitsas neadow bog soils ialine soils :hernozems way forest soils iark gray forest soils :hernozemsmonitsaa neadow cinnamon soils neadow bog soils :heltozempodzolic soils Jodzolized cinnamon forest soils >ale gray forest

rgiustoll or ustoll ,quit argiustoll

3.3-15.2

rertic argiustoll

10.2-47.6

iurnic haplaquept iatric salorthid ialciustoll ilfisol or ultisol Poralf

9.2-13.2

ialine soils dneiss granite marble and semiweathered muscovite shales

1

humus horizon contains more cobalt than d o the parent-rocks

rertic argiustoll iquic argiustoll iumic haplaquept llfisol or ultisol iapludalf Pchrept

Bulgaria Valley of Roses

granite

ikeletal soils Jarious soil types

U.S.S.R. Latvia

sandstone clays dolomite

soils o n these parent material iandy soils :layed soils

U.S.S.R. Karelia

lacustrine glacial clays moraines

slightly podzolized soils sandy loams

U.S.S.R. Southern Karelia

moraines clays glacial lake deposits

various parent

iatric salorthid

14.5-16.5 2.5-10.1 brown forest soils

)chrept

1

about 1

1

materials

soils o n these parent material

upper horizons

1.7-8.1 5.2-9 9.5-13.3 6.3-26.4

BOUS

Bulgaria

IORIZON

0.13-1.20 0.12-0.36 0.44-2.97 0.45-1.70 0.16-1.85 1.79-2.41 0.41-2.26 llfisol

1

0.55-3.3

soils formed o n moraines contain more cobalt than soils formed o n clays

i

the cobalt content is greater in the illuvial horizons

upper lavers

I

C horizon

181 COBALT 4 AVAILABLE TO PLANTS COBALT CONTENT (p.p.m.)

:OBALT TARIATIONS

3

)EFICIENCY )R TOXICITY

LFFECTS OF FERTILIZERS

REFERENCES

Stanchev. L. et al.. 1962

available cobalt varies from: traces t o 0.92

I

0.3-3.96(cobalt soluble in I N HNO,) acid-soluble cobalt is 7-62% of total cobalt 0.09-0.97 (cobalt soluble in acetate buffer. pH 4) acetate soluble cobalt is 1 4 % of total cobalt in top layers of the soils

he total content of cobalt in the upper layers depends primarily on the cobalt content of the parent-rock

available cobalt is low

Stanchev. L. and Stoilov, G.. 1964

;toyanov. D.V., 1963

LauenkrapEa. E. and Lieldiens, R.. 1961

roikka, M.A. et al., 1965 nore cobalt occurs in the soil forming rocks than in the humus horizon of the soils

folodin, A.M. and Toikka. M.A., 1966


'ARENT ROCK

SOIL TYPE

4ND PARENT LOCK CONTENT P.P.m.)

TOTAL COBALT $OIL CLASSIFI:ATION SYSTEM CONTENT 'th APPROX(p.p.m.) MATION U.S.D.A.)

nountain tundra soils

10-22

U.S.S.R. Kola Peninsula

iepheline syenites

U.S.S.R. Kola Peninsula Central and Northern Taiga

rystalline schists (garnet, granulite) with a n intrusion of norite nantle of greenish may sandy loam moraine

)odzolic soils in central and northwestern Taiga

Jossic hapludalf

)eat bog soils in north-westem Taiga

1istosol

iantle loam

oamy soils

U.S.S.R. Southern Taiga Gor'kii Region

low contents

low accumulation

)samment

Jeaty gley soils

iistosol

ierno slightly podzolic soils

clossic hapludalf

accumulation is slight accumulation is completely absent

U.S.S.R. Moscow River

g r a d a n d soils lrable soils

iquent o r aquept

26-34

U.S.S.R.

IlfisOl gray forest soils llossic hapludalf roils transitional between demopodzolic and gray forest s o h

Meshehov Plsir

n different horizons

gneoua rocks, quaternary formations, morainic deposits

strongly podzolized soils

U.S.S.R. Southern Taiga

30R I Z 0N

}lo

A0 horizon

42 horizon

eluvial horizon !luvial horizon :luvial horizon

1 u m u layer

]

z i m laver


0.6-12.7

7ARIATIONS

OR TOXICITY


REFERENCES

obalt content does not vary much along the profile


obalt accumulates in the minerals of heavy fraction, moraine is poorer than the intrusion rocks. Soil formation process determines t h e distribution of cobalt down t h e profiles in peat bog soils

Dobrovol’skiy and Aleshchukin, L.V.. 1964

he distribution of cobalt and its mobile form down the profile depends on t h e intensity of podzolization. ultivation decreases total cobalt in t h e plowed layer nobile form of cobalt accumulates during cultivation

Nikitin, A.B., 1966

he distribution of cobalt in the profile is closely connected with the degree of podzolization

Orlov. A.Ya. and Orlova, L.P.. 1966

easonal changes in cobalt content are determined by the Fe2/Fe’ ratio whic governs the redox potential of soil. Cobalt mobility is highest a t a ratio of 1

Bondarenko, G.P., 1962

Tyuryutanov. AN.. 1964


'ARENT ROCK rND PARENT LOCK CONTENT P.P.m.)

U.S.S.R. Bielonvlsia

moraine clay Bod podzolic soils loams: 1.2-4.8 Jess-like clay loams: 1.3-8.6 kcustrine clays mzodzolic ilty clay loams Luvioglacial and sod podzolic ancient alluvial aandy soils sands ilty clay loams 9 o d podzolic bog soils and sod bog soils humus carbonate and peat bog soils

SOIL TYPE

}

I

U.S.S.R. Southeastern Polesia

U.S.S.R. Bieloruasia

rod podzolic soils medium podzolized soils acid peaty gley soil humus gley soils norainic loessic clays .ght sands &e clay deposits

U.S.S. R. Bieloruasis

luvioglacial and ancient alluvial sands: 3 morainic clay loams: 8 Dessial and loesslike clay loams: 7.7 icustrine glacial clays: 13

md podzolic soils

SOIL CLASSIFITOTAL COBALT CATION SYSTEM CONTENT 7th APPROX(p.p.m.1 IMATION (U.S.D.A.) glossic hapludalf

0.4-10

glosdc hapluddf

1.06-13 0.6-6 0.2-1.8

cryorthod and glossudalf or boralf rendoll histosol

1-4.5

1

1.1-2.4

glossic hapludalf orthod hist0.01 humnquept

1

rather high

glossic hapludalf

3-3.9

glossic hapludalf

rod podzolic strongly podzolized soils histosol peaty organic soils sod podzolic sandy loams

Bod podzolic sandy glossic hapludalf clay loams sod podzolic silty glossic hapludalf clay loams


demopodzolic soils

glossic hapludalf

U.S.S.R.

demo meadow soils drained peat-bog soils leached chernozems gray forest soils

umbraquept

Ryazan Region

H0R I Z 0N

dslmOpOdZOk

rob

glossic hapludalf argiustoll or dudoll alifrol or ultisol d O S d C h.DlUd.lf

3.2-6.1 3-10

I

plow-layer


30BALT VARIATIONS

DEFICIENCY 3R TOXICITY

FFECTS O F ERTILIZERS

REFERENCES

Vil’gusevich. I.P. and Bulgakov, N.P.. 1960

0.2-0.9

0.05-1.5

largest amounts of cobalt are found in the fine fractior

Lukashev, K.I.and Petukhova, N.N.. 1962

ratio mobile to total cobalt varies from 0.08 to 0.66

Vil’gusevich. I.P., 1961

cobalt content depent to a considerable extent on the con! of cobalt in parenl material, and on tl texture of the soil distribution depen on soil forming process. Fine textured soils show a well defined eluvic horizon deficient in cobalt

Lupinovich. I.S., 1965

t

Lupinovich, I.S. and Dubikowski, G.P.. 1964

:ontent of cobalt is higher in heavier soils. Most of soils are poorly supplie with cobalt in dernomeadow soils and peat-bog soils cobalt content decreases with depth In gray forest soils cobalt content increases from the plowed layer t o the B horizon and then decreases

dernopodzolic soils are deficient in cobalt

Davydov. N.I. and Starobinets, K.S., 1963

186 COBALT 7 FOTAL COBALT SOIL CLASSIFICATION SYSTEM CONTENT 7th APPROX(p.p.m.) [MATION (U.S.D.A.)

LOCATION

PARENT ROCK AND PARENT ROCK CONTENT (R.R.m.f

SOIL TYPE

U.S.S.R.

shungite

soils on that parent material demopodzolic soil glossic hapludalf

U.S.S.R.

friable sedimentaw be& of Jurassic. cretaceous. tertiary age deluvium of serpentine basic effusive tuff

ordinary chernozems solonetzic chernozems

calciustoll

dark gray forest soils poorly developed chernozems

boralf

Ural-Sakmara lnterfluve

natrargid

calciustoll

0 IR I20N

upper horizon

4

I

26

U.S.S.R. Ustyurt

fine earth clay loam deposit of quaternary age

gray brown soils

orthid

5-7

:obalt accumulates in surface crust and humus horizon

U.S.S.R. Or’-Kumak Watershed

ancient weathering crust

solonchakous solonets

natric salorthid

140 140

A B1 82 c u b .

60

50-100 crusty solonets

natrargid

80 80

72 72-100 solodized dark chestnut soil

natric argiustoll

calcareous eroded dark chestnut soil

argiustoll

chernozemic soils gray forest soils meadow chernozem-like soil solonets solonchacks chestnut soils

ustoll alfisol or ultiiol aquic haplustoll

80

100 72 76

60-120 c.luvial-deluvial loams envelopping the weath ering crust U.S.S.R. Kuban Krasnodru Region

humus carbonate soils U.S.S.R. Kuban Krasnodar Region

natrargid natric salorthid argiustoll or haplustoll rendoll

thick clay carbon- argiustoll ate chernozems mountain forest ochrept brown soils humic carbonate rendoll soils

A Bl 82 C A A2B B1 82 carb. C carb. A1 B1 82 C

upper horizon

10

16.3 10.2

187 COBALT 7 AVAILABLE TO PLANTS COBALT CONTENT (p.p.m.1

ZOBALT VARIATIONS


EFFECTS O F 'ERTILIZERS

REFERENCES

cobalt content decreases with depth

Toikka, M.A., 1964

n clear relationship

Krym. I.Ya., 1964

exists between cobalt content in the soils and the composition of the soilforming parent material. Soils have eluvial characteristics Dobrovol'skiy. V.V., 1961

water-soluble cobalt: 5-1 0

26 36 24 4-14 18 18 14 7-10 16-13 12 11 8 5-8 6 I 4 6

1

mobile cobalt accumultes biologically in the humus and illuvial horizons and is adsorbe by clay minerals

Krym, I.Ya., 1965

1 N hydrochloric acidsoluble cobalt

2.8

Tonkonozhenko, E.V.. 1964

l.

i 2.6 4.8 1.1

poor in cobalt

ronkonozhenko. E.V.. 1964


U.S.S.R. Azerbaydzhan Kuabakh steppe of Kura-Araks Lowlands

PARENT ROC1 AND PARENT ROCK CONTEI [p.p.m.)

SOIL TYPE

p a y brown soils

SOIL CLASSIFICATION SYSTEM 7th APPROXIMATION (U.S.D.A.) orthid

I’OTAL COBALl CONTENT (p.p.m.)

HORIZON

17.2

A horizon of a

3.2

B horizon of a

Virgin SOU sod solonchacks

natrargid

virgin soil A horizon of a n imgated soil B horizon of an imgated soil

3.2-3.5

1-10

U.S.S.R.

19 soil samples

4-16

Azerbaydzhan Little Caucasus U.S.S.R. Azerbaydzhan

mountain forest soils mountain meadow soils meadow forest soils chestnut soils

U.S.S.R. Azerbaydzhan Northern Azov and Rostov Region

chernozems (North Azov) cis Caucasian chernozems

U.S.S.R. Azerbaydzhan Sal’yansk Region

serozem meadow soils solonchacks

ochrept

ustoll o r udoll

i

ustoll or udoll

12-99

aquent or aquept argiustoll or ustoll

average: 10

n

.&

humus horizon

aquic camborthid natric salorthid

U.S.S.R. Azerbaydzhan

U.S.S.R. Dagestan

U.S.S.R. Uzbekistan

carbonate meadov steppe soils solonetses meadov steppe soils solonchack-like meadow steppc soils solonchacks mead, ow steppe soils deep solonchackslike meadow steppe soils irrigated pale serozems dark non-irrigated serozems

aquic camborthid natrargid salorthid sdorthid natric salorthid

orthid xerochrept

)”

owest contents iighest contents

16.

189 COBALT 8 AVAILABLE TO PLANTS COBALT CONTEN:

ZOBALT VARIATIONS



REFERENCES

@.p.m.)

.

Pershma, M.N m a Pen’kov, O.G.,1962

Vekilova, F.I. and Borovskaya, Yu.B., 1960

;he cobalt content tends to vary wit1 the iron content

Zul’fugarlf, D.I. e t al., 1959

Shakuri. B.K., 1964

:obalt accumulates in A and B horizons

I

Shakuri, B.K. and Akhundova. G.G.. 1965

0.008-1.6

58.5

application of cobalt fertilizer has a beneficient effect o n yield of c o t t o n which increases from 9 t o 21%

Mamedov. Z.I., 1961

Zul’fugarl?. D.I. and Munalova. M.. 1966

61.5 38

35 41

Mirzaeva, K.Kh.. 1963



U.S.S.R. Turkmenistan Tedzhen Delta U.S.S.R. Amur Basin

lacustrine alluvions: 6.9 sand with gravel: 20 tertiary sandy alluvium: 1 2 stratified plain deposits: 5.8

U.S.S.R. Transural Northern Forest Steppe

SOIL TYPE


rOTAL COBALl :ONTENT P.P.m.)


salorthid

.O-30

chernozems

calciustoll

i.1

brown forest soil

ochrept

..I

brown podzolic soil gley podzolic soil meadow soil

hapludalf

1.2

humaquod humaquent

i.5 i.7

flood plain meadow soil

humaquent

1.6

podzolized chernozem gray podzolic soil meadow chernozem meadow soil

argiudalf

I5

alfisol or ultisol aquic haplustoll

i0 $0

aquent or aquept

!I

inceptisol or entisol alfisol or ultisol

3

sandy loams

Canada Nova Scotia

gravelly loams

7 1 soil samples ground water podzols humic gley soils low humic gley soils better drained regosols red-yellow podzolic soils

U.S.A. South Eastern States

U.S.A. South East North East

sandy parent material weathered before deposition (southeast) unweathered minerals in glacial drifts (northeast)

HORIZON

3.9-9.3

umbraquult humaquept haplaquept

@15 cm 0-30 c m

psamment rhodustult or rhodudult

sandy and loamy sand soils: podzolic soils humic gley soils regosols

alfisol or ultisol humaquept psamment

1.39

podzolic soils humic gley soils alluvial soils

alfisol or ultisol humquept fluvent

1.57-2.23 t.42

1.19 1.71

i.97

191 COBALT S AVAILABLE T O PLANTS COBALT CONTENT (P.P.m.)

:OBALT JARIATIONS



REFERENCES

Grazhdan. P.E.. 1959

1.55 4.5 2.03

biogenetic accumulation of cobalt in humus horizon anc decrease of cobalt content in A 2 horizon

Kovda, V.A. and Vasil'eyvskaya, V.D.. 1958

naximum amounts of cobalt occur in the top horizon

Dborina, M.G.. 1965

2.30 :obalt sprays a t the Smeltzer. G.G. et al., 1962 rate of 4 Ib/acre C o S O , cause a significant increase in cobalt content of herbage b u t hav little effect o n dry matter yield esa cobalt is extracted from t h e imperfectly to acidpoorly drained dithi soils t h a n from zone t h e well drained extract- soils

2.5%

iccording t o soil types deficienci in cattle or shee appear when ex tractable cobalt is less than 0.02 0.03 or 0.05

Alban, L.A. and Kubota, J., 1960

0.06-3.74 cobalt the differences in cobalt contents are due t o parent material, weatherec or unweathered, as well as t o the relationship of the distribution of cobalt and iron

Xubota. J. and Lazar. V.A.. 1960


P A R E N T ROCK AND P A R E N T ROCK CONTENT (p.p.m.)

S O I L TYPE

S O I L CLASSIFIl’OTAL COBALT CATION SYSTEM CONTENT 7th APPROX[p.p.m.) IMATION (U.S.D.A.)

U.S.A. New England

glacial drifts derived from granitic rocks and wanodiorite undifferentiated drift deposits mixed lacustrine and marine deposits

sandy t o tine sandy loam podzols brown podzolic

spodosol

1.6-7.6

orthod

1.2-6.6

umbraquult

1.9-6.7

orthod humaquept

7.7-12.6 7-14

fluvent

4.8-11.2

spodosol

D.63

soils ground water podzols brown podzolic low humic gley

SORIZON

’

A p horizon

soils well drained

PlUVlal

U.S.A.

coarse textured podzola ground water podzols low humic and humic gley soils well drained red yellow podzolil and gray browr podzolic soils

Eastern States

haplaquept and humaquept rhodustult or rhodudult alfisol or ultisol

1.86

hard limestone calcareous sandstone marl terra rossa terra rossas alluvium + aeolian deposits

papynw plant remains Mali Republic Savannah Zon black rocks

terra r o w brown red sandy

Al,

A2 horizons

6.96

:OP- 6 cm horizon

42 soil samples

suriaaam

Israel

unbraquult

xerochrept nerochrept

LO

3.3

soil rendzinas of valley rendoll fluvent alluvial soil brown soil of xerochrept semiarid region

5.9-6.1 6.0-6.9 8.1-8.8

salorthid desert alluvial hydrohalomorphic soil loess muck soil histosol

1.7-2.1

red brown clay oxic haplustalf loams light brown alluvia fluvent soils red brown soils haplustalf

3.4-4.5

horizons: 0-30 cm 30-60 cm 60-90 em

6.1-8.3 3.4-3.8

3.3-6.3 1.3-3.8

I

arable layer

lea COBALT 10 ~~

AVAILABLE TO PLANTS COBALT CONTENT (p.p.m.)

!OBALT 'ARIATIONS



REFERENCES

U low cobalt con-

deficiencies in cattle appear in these regioni

m o u n t s such M 6 lb of cobalt per acre applied as CoSO,. raise significantly the cobalt levels in b o t h legumes and grasses

Kubota, J., 1964

tents are related to law inherited amounts of cobalt The downward leaching of the cobalt from t h e A to t h e B horizons has an important effect. Surface horizons A 1 o r A1 of podzols, brown podzolic soils and groundwater podz commonly have about 213 as muck cobalt as is presen in the underlying 1 horizons 0.0:

0.2c

3.2

2.5% 15 acetic acidex70 tract- 11 of toable tal cobalt, cobalt PH 2.5 46

0-1.9 pH 2.5; 2.5% acetic acidsoluble cobalt 2.1-2.3 0.2-0.8 1.1-1.3 0.8-1.5 0.9-1.7

7

21.6 7.4-24

a

18.5-21.1 13.3-21.2 10.7-19.'

< 2

P

i e cobalt present is fairly easy to extract, principally from surface horizons

5eficiency in ruminant animals

Kubota, J.. 1965

&en, J.G.P. and Ehrencron. V.K.P.. 1964

obalt contents are positively related to clay contents ieficient soils

Ravikovitch. S. e t al., 1961

3 0.4-0.65

Q"

26-27

.uH

' 26-28 9-17

1 -

0.8-1.4

0.95-1.l

5

Peyve, Ya.V., 1963 nitric soluble

194

COBALT 11 LOCATION


Dahomey

sandy clay tertiary sediments

Ghana phyllite granite G1 pegmatite randy parent material B2 hornblende. schists 8 2 basic material

Ivory Coast

granite, schists charnockite

SOIL TYPE


rOTAL COBALT ZONTENT :P.p.m.)

slightly ferrallitic clay soil slightly ferrallitic clay soil tropical fermginous soil slightly ferrallitic “terre d e barre’ soil tropical black soil

haplorthox

23-11

haplorthox

< 3-30

tropept or ustalf or ustult eutrorthox

2-16

< 3-6

vertisol

10-60

eutrorthox

:10

19 forest soil profiles: slightly desaturatec ferrallitic soils lithosol desaturated ferrallitic soil tropical eutrophic brown soil slightly desaturatec ferrallitic soil more or less leached ferrallitic soils more o r less leached ferrallitic

IORIZON

different horizons

LO

eutisol kcrox

10-30 :10

eutropept

100-200

eutrorthox

50-100

ultisol

traces - 2 5

ultisol

1-10

hydromorphic low humiferou: deep pseudogle soil black humiferous erosion ranker slightly ferrallitic red femsol ferrisol brown earth highland red soil

ochraquept

3-20

slightly desaturated ferrallitic soils leached, hydromorphic gray ferruginous soi slightly evolved erosion soil mineral hydromorphic pseud gley soil sllghtly evolved erosion soil slightly desaturated ferrallitic solls

different horizons

SOilS

schists

charnockite amphibolite schist amphibolite


quartz, micaschist: migmatite. gneiss. granite granite, gneiss itabirite young alluvions amphibolite gneiss, charnockitt granite

different horizons haplumbrept

1

ochrult

30-60

ochrult ochrept orthox

30 50 3

eutrorthox

1

ochraquult orthent

traces - 3

8

ochraquept orthent

8

eutrorthox

3-9

different horizons

195

COBALT 11 ~

AVAILABLE TO PLANTS COBALT CONTENT (p.p.m.)

BALT RIATIONS

3EFICIENCY 3R TOXICITY

:FFECTS OF FERTILIZERS

tEFERENCES

ialt accumulates in surface horizon cobalt content increases with increasing depth; cobalt content generally varies with clay content

Pinta, M . and Ollat. C.. 1961

d t content is found t o be related to the underlying geological formations

Bumdge, J.C. and Ahn. P.M., 1 9 6 5

Riandey. C., 1 9 6 4

cobalt accumulates in clayey horizon

Boulvert. Y., 1 9 6 6



SOIL TYPE

SOIL CLASSIFICATION SYSTEn 7th APPROXIMATION (U.S.D.A.)

l'OTAL COBALT ZONTENT :Pam.)


young alluvions

mineral hydromorphic pseudogley soil ferrisol intergrade red ferruginous soil slightly ferrallitic soils slightly ferrallitic

ochraquept

LO

ochrult

I0

eutrorthox

50

eutrorthox

30

eutrorthox

10-60

haplochrult or normulstalf haplochrult or normulstalf orthent

30-60

20-100

aquert

100-300

ochrept

i0

slightly evolved hydromorphic deposit soil gray fenuginous soils hydromorphic slightly humiferous deep pseudogley soils leached gray ferruginous deep pseudogley so&

aquic udifluvent

LO

tropept or ustalf or ustult ochraquept

}

ochraquult

8

saline soils,unleached alkali soils, humic gley soils gray fenuginous

salorthid. natrargid, humaquer

10-20

tropept or ustalf or ustult ustochrept

i

quartzite gneiss migmatite

IORIZON

soils amphibolite. charnockite migmatite, gneiss

amphibolite

gneiss

Chad

gneissamphibolite

sandy clay material

Chad

[

I

clayey sediments

sandy and clayey sediments sandy sediments arkose, arkosic sandstone clayey sediments

clayey loam sediments sandy clay nedimentr

slightly ferrallitic soils leached gray ferruginous soils leached gray ferruginous soils slightly evolved erosion soil hydromorphic lithomorphic vertisols very slightly leached red . ochre soil

soils subarid lsohumic soils gray ferruginous pseudogley soils, ferrallitic soils hydromorphic gley soils topomorphic vertisols halomorphic. hydromorphic alluvial soils topomorphic vertisolr

ochraquult oxtpols

30-40

upper horizon

3-10

traces - 3

traces - 30

humaquept aquert

different horizons

10-20

plic xerofluvent

10-30

aquert

20-9 6

p

upper horizon

197


ZOBALT VARIATIONS



REFERENCES

Boulvert. Y.. 1 9 6 6

iobalt content increases with increasing depth

Vizier, F., 1 9 6 6

:obalt content varier very slightly down the profiles, it incressc with depth

Pias, J., 1 9 6 8



East Africa

Madagascar

SOIL CLASSIFIFOTAL COBALT CATION SYSTEM CONTENT 7 t h APPR,OX(p.p.m.) IMATION (U.S.D.A.)

< 0.02-9

131 soil samples 7 2 soil samples

sandy clay alluvium

sandy clay alluvium schists granite sandstone cipolin gneiss gritty limestone Madagascar alluvions mark, basalts sandstone material sandy hard crust basic rock, limestone, granite limestone, volcanic ashes basalts China (North Easter1 and Inner Mongolia

SOIL TYPE

basalts

0.08-0.63

ilightly evolved flood terrace soil ilightly evolved alluvial bank soil ‘mangrove soil” rertisol

hapludent

3-21

fluvent

8-1 8

cray ferruginous soil ‘errallitic red soil [ray ferruginous soil ,eddish-brown humiferous ferrallitic soil eached slightly ferrallitic red soil ,lack rendzinas

tropept or ustalf or ustult orthox tropept o r ustalf or ustult haplohumox

hydraquent vertisol

5-12

15-18 14-39

rendoll

1-10

:ray ferruginous soils ‘errallitic soils

tropept or ustalf or ustult oxisol

‘errallitic soils

oxisol

i 11 soil profiles wown forest soils

ochrept

3-5 horizons i n a profile

15

18-53

humaquept. aquept or aquent salorthid vertisol tropept or ustalf o r ustult

surface horizon

19-25 12-2 5

ustult

iydromorphic soils, hydromorphic gley soil, saline soil iertisols :ray ferruginous soils

HORIZON

I

15-30

traces 3

upper horizon

15-30 15-20

3 23 (an average) :obalt concentrations greatly exceed those recorded for soils of Europe and North America

accumulation in A horizon

199 COBALT 13 AVAILABLE TO PLANTS COBALT CONTEN (p.p.m.)

COBALT VARIATIONS

1 DEFICIENCY OR TOXICITY

EFFECTS O F FERTILIZER,S

REFERENCES

cobalt c o d e h t does n o t always decrease with increasing depth

Chamberlain, G.T.. 1959

PH and organic matter no pronounced

Hervieu, J. and N a l o v i E , Li.. 1966

nificant effect o n cobalt content b u a reducing mediun aids cobalt concen tration. Cobalt C O I tents are higher in evolved soils. Cobalt content decreases with increasing depth in soils evolved in sit

:obalt accumulates in clayey horizon. Cobalt content depends o n soilfor ing process. pH an organic matter content have no el fect on cobalt con tent

NaloviE, Lj.,1969

Fang. C.L. et al.. 1963

200

COBALT 14 SOIL TYPE

SOIL CLASSIFIZATION SYSTEM 7th APPROX.MATION :U.S.D.A.)

POTAL COBALT :ONTENT P.P.m.)

3 alkali s o h

Ruventic natric salorthid 'luvent

1.6-29.1

AND PARENT ROCK CONTENT

Uttar-Pradesh

3 adjoining cultivable s o h

India Bombay granite alluvium basalts

India Maharashtra Konkan

India Punjab

India Gujarat

quartz. feldspar, mica, h o m blende, t o u r m a line, magnetite, epidote, rutile

i.6-28.6

lORIZON

different horizons

LOO0 soil examples iandy soils .oamy sandy soils :layey and lehm soils

2 profiles of Konkan region L profile of medium black soil of Poona

rertic eutropept

16-28

1 soil profiles of

'luvent

i.6-36A

18-68

t h e alluvial soils of the great plains of t h e Indus and Ganges

Lnvestigations o n tl in soils

available cobalt

accumulation in B horizon

201


7OBALT JARIATIONS


iEFICIENCY IR TOXICITY

Singh. S. and Singh, B., 1966

ivailable cobalt increases with decrease in pH. Cobalt level in t h e 108 is a function of the organic matter c o n tent of the soil. N o definite relationshi] between calcium carbonate and available cobalt content. There is a positive relation between total coba and fineness in texture of alkali soils. Total and available cobalt in surface layers have lower values than in subhorizons

Duarte, U.M. e t al., 1961

acid-soluble cobalt is very low in alkalin sandy soils and in black soils on basa Cobalt content depends on degree of evolution of the soil 0.056-0.46. pH 2.5 2.5% acetic acid-

soluble cobalt

REFERENCES

Badhe, N.N. and Zende, Zende, G.K.. 1962

he level of exchange-

able cobalt is positively correlated with organic carbon content o m l a t i o n between total cobalt content and soil texture. N o relationship between calcium carbonate, organic calcium contents. pH and total cobalt content

lnly in sandy soils is cobalt content marginal, and its deficiency to be expected. A l l o er soils are well supplied with cobalt

I

Zandhawa, N.S. and Kanwar. J.I., 1964

Reddy, K.G. and Mehta, B.V., 1961

202

COBALT 16 LOCATION

PARENT ROCK AND PARENT ROCK CONTENT [p.p.m.)

SOIL TYPE

India Gujarat

L9 soil samples

India Gujarat

B representative

India Gujarat

India


soils: goradu soils (yellowish-brown alluvial sandy loam) calcareous soils

,Id and new alluvium derived from trap and limestone Pleistocene and recent sediments from granites. metamorphic and basalts sediments derived from deccan trap. basalt and sandstone

POTAL COBALT ZONTENT :Pam.)

12.4 to 47.9

>lack soils

vertisol

38-47

llluvial soils

fluvent

10-29

ieltaic alluvium

fluvent

8-13

medium black soil

vertic eutropept

Lnvertiintions on c mlt in Indian soils

15-42

HORIZON

different horizons


ZOBALT VARIATIONS

0.12-2.1.pH 2.5.2.55 acetic acid-soluble cobalt. 16 soils COI tain less than 0.25

.here is n o significant correlation between available cobalt and soil pH, organic matter, CaCo, and clay contents, b u t there is a positive correla tion between total cobalt content and clay content. Iron content is highly correlated with total cobalt conten


:otal cobalt is generally lower in the surface than in t h e lower horizons. Available cobalt decreases with depth in goradu soil and is higher in the t o p layer than in the subsurface horizons in most soils. There is generally a significant correlation between total cobalt and total iron. and between total cobalt and clay content. Except for goradu soil, available cobalt is unrelated t o pH or organic matter levels


0.1 to 0.6

I

PH 2.5;2.5% acetic acidsoluble cobalt

)EFICIENCY )R TOXICITY


REFERENCES

I

I

I

0.32-0.95 pH 2.5; 2.5% acetic acidso1ub 1e cobalt

0.20-0.44

0.27-0.32 0.15-0.27

Raychaudhuri, S.P. and Datta Biswas, N.R., 1964

.

Datta. N.P.. 1964



Australia Queensland Wallum

Australia Queensland Brigalowlands

Australia Queensland

Australia Adelaide

South-East

Australia Central Region (Todd River)

SOIL TYPE


virgin lateritic POdZ015 lateritic podzols under pasture virgin low humic gley soils low humic gley soils under pasture

ultisol

1 3 profiles of

ustochrept

I'OTAL COBALT ZONTENT :p.p.m.)

I

ultisol humaquept humaquept

gray-brown soils of heavy texture with acid substrata :layey sediments, sandst one

5 gray and brown

soils of heavy texture iiorite. basalts, 5 black earths mixed alluvium 4 red brown earths igneous, basic, 4 solodized solongranitic rocks etses granodiorite, 3 krasnozems basalts 2 red earths 2 lateritic podzolic soils 1 terra rossa ,imestone 1 rendzina sandstone 1 red podzolic soil

ustochrept

L2-16

vertisol humox natrargid

$1-72 18-34 4.5-1 5

oxisol xerochrept ultisols

3-66 3.4-3.5 1.2-1.9

xerochrept rendoll ustalf

21

terra rossas

xerochrept

3.5-30 L.9-10

rendzinas

rendoll

5.3-18 < 2

terra rossas

xerochrept

2-15 EFICIENCY )R TOXICITY

REFERENCES

Tiller, K.G., 1963

cobalt has some tendency t o higher values i n the horizons of greatest clay content Zobalt deficiency in sheep and cattle is recorded o n krasnozems and on podzolic soils b u t n o t on the brown and black earths

cobalt content is uniform down the profile

,FFECTS O F 'ERTILIZERS

Nicolls. K.D. and Honeysett, J.L.,

1964

Tercinier, G.. 1964

Tercinier, G.. 1966



SOIL TYPE

TOTAL COBALT SOIL CLASSIFICATION SYSTEM CONTENT 7 t h APPROX(p.p.m.) IMATION (U.S.D.A.)

New Caledonii

dolerite, slaggy basaltic tuffs

brown soils, reddish-brown vertic soils, more o r less degraded ferrallitic soil.. slightly evolved erosion soils slightly evolved deposit soils, colluviumalluvium soils rendzina-like soils

vertic eutropept, vertic oxleutropept oxisol

basaltic sediments

semi-peaty soil calcareous sands coralline limestone gray alluvial soil coralline limestone more or less humiferous hydromorphic volcanic pumices humocarbonated soils Polynesia Moorea Island

orthent orthent fluvent rendollic eutrochrept hydraquent fluvent aquic lithic rendoll

aquic haplumbrepl

volcanic alluvium

more or less humiferous hydromorphic

plain bog

semi-peaty hydro- hydraquent morphic soils phintaquox indurated ferrallitic soils oxisol more o r less degraded ferrallitic soils undegraded ferorthox rallitic red soil stony gray brown haplumbrept very humiferous young soils

HORIZON

!1

70-240

20-75

]

1-4

26-75

alluvial soils

basalts and andesitic basalta ancient basaltic debris basaltic debris

11 8-23 5-13

15 20-120

upper horizon

209

COBALT 18 AVAILABLE TO PLANTS COBALT CONTENT

JOBALT VARIATIONS



REFERENCES

(p.p.m.)

Tercinier, G.. 1966

he distribution of cobalt down the profiles depends on soil type; it is related to the content of humus

Tercinier. G.,1963

210

COPPER 1 LOCATION


SOIL TYPE


U.S.S.R. Latvia

ioarse morainic clay loams containing dolomite

sod weakly podzolic soils sod medium podzolic soils sod gleyed soils humic sod gleyed soils leached sod carbonate soils gleyed podzolic

cryoboralf

POTAL COPPER >0N TENT .P.P.~.)

HORIZON

cryoboralf haplaquept humaquept eutrochrept albaqualf

soils cultivated sod podzolic soils

haplorthod

U.S.S.R. Karelia

acustrine glacial clays, moraineL

slightly podzolizec and sandy loam

3.69-9.49

upper horizon

U.S.S.R. Kola Peninsul;

nepheline syenites with mantle deposits of igneous rocks and quaternary formations

mountain tundra soils

$0 (on average)

A (peaty horizon) B

U.S.S.R. Kola Peninsul; Northern and Central Taiga

$0 (on average)

xystalline schists taiga soils: (garnet, podzolic soils of central part of granulite) conthis region taining an i n t r u sion of norites: 1000 podzolic soils of the crystalline northwestern base is covered part of this with a mantle region o f greenishgray sandy loam moraine:

55 LOO

A0 A2 B C

glossic hapludalf

50 40 60 50

A0 A2 B C

histosol

75 30

AP P1 P2 C AP P1 P2 C

glossic hapludalf

100 20

95

north-western peat bog soils

50

LOO

U.S.S.R. Southern Taiga

strongly podzolized sandy soils peaty gley soils

haplorthod

derno slightly podzolic soils

glossic hapludalf

histosol

poor accumulation ilight accumulation topper absent

A2 horizon eluvial horizon eluvial horizon

211 COPPER 1 AVAILABLE T O PLANTS COPPER CONTENT (p.p.m.) 0.01-1.10 0.76 1.72 3.35 1.08

0.90 0.41

I

VARIATIONS

1N hydrochloric acidsoluble copper


1-1.45 that is to say 1 % of total copper

COPPER



REFERENCES

:opper fertilizers have a good effect o n yields of barlei grain, green corn, even flax straw the total copper content of the so2 is u p t o 80 p.p.m.

Peyve. Ya.V. e t el., 1964

...

Toikka, M.A., 1965 the concentration of copper in hydrochloric acid extract. increases gradually and slightly from bottom to t o p horizons and hardly in the uppermost peat horizon


Dobrovol’skiy. V.V. and Aleshchukin, L.V.. 1964

;: i:;

1 N hydro> chloric acid-soluble copper

9.5 4.4 4 .O 4.7 ;

listribution of copper in the profile is closely connected with the degree of podzolization

Orlov, A.Ya. and Orlova, L.P., 1 9 6 6

212 COPPER 2 ~~

LOCATION

U.S.S.R.

~

~

'ARENT ROCK LND PARENT lOCK CONTENT P.P.m.)

SOIL TYPE

Oacial sands luviatile and dune sands

10 soil samples

IMATION traces -

Studies and biblio

iphical references o n copper in the soils of U.S.S.R.

gray brown soils

orthid

15-38

;urface horizon


bottomland soils (grassland soils)

aquept or aquent

69-72

numus layer

U.S.S.R. Meschov Plain

gray forest soils soils transitional between dernc podzolic and gray forest soi

alfisol o r ultisol alfisol o r ultisol

40

D-20 crn layer

U.S.S.R. Smolensk Region

5 types of soil

U.S.S.R.

U.S.S.R. Ustvurt

U.S.S.R. Lower Volga

U.S.S.R. Southern Ukraine

ine earth clay loam deposit of quaternary age

10-20

landscape asso ciations ~ n c i e n alluvial t sands nuvio-glacial sand: incient marine sands iuaternary marine sands

steppe chernozems

calciustoll

chestnut soils and other soil types

argiustoll

southern chernozems ordinary chernozerns sandy loamy chernozems

calciustoll

poor:. traces - 5 poor: 5-8 2-56 6-120

10-43

calciustoll

2.0-3 6.7

calciustoll

1.8-8.4

0-20 crn layer

213 COPPER 2 AVAILABLE TO PLANTS COPPER CONTENT (v.p.m.)

ZOPPER VARIATIONS

traces - 1.2 (copper soluble in complexon 111)

total copper increases with increasingly finer fractions, it is higher in soils from glacial sands than in those from fluviatile o r dune sands. Available copper decreases with depth and is higher in the A 1 than in the A 2 horizon

IEFICIENCY R TOXICITY


REFERENCES

Czarnowska, K.. 1964

Kovda, V.A. e t al., 1964

14-60(water-soluble copper)

the maximum cont e n t of watersoluble copper is found in humus horizon under the cnlst


4-32

seasonal changes in copper content are determined by t h e Fe , /F e , ratio whicl governs the redoxpotential of soil

Bondarenko, G.P.. 1962

ryuryukanov, A.N. and Vasil’evskaya. V.D.. 1964

Vasil’evskaya. V.D.. 1965

0.9-10.7 0.66-6.6 0.33-3.2

t

J

10-25% of total copper

.he distribution of copper down the profile depends on relief. humus content, accumulation or removal of products of weathering and on soil formation processes

Vakulin, A.A. and Mokiyenko, V.F., 1966

.he upper soil horizons are usually richer in copper than the lower ones

Dobrolyubskii, O.K. and Kozulya, T.M., 1966

214 COPPER 3 LOCATION

PARENT ROCK AND P A R E N T ROCK CONTEN' (p.p.m.)

S O I L TYPE

SOIL CLASSIFICATION SYSTEM 7th APPROX[MATION (U.S.D.A.)

r O T A L COPPER ZONTENT :P.P.m.)

U.S.S.R.

moraine clay loams: 8-23 loessklike clay loams: 5-45 lacustrine clays silty clay loams fluvio-glacial and old alluvial sands

sod podzolic soils

glossic hapludalf

11-22

sod podzolic soils sod podzolic soils sod podzolic sandy soils sod podzolic bog

glossic hapludalf glossic hapludalf glossic hapludalf

10-33 7.7-25 1.6-13

cryorthod

14-40

Bielorussia

10RIZON

soils silty clay loams

U.S.S.R.

lake-clay deposits

Bielorussia morainic loessic type of clays

U.S.S.R. South-Eastern Polesie

parent rocks are poor in copper

U.S.S.R.

rendoll histosol

uncultivated peaty soils

histosol

peaty organic soilr sod podzolic soils sod podzolic soil

peat podzolic, medium podzolized soils weakly podzolizei peat podzolic sandy soils peat gley soils

dernopodzolic soils

Bielorussia

U.S.S.R.

humus carbonate and peat bog soils

fluvioglacial and

sod podzolic

sands: 3.6 loessial and loesslike clay loams: 11.3 morainic clay loams: 17.4

loams sod podzolic silty clay l o a m

7-41

1-5

yy;sic hapludalf

aquod haplorthod

2-10

3001

histosol

glossic hapludalf

4.2-7.4

Bielorussia

lacustrine glacial clays: 26.2

sodpodzolic sandy clay loams

10.9 glossic hapludalf

8.8-10.8

4-20 (12 on average)

ower horizons are poor in copper

21b COPPER 3 AVAILABLE TO PLANTS COPPER CONTENT (p.p.m.)

COPPER VARIATIONS


ZFFECTS O F FERTILIZERS

REFERENCES

Vil’gusevich. I.P. and Bulgakov, N.P.,

1960

Manskaya. S.M.et al.,

the copper content is higher in well humified horizons humic and fulvic acids are capable of forming insoluble compounds with copper a t pH 2.5-3.5 and pH 6 respectiv Y

1960

I

Vil’gusevich, I.P.. 1961

mobile copper:

1.37-27 available copper

=o

total copper in peaty organic soils. and 0.04 in sod podzolic soils copper remaining in peat gley soils is fixed firmly in organic complexes, ii not extracted from these by water or other solvents and is unavailable for Plants

1962

Lupinovich, I.S. and Dubikowski, G.P..

the content of copper is higher in heavier soils

0.2-3.6

(1.3)

0.4-2.8 (1.20)

1964 ipplication of COPper fertilizers is useful

0.4-1.8 (0.74)

0.7-2

Lukashev, K.I.and Petukhova, N.N.,

in peat swampy soils copper deficiency of 5 plants often occurs

lates in the humic horizon of coarsetextured sandy and sandy loam soils. Fine textured soils

Lupinovich, IS.. 1965



SOIL TYPE

SOIL CLASSIFITOTAL COPPER CATION SYSTEM CONTENT 7th APPROX(p.p.m.) IMATION (U.S.D.A.)

U.S.S.R. Amur-Basin

granite: 23 lacustrine alluvions: 16 sand with gravel: 10 tertiary sandy alluvium: 12 stratified plain deposits: 39

brown forest soil thick meadow soil brown podzolic soil gley podzolic soil

ochrept aquent or aquept

49 39

hapludalf

59

humaquod

72

floosglgfn

aquent or aquept

93

meadow soil chernozem

calciustoll

30

calciustoll and natrargid

60

U.S.S.R. Ural-Sakmara interfluve

friable sedimentary beds of Jurassic, Cretaceous, Tertiary age serpentinite eluvio-deluvium of diabase tuff

solonetzic and ordinary chernozems poorly developed chernozems poorly developed chernozems dark gray forest

calciustoll boralf

HORIZON

surface horizon

67 very high

soils U.S.S.R. Krasnodar Region Kuban

chemozemic soils gray forest soils meadow chernozem-likc soils

calciustoll alfisol or ultisol aquic or calciustol

U.S.S.R. Krasnodar Kuban

thick clay carbonate chernozems mountain forest brown soils humic carbonate soils

argiustoU

28.8

ochrept

63

rendoll

32


natric salorthid

crusty solonets

natrargid

rolodized dark chestnut soil

natric argiustoll

164 168 190 228-292 64 70 64 46-60 88-96 92 80 60 64-200

dark chestnut soils

argiustoll

U.S.S.R. Or'-Kumak Watershed

weathering crust of the elluvia of basic rocks

sluvial deluvial loams overlapping the weathering crust of the eluvia of h a r i c rnrks

upper horizon

0-20cm layer

4 31 32 car. 41 31 32 car.

4 428 31 32 car.

:car. 4 31

32 car.

217 COPPER 4 AVAILABLE TO PLANTS COPPER CONTENT (v.p.m.)

COPPER VARIATIONS

IEFICIENCY I R TOXICITY

:FFECTS OF 'ERTILIZERS

REFERENCES

biogenetic accumulation of copper in humus horizon. A2 horizon is poor

Kovda, V.A. and Vasil'eyvskaya. V.D.. 1958

copper is distributed uniformly in the profile. A high c o n tent of copper is found in soils o n tuffs of basic effu-

Krym. Ya.1.. 1964

I

of copper through the profiles is related to processes of removal or accumulation

3.8-4.8 similar values as in chernozemic

copper is only slightly mobile in all the soils

Tonkonozhenko, E.V., 1964

soils Tonkonozhenko. E.V., 1964

1 N hydrochloric

2.5

copper

J

32.6 31.8 16 4.8-8.6 12 19.2 13.5 6.4-12 18 11.6 10.4 12.4 7.2-13.6 7.8-40 8-25 13-20 4-24 '


mobile copper accumulates biologicalli in the humus and illuviai horizons; the climatic conditions of the dry steppe enable the large amounts of total cop. per originally present during soil formation t o persist in the ancient weathering crust and in the soils

Krym. 1.Ya.. 1965

218 COPPER 5 PARENT ROCK A N D PARENT ROCK CONTENT :p.p.m.)

SOIL TYPE

SOIL CLASSIFITOTAL COPPER CATION SYSTEM CONTENT 7th APPROX(p.p.m.) IMATION (U.S.D.A.)

HORIZON

U.S.S.R. Northern Azov Rostov Region

chernozems

calciustoll

21 (northern Azov) 22.5 (Rostov Region)

upper horizon upper horizon

U.S.S.R. Moldavia

chernozems soils of vineyards and orchards

calciustoll

35-44 up t o 80 when sprayed over long periods

U.S.S.R. Azerbaydzhan Sal’yansk Regic

serozems meadow soils solonchaks

aquic comborthid

U.S.S.R. Uzbekistan

imgated pale serozems dark unirrigated serozems

LOCATION

salorthid aridisol xerochrept

1

average content high content

J

burozems dark and typical

xerochrept.

serozems solonchaks

aridisol, salorthid

U.S.S.R. Uzbekistan Golodnaya

virgin and cultivated pale serozems

aridisol

18-22

U.S.S.R. Turkmenistan Tedzhen Delta

sandy. almost structureless takyr soils

salorthid

7-30

U.S.S.R. Turkmenistan Amu-Dana

irrigated meadow soils

aquent or aquept

15-33

Poland West Primor’e

alluvial soils waterlogged soils sandy and sandy loamy soils chernozems light pod7olic soil

fluvent aquent psamment urtoll

16

to

36*6 0-30cm layer of virgin soils

219 COPPER 5 AVAILABLE TO PLANTS COPPER CONTENT (p.p.m.)

2OPPER TARIATIONS

I

:opper content is greater in the B than in the A horizon of northern Azov chernozems and is greater in the B2 than in t h e A horizon of cis caucasian chernozems

mobile copper is low

DEFICIENCY O R TOXICITY

3/i of the total copper in soil occurs in available forms

0.03-6

REFERENCES

Shakuri. B.K.. 1964

!5 t o 50 p.p.m. are toxic for maize and oats

*h to

:FFECTS O F ‘ERTILIZERS

pplications of ma nure and mine1 fertilizers and high contents c organic matter crease the toxil action of c o p p

Timoshenko, A.G..

1959

Shakuri, B.K. and Akhundova, G.G.,

1965 Mirzaeva, K.Kh., 1963

mobile copper is high mobile copper is low

9.6-16( 1 N hydrochloric acidsoluble copper) in arable layer of irrigated soils. Available copper represents 36.6 t o 66.674 of the total copper

Kruglova. Ye.K.. 1962

mgation increases the copper contenl slightly down t o 100 cm

Grazhdan, P.E., 1959

3.25-11.75(1N nitric acidsoluble copper)

the soils have a good supply of copper soluble in 20% hydrochloric acid

:opper amounts increase as texture becomes heavier and degree o f cultivation increases

Atlavina. S.A.. 1965

)H has a little effect on mobility of cop

Chudecki. Z., 1963

per. Differences in contents of copper in different horizons are greatest in podzolic and alluvial soils

I

I



Czechoslovakia

micaceous paragneiss: 94.6 glauconitic sandstone: 66.3 clay stones: 48.9 dolomite: 36.3 clays and hillside loams: 35 talcites: 27 tarbonaceous sand stones: 26.6 loess and loess loams: 23.8

Czechoslovakiz

OIL TYPE

iOILASSIFI>ATION SYSTEM rth APPROXMATION U.S.D.A.)

POTAL COPPER ZONTENT :P.P.m.)

mown earth soils

xhrept

highest contents fairly high contents

oasalt. permocarboniferous clays loess loams. marl, quartzy biotite, granodiorite randy marls

50-59

iumus carbonate soils Czechoslovakir Beskydy Mountains

flysch zone slates. sandstones

rendoll

23 lowest contents

;oils o n these parent material

Czechoslovakir

L8 soil profiles


:rassland soils

10-35

aquent or aquept

36 to 100

-

HORIZON

221 COPPER 6 AVAILABLE TO PLANTS COPPER CONTEN: @.p.m.)

COPPER VARIATIONS



REFERENCES

Jurifi, C., 1966

copper is well distri-

copper content is

BeneS. S., 1964

BeneS. S.. 1963

zons of loamy soils on slates. Copper is subject t o leaching from the B horizon of acid sandy soils :opper content of soils no copper toxicity depends o n parentis encountered. rock and soil type: Copper content soil forming process is sufficient influences its distrifor crops bution

hnelhaus, V. and Valek. B., 1964

:opper content increases with

SaviE, B., 1964

222

COPPER I LOCATION

PARENT ROCK A N D PARENT ROCK CONTEN'I (P.P.m.)

Hungary Southeastern Ransdanubia Bulgaria

Bulgaria

Sasalts

gabbro

granites, sands

Rumania Cluj Region

Rumania Olt Region

Norway


brown forest soils grassland soils chernozems

ochrept aquic udifluvent calciustoll

loess eruptive rocks schists. limestone:

TOTAL COPPER CONTENT (P.P.m.)

IORIZON

average contents

140

andesitic eluvia Pliocene deposits

mdesite, Pliocene clays

Rumania Dobrudja

SOIL TYPE

5

northern chernozems southern chernozems smonitsas cinnamon forest soils light gray forest soils podzolized cinnamon forest soils roils on these parent rocks meadow bog soils of t h e Danube b ott omlands peat soils thick slightly mineralized soils

calciustoll vertic argiustoll argiustoll

38-60

alfisol or ultisol surface horizon

hapludalf

1.5-11.2 humic haplaquept

histosol

45 4-40 4-13


argiustoll

25.8-44.6

ochrept spodosol

10.8 10

chernozems

calciustoll

red-brown and red forest soils podzols

ochrept

high contents medium contents}

spodosol

low contents

zonal soils skeletal soils rendzinas

ustoll orthent rend011

26.1

sandy, silty, peat soils clayey soils

2.

ll.

low contents higher contents

223 COPPER 7 AVAILABLE TO PLANTS COPPER CONTENT (p.p.m.)

zopper tends t o accumulate in the B horizon, especiall! in brown forest sa

the available copper content is 25-50% of the total coppei content

DEFICIENCY on TOXICITY

2OPPER VARIATIONS

IFFECTS O F "ERTILI ZERS

REFERENCES

Czopf, J., 1964

I

:here is a considerable variationin content. b o t h within and between soil types] Soils are enriched in copper by biolo accumulation

Gyurov, G. e t al., 1962

;he copper content soils depends o r parent-rock and soil formation process

Donchev. 1.. 1959

Nemes, M. and Bilaus, C..1959

Biljescu, N. and Bgjescu, I., 1960

Bxjescu. 1. and Chiriac, A , , 1962

1 N hydro-

copper content increases with increasing organic matter content

distinctive d d ciency s y m p t o m s in crops are associated with less than 1 p.p.m. o f copper in soils

Semb. G. and (pien. A,. 1966

COPPER 8 LOCATION

SOIL TYPE

$OIL CLASSIFIZATION SYSTEM 7th APPROX[MATION :U.S.D.A.)

Germany (D.D.R.)

grassland soils

iquept or aquent

Germany Eastern Bavaria

parabraunerde pararendzinas pseudogley soils

ichrept !ypic eutrochrept naplaquept

Wales

Scotland

'ARENT ROCK 4ND PARENT ZOCK CONTENT P.P.m.)

hyolite nixed drifts lolerite wmice tuff nixed drifts erpentine till ,livine gabbro ti

lndesitic moraine xanitic tlll

wanitic gneiss till luartz micaschist till ilurian slate till iandstone till

1

Spain High Plains of Guadiana

'-15-25

different horizons

haplorthod

10-40

gleyed B and C horizons

iystic eutrochrept dderaquod

15-30-20

gpodosol

15-30-50

ipodosol

15-30-40

haplaquept

5-20-40

dderic cryaquod

ess than 5

I and 5

3 50

soils with lateritic concretions

hapludent

1-18.7

(on average: 5.3)

red lehm remains

I

different horizons

surface layer

vineyard and orchard soils

Pliocene sediments

in different horizons

naplorthod

France South-East

France

HORIZON

3-10 .50 20 8-12 10-150

soils on these parent-rocks

brown podzolic soil freely drained brown podzolic soil with gleyed B and C horizons brown forest soil freely drained peaty gleyed podzol with iron pan poorly drained podzol freely drained podzol freely drained non calcareous gley soil poorly drained peaty podzol with iron pan

rOTAL COPPER :ONTENT P.P.m.)

22s

COPPER 8 AVAlLABLE TO PLANTS COPPER CONTENT (p.p.m.)

2OPPEK JARIATIONS

DEFlClENCY I R TOXICITY

CFFECTS OF 7ERTlLIZERS

REFERENCES

copper supply is good in 21% of the soils: >7.6; it is medium in 46% of the soils: 6-7.5; and it is pool in 33% of t h e soils: alrl)

h1ac.h cotlon s o i l rric.diuiri black soil

l o p soil 60 c i i i and lnore

241 COPPER 16 AVAILABLE 1'0 PLANTS C o P P t i n CONTENT (p.p.m.)

COPPER VARIATIONS

REVERENCES

2.55 (0.2 M E.D.T.A soluble copper)

opper sprays a t 0.5 or 1 Ib-acre increase the grain yield significantly and the uptake an1 content in the grai of phosphorus, nitrogen and copps $oiltreatments are less effective than sprays

Dakhore, H.C. et al.,

1963

Duarte. U.M. e t al.. 1961

copper soluble in acids reaches up to 300

there is a positive , 111 soil samples are correlation between obviously well

Zandhawa, N.S. and Kanwar, J.I., 1964

traces-0.40 (pH7 1 N ammonium acetate soluble copper)

Bhumbla, D.R. and Dhingra, D.R..1964

greatest accumulatior of available coppe

Neelakantan. V. and Mehta, B.V.. 1962

greatest accumulatior of available coppe

medium black soils

1

0.o:bI .93

all soils are well sui plied with total and available

maximum accumulation of available copper is found in

...".....-.."..

I

Mehta. B.V. e l al.. 1964


'ARENT ROCK i N D PARENT LOCK CONTENT P.P.m.)

India Gujarat rlluvium (old and new) derived from trap and limestone Pleistocene and recent sediments derived from granites, metamorphic crystalline and basalt leccan trap basalt. sandstone India Vidarbha

rap rocks 'ocks of mixed Origin

SOIL C L A S S I N CATlON SYSTEh 7th APPROXIMATION (U.S.D.A.)

TOTAL COPPER CONTENT (p.p.m.1

oil group: )lack

vertisol

82-156

duvial

fluvent

24-62

nedium black

vertic eutropept

28

,lack cotton soils (30-70% of clay) Jaddy soils (sandy clays)

vertisol

iOlL TYPE

ochraquept

11-175 5 soils: (20 35 soils: 20-50 17 soils: 50-100 7 soils: more than 100

Western India

64 soils

India Maharashtra

2 red sandy loams 3 redloams I 1 laterite clay 10 black clays

1 saline loam

{ xerochrept

44-87 103-125 205 77-234 100-112 55 77-100 I14-lIiO

c1av.i

I

HORIZON

243 COPPER 17 AVAILABLE T O PLANTS COPPER CONTENT (p.p.m.)

0.62-0.70

ZOPPEK VARIATIONS

IEFICIENCY I R TOXICITY

:FFECTS OF 'ERTILIZEKS

tEFERENCES

Raychaudhuri, S.P. and Datta Biswas, N.R., 1964

1 I

1 N ammoni acetate soluble copper

1

0.38 1N

J

0.720-0.921

acetate soluble copper

ivailable copper is creases in the lower lavers

there is a negative copper soluble wi correlation N ammonium between pH and acetate varies from available copper; 0.03 t o 1.93 there is a positive 38 soils: 0.1-0.5 25 soils: more than 0 .

.n,S.K. e t al..

:tatus of available copper is quite adequate; little possibility of significant croi

Kaviman 1964

all soils are well supplied with available coppf f o r normal plant growth

geelakantan. V. and Mehta. B.V., 1962

Ranadive, S.J. e t al.. 1964

244

IODlNE 1 LOCATlON


U.S.S.R. Latvia

SOIL TYPE

SOIL CLASSlFlCATION SYSTEM 7th APPROXIMATION (U.S.D.A.)

bog soils of low peat moors sandy soils loamy sandy soils loamy soils sandy loam sod podzolic soils sod carbonate loamy soils

haplaquept

glossic hapludalf eutrochrept

U.S.S.R. Latvia

fen bogs dernopodzolic sandy soils soils o n sandy river deposits

humaquept glossic hapludalf

U.S.S.R. Moscow Region

dernopodzolic soils derno moderately podzolic soils peat gley soils peat soil of terraces

glossic hapludalf glossic hapludalf humaquept

U.S.S.R.

Investigations and bibliographic

references on iodine in

soils of U.S.S.R.

u.s.s.n.

fluvioglacial sands

forest soils neutral valley b o t t o m soils contemporary alluvial deposits

ochrept aquept or acluent

moraine clay loams silty clay loams silty clay loams

sod podzolic soils sod podzolic soils sod podzolic bog and sod bog soils sod podzolic soils sod podzolic sandy soils

glossic hapludalf glossic hnpludalf glossic hapludalf

humus carbonate and peat bog soils

rendoll and histosols

Valley of Moskva

U.S.S.R. Bielomssia

lacustrine clays fluvioglacial and old alluvial sands

U.S.S.R. Kaluzha Region

moraine deposils

U.S.S.R. Armenia-Radzan

U.S.S. R. Amur Basin

sandy loamy soils sandy dernododzolic soils dernopodzolic soils ancient cultivaled soils sod meadow soils bog soils of contemporary valley bottoms

30 soil samples 39 soil samples meadow steppe soils mounlain forest soils subalpine soils

granile: low conlents lacustrine alluvions (fine clay loams): high contents sand with gravel tertiary sandy alluvions: low contents stra1ifit.d plain deposits: high con ten 1s

glossic hapludalf glossic hapludalf

aquept haplaquept

aquept ochrept

gley podzolic soil brown forest soil

ochraquult ochrept

brown podmlic soil thick niradiow soil

hapludall humaquepl

flood plain meadow soil

h u ni aqu epl

245 IODINE 1 TOTAL IODINE CONTENT (p.p.m.)

HORIZON

0.83-7.85(3.07 o n average)

} 0.234.98 (0.62o n average) } 0.23-1.86(0.92o n average)

IODINE VARIATIONS

REFERENCES

iodine content increases with increasing organic matter and with the closeness t o the sea

Karelina, L., 1961

0.38-3.47 3.61-25.38(0.61o n average) average: 0.81 very low 1.55 1.10 18.02 23.75

Karelina, L., 1961

41 horizon 41 horizon

iodine content decreases in eluvial horizon heavy soils rich in organic matter have high iodine contents

Zyrin. N.G. and Bykova. L.N.,1960

Kovda. V.A. e t aI., 1964

high iodine content

2.3 2.1-2.7 1.2-3 2.2 1.6-2.1 1.8-3.6

} lack soils

vertisol

.5-1.8

%lluvialsoils

fluvent

.5-3.1

medium black soil

vertic eutropept

line. basalts sediments derived from Deccan trap basalt, sandstone

..28

HORIZON

333 MOLYBDENUM 18 ~~

AVAILABLE TO PLANTS MOLYBDENUM CONTENT (p.p.m.) 5-9.6%

1.3-2*3%

I

of total molybdenum

1

EFFECT O F FERTILIZERS

high content of clay and high content of free iron and aluminium oxides make molybdenum less available in regur and lateritic soils nolybdenum content molybdenum concentrations are n o t depends o n soil for entirely satisfacmation process and tory is n o t related t o thc nature of the paren rock

~~

REFERENCES

Chatterjee, R.K. and Dakshinamurti, C.. 1962

Duarte, U.M. e t al.. 1961

Datta. N.P., 1964

0.012-0.26

molybdenum deficiency symptom in rice, tobacco, beans .vailability o f molybdenum decreases w h increasing organic matter; availability of molybdenum seems to increase w h rise in alkalinity; it increases with incre re in CaCO, content of the soils and it is higher a t higher percentagl >f clay

0.188-0.578 0.180-0.251

0.07-0.09

0.05

DEFICIENCY O R TOXICITY

I I

0.02-0.5

0.04-0.13

MOLYBDENUM VARIATIONS

~

PH 2.5. 2.5% acetic acidsoluble molybdenum

application of molybdenum fertilizers is effective

Reddy, G.R.,1964

Kavimandan. S.K. et al.. 1964

Raychaudhuri. S.P. and Datta Biswas, N.R.. 1964

334 MOLYBDENUM 19 LOCATION

PARENT ROCK A N D PAR’ENT ROCK CONTEN

SOIL TYPE

HORIZON MATION

(p.p.m.)

(p.p.m.1

(U.S.D.A.) _____-_ India Gujarat

India Uttar Pradesh

Gangetic alluviu

1.

goradu soil (yellowish brown alluvial sandy loam) medium black soi black cotton soils

vertic eutropept vertisol

3 virgin alkali soil

fluvent

0.40-2.78

3 cultivated alkali soils

fluvent

(average 1.62) 0.60-3.13 (average 1.56)

1

0.5-4.1

335

MOLYBDENUM 19 AVAILABLE TO PLANTS MOLYBDENUM CONTENT (p.p.m.)

MOLYBDENUM VARIATIONS


(average: 0.40)

REFERENCES

I molybdenum cont e n t is above t h e limit of deficiency

0.1 5-1.38 0.1 (average: 8-0.59 0.80)

EFFECT OF FERTILIZERS

I

29.4-65) per- total molybl 16.S/iO]~?1 content decreases

slowly with increasing depth and moly b- with increasing denum sesquioxide content in the two soil types; in alkali soils available molybdenum content increases with increasing CaCO, content and increasing pH

Mehta. B.V. e t al.. 1964

Singh, S. and Singh, B., 1966

336 NICKEL 1 LOCATION


Finland

Studies and bibliographical references on nickel in soils of Finland

SOIL TYPE

~~

I

Finland

Scotland


375 surface layer soil samples sandy soils clay and fine mineral soils lake mud soils raw peat soils serpentine till olivine gabbro till

I

orthent

histosol

brown podzolic soil, freely drained brown podzolic soil with gleyed B and C horizons, imperfectly drained brown forest soil, freely drained peaty gleyed podzol with iron Pan podzol freely drained podzol freely drained non-calcareous gley soil poorly drained peaty podzol with iron pan

haplorthod haplorthod

brown earths

ochrept

podzols

spodosol


grassland soils

aquept or aquent

Poland Wielkopolska

alluvial soils chernozems podzols peat soils

fluvent calciustoll spodosol histosol

Poland Holy Cross Mountains Regior

sandy soils

Poland Kielce Region

rrndzinas

andesitic moraine granitic till granitic gneiss till quartz mica schist till Silurian slate till sandstone till Germany Mittelgebirge

Czechoslovakia

Rumania Transylvania

olivine. nephelinite. diabase. granodiorite, gneiss, phyllite quartz porphyry

serpentine

ochrept ferrod or sidrraquod spodosol spodosol haplaquept placaquod

rendoll

48 different soil type profiles 80% of soils contain nickel


calciustoll ochrept spodosol

337 NICKEL 1 3ORIZON

TOTAL NICKEL CONTENT (Pam.)

AVAILABLE TO PLANTS NICKEL CONTENT (p.p.m.)

NICKEL VARIATIONS

REFERENCES

Sillanpaa. M., 1962 low content

high content

nickel content increases with increasing clay content

Makitie. O . , 1962

soluble nickel content depends on

Swaine, D.J. and Mitchell. H.L.. 1960

l o w content

104-61

600-5000 70

Cleyed B and C horizons

J

25-15 4-1 5 40-80

80-150 40-100 8-20

.

pH 2.5, 2.5% acetic acidnickel

different horizons

A. B. C horizons

o n that o f parent rock and of

iumus horizon

’

tent] high

content

nickel content increases with increasing thick-

traces-40 highest contents are originating from serpentine high content medium content insignificant content

I

SaviE. B.. 1964

hydrochloric acidsoluble nickel

ioluble nickel contents are highest in the upper soil horizon

iccumulation ir (B)/C horizon

Fielder. H.J.,1966

weathering and soil Kabata-Pendias. A. and G a l c z h k a . B.. forming process 1965 result in a higher nickel content in the soils than in the parent rock rolubility of nickel de- Kabata-Pendias, A,. 1966 creases with depth in t h e profile and is related t o organic matter content iickel contents of soils Smelhaus. V. and Valek. B.. 1964 depend on parent rock and soil type. b u t soil forming process influences the nickel distribution

338 NICKEL 2 LOCATION

PARENT ROCK A N D PARENT ROCK CONTENT (P.P. m.)

Rumania Olt Region

SOIL TYPE


chernozems

calciustoll

red brown and red forest soils

ochrept

podzols

rpodosol calciustoll or argiustoll orthent rendoll

Rumania Dobrudja

loess eruptive rocks. schists limestone

zonal soils skeletal soils rendzinas

U.S.S.R. Kola Peninsula

nepheline-syenites predominate. igneous rocks. quaternary formations with a mantle of weathering deposits

mountain tundra soils

U.S.S.R. Kola Peninsula Central and Northern Taiga

crystalline schists (garnet, amphibole, granulites) with an intrusion o f norites: 300 the crystalline base is covered with a mantle of greenishgray sandy loam moraine: 85

podzolic soils in Central Taiga podzolic soils in North-Western Taiga peat bog soils in North-Westem Taiga

U.S.S.R. Ustyurt Region


gray brown soils

orthid


grassland soils arable soils

aquent or aquept

U.S.S.R. Meshchov Plain

gray forest soils and soils transitional between dernopodzolic and gray forest soils

alfisol glossic hapludalf

U.S.S.R. Snolensk Region

5 types of soil-landscape associations

glossic hapludalf histosol

U.S.S.R.

U.S.S.R. Lower Volga

ancient alluvial sands ancient marine sands fluvio-glacial sands quaternary marine sands

steppe chernozems chestnut soils and different other soil types

calciustoll argiustoll

339 NICKEL 2 TOTAL NICKEL CONTENT (p.p.m.)

HORIZON

4VAlLABLE TO PLANTS ‘TICKEL CONTENT :p.p.m.)

NlCKEL VARIATIONS

high con-

REFERENCES

6aje;cu, N . and Bajescu. I., 1 9 6 0 arable layer

content low content

30.8

12 27

nickel content of soils 6ajescu. I. and o n schists and Chiriac, A., 1962 limestone depends o n parent rock A0 peat horizoi B horizon

50-300 10-30 10-50

Dobrovol’skiy, V.V.. nickel content varies 1963 slightly within the profiles: there is a biogenetic accumu. lation

!

races-60 1-2.1 different horizons

1.2-4.9

1 N hydrochloric acidsoluble nickel

nickel accumulates in Dobrovol’skiy, V.V. and Aleshchukin, L.V., A0 horizon and in 1964 clay fraction of podzolic soils; then is

ness of moraine 5-10

different horizons

‘-20 (watersoluble nickel)

total and water-soluble Dobrovol’skiy. V.V.. 1961 nickel accumulate horizons Kovda. V.A. e t al., 1964

69-112

humus horizon

30

D-20 cm laver

9-26 traces traces-2 5 absent 30.47

-30

Bondarenko. G.P.,1962 seasonal changes in nickel content are determined by the Fe,O, ratio which governs the redox potential of soilnickel; mobility is highest a t a ratio o 1 Tyuryukanov. A.N. and Vasil’evskaya, V.D.. 1964 Vasil’evskaua, V.D.. 1965 iistribution of nickel Vakulin. A.A. and through the profile Mokiyenko, V.F.. depends on relief, 1966 humus content, soil forming process, accumulation o r removal of weathering products

340 NICKEL 3 ~

~

LOCATION


SOIL TYPE



moraine clay loams: 3.5-6 loess-like clay loams: 25-35 lacustrine clay deposits fluvioglacial and ancient alluvial sands silty clay loams

sod podzolic soils sod podzolic soils sod podzolic soils sod podzolic soils

glossic hapludalf glossic hapludalf glossic hapludalf glossic hapludalf

sod podzolic bog and sod bog soils

cryorthod and glossudalf o r boralf rendoll. histosol

humus carbonate and peat bog soils U.S.S.R. Bielorussia

morainic loessic clays lake clay deposits sands

U.S.S.R. South Eastern Polesie


U.S.S.R. Ural-Sakmara lnterfluve

fluvioglacial and ancient alluvial sands: 7 morainic clay loams: 22 loessial and loess-like clay loams: 24 lacustrine glacial clays: 4 0 friable sedimentary beds of Jurassic, cretaceous, tertiary age serpentine eluvio-deluvium of tuff

orthod spodosol

sod podzolic soils medium podzolized soils acid peaty gley soils humus gley soils

glossic hapludalf orthod histosol humaquept

1

sod podzolic soils of different textures

ordinarv chernoiems solonelzic chernozems dark gray forest soils dark gray foresl soils poorly developed cherno7ems poorly developed chernozems

calciustoll natrargid

} boralf

}

calciustoll

19 soil samples

U.S.S.R. Azerbaydzhan Little Caucasus U.S.S.R. Or’Kumak Watershed

sod podzolic soils sod podzolic strongly podzolized soils

ancient weathering crust o f basic rocks

eluvial deluvial loams overlapping the weathering crusl or eluvia of rocks

crusty solonets

natrargid


natric salorthid

solodized dark chestnut soil

natric argiusloll

calcareous eroded dark chestnut soil

argiustoll

341

NICKEL 3 TOTAL NICKEL CONTENT (p.p.m.)

HORIZON


NICKEL VARIATIONS

REFERENCES

Vilgusevich. I.P. and Bulgakov. N.P., 1960

5.6-19 5.3-36 3-9.6 3.1-14 3-14

Vilgusevich, I.P., 1961

available nickel content varies from 0.37 t o 3.47 available nickel varies from 0.22 t o 0.38 total

}

nickel accumulates in fine fractions

0.7-20

absent accumulation c nickel in humic horizon; eluvial horizon of pod201s is deficient in nickel

1

nickel is equally distributed through t h e profiles nickel accumulates in illuvial horizons nickel accumulates in humic horizons

66

133

nickel content depends Lupinovich. I.S., 1965 o n the content o f I parent rock, texture of soil, soil-forming process and biogen ic accumulation Krym. I.Ya., 1964

Vekilova. F.I. and Borovskava, Yu.B.. 1960

20-73

52 64 64 80-96 16 76 76 56-92 64-68 72 64 56 44-56

Lukashev, K.I. and Petukhova, N.N.. 1962

A B1 82 car.

C A B1 B2 car. C A A2-B B1 62 car. Z car. A1 61 82 C

9.2 20 14 7-10 14 15 8. 2.5-4 8.4 8.4 8.4 9.2 2.4-10.8 10-4 12-13.6 8.8-12 3.2-11

mobile nickel accuKrym. I.Ya., 1965 mulates biologically in the humus and illuvial horizons

342

NICKEL 4 LOCATION

SOIL TYPE



salorthid

granite: less than 5

brown forest soil

ochrept

lacustrine alluvions: 30 tertiary sandy alluvions: 1 2

chernozem brown podzolic soil gley podzolic soil meadow soil flood plain meadow soil

calciustoll hapludalf humaquod aquent o r aquept aquent or aquept

19 forest soil profiles: slightly desaturated ferrallitic scils slightly desaturated ferrallitic soils lithosols desaturated ferrallitic soils tropical eutrophic brown soil slightly desaturated ferrallitic soil

eu trorthox eutrorthox eutisol acrox eutropept eutrorthox

PARENT ROCK AND PARENTROCKCONTENT (p.p.m.)


U.S.S.R. Amur Basin

stratified plain deposits: 2 0 Ghana phyllite granite G1 pegmatite sandy parent materials B2 hornblende, schists B2 basic material Dahomey

Ivory Coast

sandy clay sediments

slightly ferrallitic clay soil slightly ferrallitic clay soil tropical ferruginous soil

tertiary sediments

slightly ferrallitic “terre de barre” soil tropical black soil

amphibolite granite schists

amphibolite schists chamockite


quartz. micaschists, migmatite. granite granite itabirite gneiss

ferrisol brown earth red soil more or less leached ferrallitic soils ferrallitic soil hydromorphic humiferous with deep pseudogley soil slightly ferrallitic red ferrisol black humiferous erosion ranker very leached ferrallitic soils

haplorthox haplorthox tropept or ustult or ustalf eutrorthox vertisol ochrult ochrept orthox ultisol oxisol ochraquept ochrult haplumbrept pale ustult o r pale udull

slightly desaturated ferrallitic soils

eutrorthox

leached hydromorphic gray ferruginous soils slightly evolved erosion soil slightly ferrallitic soils

ochraquult orthent eutrorthox

343 NICKEL 4 ~~

TOTAL NICKEL CONTENT

H 0R I Z 0N

~~~


NICKEL VARIATIONS

REFERENCES

~~

Grazhdan, P.I., 1959

40-100

5

A1 A/B-B C

5 14 49 18 29

biogenetic accumula- Kovda, V.A. and Vasil’eyvskaya. V.D.. tion of nickel in t h e humus horizon lg5*

I

42

23 25-50 10-20 20 hyllite granite Sl pegmatite randy parent material B2 hornblende. schists 82 basic material

19 forest soil profiles: slightly desaturated ferrallitic soil slightly desaturated ferrallitic soil lithosol desaturated ferrallitic soil tropical eutrophic brown soil slightly desaturated ferrallitic soil

eutrorthox eutrorthox eutisol acrox eutropept eutrorthox



U.S.S.R.


Amur Basin

Ghana

Dahomey

slightly ferrallitic clay soil slightly ferrallitic clay soil tropical ferruginous soil ;ertiary sandy clay sediments

slightly ferrallitic “terre d e barre”

haplorthox haplorthox tropept o r ustalf or ustult eutrorthox

soil tropical black soil

vertisol

161 VANADIUM 2 HORIZON

TOTAL VANADIUM CONTENT (p.p.m.)

AVAILABLE TO PLANTS VANADIUM CONTENT (p.p.m.)

accumulation of vanadium in humic horizon

I }

VARIATIONS

vanadium content Lupinovich. I.S., 1965 depends on the content of parent material and texture of the soil: the dis- I tribution of vanadium down the profile depends on soil forming process and biological accumul ion Kobiashvili, V.I., 1964

high contents

545 (watersoluble vanadium)

16-170

possible increased concentrations of vanadium in the compacted horizoi above t h e gypsum horizon

Grazhdan. P.E., 1959

40-100

120 72 24 89 290 130 160 310 140 50-200 50-60 100-200 10-30 20-100 200-300 60-125 10-150 15-86 46-120 85-160

Dobrovol'skiy, V.V.. 1961

A1 AIB B

C

t

there is generally an accumulation of vanadium in t h e humic horizon ant a decrease of vanadium in t h e A 2 horizon

Kovda, V.A. and Vasil'eyvskaya, V.D., 1958

Burridge, J.C.and Ahn. P.M.,1965 different horizons

different horizons

vanadium content increases generally with increasing depth and varies with clay content: in the slightly ferr litic clay soil. the accumulation of vanadium is below 100 cm

Pinta, M. and Ollat. C.. 1961

362 VANADIUM 3 LOCATION


SOIL TYPE


Ivory Coast

amphibolite

ferrisol brown earth slightly ferrallitic red ferrisol hydromorphic low humiferous deep pseudogley soil more or less leached ferrallitic soils more or less leached ferrallitic soils very leached ferrallitic soils black humiferous erosion ranker

ochrult ochrept ochrult ochraquept

amphibolite. schists schists granite charnockite Central African Republic

granite itabirite quartz, mica schists, migmatite. amphibolite, gneiss, granite


young alluvions charnockite, gneiss. migrnatite. amphibolite charnockite. gneiss, amphibolitt migmatite amphibolite

Chad

clayey sediments arkose, arkosic sandstone sandy and cleyey sediments sandy sediments clayey loam sediments sandy clay sediments clayey sediments

Chad

gneiss amphibolite

sandy clay material

leached hydromorphic gray ferruginous soils SUnhUy evolved erosion soil slightly desaturated ferrallitic soils

ultisol ultisol ultisol haplumbrept ochraquult orthent eutrorthox

mineral hydromorphic pseudogley soils slightly ferrallitic soils

ochraquept

leached gray ferruginous soils

haplochrult or normustalf orthent aquert

slightly evolved erosion soils hydromorphic, lithomorphic vertisols

eutrorthox

salorthid, natrargid, humaquept oxisol tropept or ustalf or ustult xerochrept subarid isohumic soils ochraquult gray ferruginous pseudogley soils halomorphic hydromorphic alluvial salic xerofluvent soils aquert topomorphic vertisols humaquept hydromorphic gley soils

saline soils, unleached alkali soils, humic gley soils ferrallitic soils gray ferruginous soils

slightly evolved hydromorphic deposit soil hydromorphic slightly hurniferous gley soils hydrornorphic slightly humiferous with deep pseudogley soils gray ferruginous soils leached gray ferruginous with deep pseudogley soils

aquic udifluvent haplaquept ochraquept tropept or ustult or ustalf ochraquult

363 VANADIUM 3 ~~~~

TOTAL VANADIUM CONTENT (p.p.m.)

HORIZON

100 80 60-100 20-80

different horizons

30-100 20-100 30-50 30


VANADIUM VARIATIONS

REFERENCES

vanadium accumulates generally in clayey horizon; lower horizon is poor in vanadium

Riandey, C.. 1964

Boulvert, Y..1966

3-10 different horizons

10 10-40

Boulvert. Y . . 1966

60-85 60-150

different horizons

30-200 100-300 200-300 55-120 20-250 15-50 traces-25 20-100 100-260

30-95 25 60 60

}

6-10

1

I

vanadium content increases with increasing depth in all soil types

Pias. J., 1968

vanadium content increases with increasing depth in a l l soil types

Vizier. J.F., 1965

upper horizon

upper horizon

364

VANADIUM 4 LOCATION

Madagascar


SOIL TYPE

marl, basalts alluvium

vertisols saline soil. hydromorphic soil

sandy hard crust. sandstone material. limestone, basic rock gneiss. metamorphic acid rock granite. limestone, basalts, voicanic ashes Madagascar.

sand and sandy loams sandy clay sediments

1

ustult rendoll

basalts

111 profiles of different soil types brown forest soils

ochrept

hapludent fluvent hydraquent vertisol tropept or ustalf or ustult orthox haplohumox

}

different soil types clayey sediments, sandstone, limestone diorite. basalts, alluvium, igneous rocks granitic rocks granodiorite, basalts limestone

Australia Queensland Brigalowlands

hydromorphic gley soil gray ferruginous soils gray ferruginous soils slightly ferrallitic soils ferrallitic soils

vertisol salorthid, aquent o r aquert humaquept tropept o r ustalf o r ustult eutrorthox oxisol

gneiss gritty limestone

lndia Australia Queensland

CATION SYSTEM 7th APPROXIMATION (U.S.D.A.)

slightly evolved flood terrace soil slightly evolved alluvial bank soil “mangrove” soil ver t iso1 gray ferruginous soil gray ferruginous soil ferrallitic red soil reddish-brown humiferous ferrallitic soil leached slightly ferrallitic red soil black rendzina

sandy clay alluvium schists sandstone granite cipolin

China North Eastern Inner Mongolia

SOIL CLASSIFI-

5 gray and brown soils of heavy texture 5 black earths 4 red-brown earths 4 solodized solonetses 3 krasnozems 2 red earths 2 lateritic podzolic soils 1 terra rossa 1 rendzina

13 profiles of gray brown soils of heavy texture with acid substrata

ustochrept vertisol humox natrargid oxisol xerochrept ultisol xerochrept rendoll ustochrept

am VANADIUM 4 TOTAL VANADIUM CONTENT (p.p.m.)

HORIZON

70-180 90


VANADIUM VARIATIONS

REFERENCES

vanadium content increases with increasing depth

Nalovirc, Lj., 1969

vanadium content increases with increasing depth

ValoviE, Lj., 1969

30-60 100-300 90-110 70-130 75 95 130 95 47 19 28 125 170 390 average: 92;concentrations of

Fang. C.L. e t al.. 1963 accumulation

those recorded

for roils of Europe and North America Sinha, R.C.P. and Banerjee, B.K.. 1965

58-346 140-180 140-200 120-130 86-130 120-270 160-170 120-200 220 160

five horiwr

in a proflle

Oertel, AX. and vanadium is present Giles, J.B.. 1963 a t lower concentrations in the surface soils than in the profile as a whole; that is a result of weathering

vanadium concentration does n o t vary in acid substrata

Giles. J.B.. 1964

366 VANADIUM 6 LOCATION

SOIL TYPE


terra rossas

xerochrept.

rendzinas

rendoll

terra rossas

xerochrept

rendzinas

rendoll

slightly evolved deposit soils reddish-brown soils reddish-brown soils brown eutrophic soils

orthent eutropept

quartz, limestone-cemented tlyach. slag- basaltic tuffs

erosion soils. slightly evolved deposit soils, eutrophic brown soils, solodized solonetses. vertisols, reddish-brown vertic soils, more or less degraded ferrallitic soil

orthent, eutisol, eutropept natrargid vertisol. vertic oxic eutropept ultisol

basaltic sediments, calcareous sand. coralline limestone

rendzina-like soils, semi peaty soils. gray alluvial soil

coralline limestone, volcanic pumices

more or less humiferous hydromorphic humocarbonated soils

rendollic eutrochrept. humbraquept. fluvent aquentic hapludoll

volcanic alluvium

udifluvent more o r less humiferous hydromorphic alluvial soils humaquept semi-peaty hydromorphic soil plinthaquox indurated ferrallitic soils more or less degraded ferrallitic soil oxisol haplumbrept stony gray brown young soils

PARENT ROCK AND PARENT ROCK CONTENT (p.p.m.1

Australia Adelaide

South East

New Hebrides

acid pumices o n basic slags basaltic slags

New Caledonia

Polynesia Moorea Island

basalts, andesitic basalts basaltic debris Hawaiian Islands

1

xerochrept

different soil types humic ferruginous latosols

haplohumox

367

VANADIUM 6 TOTAL VANADIUM CONTENT (p.p.m.)

HORIZON

120-320 130-250

surface horizon calcareous subjacent horizon surface horizon calcareous subjacent horizon surface horizon calcareous subjacent horizon surface horizon calcareous subjacent horizon

170-290 140-220 82-160 190-270 26-110 200-280

I

}

VANADIUM VARIATIONS

REFERENCES

tions are equal in surface and calcareous horizons in soils of Adelaide: vanadium concentrations are generally greater in calcareous horizon than in surface horizon in soils of S o u t h East: vanadium content depends on that of the parent rock vanadium concentrations are constant with depth

40-90

i


Tercinier. G., 1964

Tercinier, G.. 1966 70-90

upper horizon 2-7

traces-2 35-110 15 30-105 80-120 50-100 190-1520 (average 450)

highest concentration

I

upper horizon

surface horizon

the variation of Tercinier, G., 1963 vanadium concentration through the profile depends on soil type and humus content vanadium concentration depends o n parent material and weathering process

Nakamura. M.T. and Sherman, G.D.. 1961

368 ZINC 1 LOCATION

PARENT ROCK SOIL TYPE AND PARENT ROCK CONTENT (p.p.m.)

Finland

Investigations on z

c in s o h

Scotland

serpentine till

brown podzolic soil. freely drained peaty aleyed podzol with iron pan poorly drained

granitic till

TOTAL ZINC SOIL CLASSIFICATION SYSTEM CONTENT 7th APPROXI(p.p.m.) MATION (U.S.D.A.)

of Finlanc haplorthod terrod or sideraquod

240 soil samples loams sands

Denmark

France

Studies on zinc deficiencies in plants

Italy

Water culture experiments in green-house

I

Netherlands

Germany Eastern Bavaria

parabraunerde pararendzinas pseudogiey soils

ochrept typic eutrochrept haplaquept

Poland

128 soil samples slightly loamy sands alluvial soils peat soils black earths

fluvent histosol celciustoll

alluvial soils

fluvent

chernozems

calciustoll

podzols

spodosol

peat soils

histosol

alluvial soils waterlogged soils in depressions u d y and sandy loamy soils chernozems light podzolic soil

fluvent hapludent

Poland Wielkopolska

Poland West Primor’e

calciustoll glossudnlf

, HORIZON

369 ZINC 1 AVAILABLE TO PLANTS ZINC CONTENT (p.p.m.)

ZINC VARIATIONS

IEFICIENCY 3R TOXICITY

EFFECT O F FERTILIZERS

1

REFERENCES

I

Sillanpiti. M..1962

Trace Elements in Soils (Developments in Soil Science)

Trace Elements in Soils

Trace Elements in Soils and Plants

Volcanic Ash Soils, #21 (Developments in Soil Science)

Volcanic Ash Soils, #21 (Developments in Soil Science)

Trace Elements in Fuel

Trace Elements in Soils and Plants, Fourth Edition

Trace Elements in the Environment

Trace Elements From Soil to Human

Trace Elements in Soil: Bioavailability, Flux, and Transfer

Trace Elements

Fractals in Soil Science

Permafrost Soils (Soil Biology)

Biogeochemistry of Trace Elements in the Rhizosphere

Trace Elements in Man and Animals 10

Trace Elements in Man and Animals 10

Proximal Soil Sensing (Progress in Soil Science)

Determination of Trace Elements

Development of Pedotransfer Functions in Soil Hydrology, Volume 30 (Developments in Soil Science)

Remote Sensing in Soil Science

Soil Ecology Research Developments

Soil Ecology Research Developments

Soil Mechanics for Unsaturated Soils

Elements of soil mechanics

Elements of soil physics

Elements of Soil Mechanics

Elements of soil physics

Natural Attenuation of Trace Element Availability in Soils

Vital Soil, Volume 29: Function, Value and Properties (Developments in Soil Science)

Modern Soil Microbiology (Books in Soils, Plants, and the Environment)

Bio-Geo Interactions in Metal-Contaminated Soils (Soil Biology, 31)

Trace Elements in Soils (Developments in Soil Science)