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TB026-1929.Pdf Magnesium and Calcium in Zeolitic Soils Item Type text; Book Authors Breazeale, J. F. Publisher College of Agriculture, University of Arizona (Tucson, AZ) Rights Copyright © Arizona Board of Regents. The University of Arizona. Download date 27/09/2021 10:36:46 Link to Item http://hdl.handle.net/10150/190616 CONTENTS Page Introduction '—37 Solubilities of Magnesium and Calcium Carbonates 38 Base Replacement 40 Preparation of Soil Samples 41 Effect of Common Ions in Solution 42 Effect of Calcium Carbonate upon Base Replacement 48 Experiment with Calcareous, Magnesium-Zeolite Soil 50 Equilibrium Between Magnesium and Calcium in a Non-Calcareous Soil 51 Effect of Basic Magnesium Carbonate upon Base Replacement 53 Magnesium Carbonate in Black-Alkali Soils 55 Effect of Magnesite upon Base Replacement, When no Carbon Dioxide is Present 57 Effect of Dolomite upon Base Replacement When no Carbon Dioxide is Present 58 Effect of Carbon Dioxide upon Base Replacement 58 Base Replacement Property of Dolomite in a Saturated Solution of Carbon Dioxide 60 Reaction between Magnesium Zeolite and Calcium Carbonate 60 Reaction between Barium Zeolite and Calcium Carbonate 62 Reaction between Calcium Zeolite and Calcium Carbonate 62 Summary 64 Bibliography 65 TABLES Table I.—Base Replacement in a Sodium-Zeolite Soil as Affected by a Common Ion in Solution 43 Table II.—Base Replacement in a Potassium-Zeolite Soil as Affected by a Common Ion in Solution 43 Table III.—Base Replacement in a Mixture of Sodium-Zeolite and Calcium-Zeolite Soils as Affected by Common Ions in Solution 44 Table IV.—Base Replacement in a Mixture of Potassium-Zeolite and Calcium-Zeolite Soils as Affected by Common Ions in Solution 45 Table V.—Base Replacement in a Mixture of Barium-Zeolite and Calcium-Zeolite Soils as Affected by Common Ions in Solution -.47 Table VI.—Base Replacement in a Mixture of Magnesium-Zeolite and Calcium-Zeolite Soils as Affected by Common Ions in Solution 48 Table VII.--Replacement oi Sodium by Magnesium in a Calcareous, Black-Alkali Soil in the Presence of Sodium Chloride 48 TABLES—Continued Table VIII.—Equilibrium between Magnesium and Calcium in a Calcareous, Calcium-Zeolite Soil 49 Table IX.—Equilibrium between Magnesium and Calcium in a Calcareous Magnesium-Zeolite Soil .• 51 Table X.—Equilibrium between Magnesium and Calcium in a Non- Calcareous, Calcium-Zeolite Soil 52 Table XI.—Equilibrium between Magnesium and Calcium in a Non- Calcareous, Magnesium-Calcium-Zeolite Soil 53 Table XII.—Effect of Basic Magnesium Carbonate on Base Replacement Reactions in a Calcareous, Calcium-Zeolite Soil 54 Table XIII.—Effect of Basic Magnesium Carbonate in Base Replacement Reactions in a Calcareous, Magnesium-Zeolite Soil 55 Table XIV.—Effect of Basic Magnesium Carbonate upon Base Replace- ment in a Sodium-Zeolite Soil in the Presence of Sodium Chloride ......56 Table XV.—Effect of Magnesite upon Base Replacement Reactions in a Calcareous, Calcium-Zeolite Soil , 57 Table XVI.—Reaction between Magnesium Zeolite and Calcium Bicarbonate 59 Table XVII.—Reaction between Calcium Zeolite and Magnesium Bicarbonate in a Non-Calcareous Soil 60 Table XVIII.—Equilibrium between Magnesium Zeolite and Calcium Carbonate, and "Build-up" of Soil Zeolites 61 Table XIX.—Equilibrium between Barium Zeolite, Calcium Carbonate and "Build-up" of Soil Zeolites - , 62 Table XX.—Equilibrium between Calcium Zeolite, Calcium Carbonate, and "Build-up" of Soil Zeolites 63 ILLUSTRATIONS Fig. I.—Illustration of apparatus used in percolating soils 41 MAGNESIUM AND CALCIUM IN ZEOLITIC SOILS By J. F. BREAZEALE INTRODUCTION The development of irrigation agriculture in the United States during the past few decades, has brought up many prob- lems, among which some of the most important are those asso- ciated with the presence and accumulation of soluble salts, or alkali, in the soil. For a long time the agriculturists in the irrigated regions were interested in alkali chiefly because of its toxicity to grow- ing plants, and their efforts at reclamation and many of their irrigation practices were inspired by the desire either to reduce the concentration of the alkali already in the soil, or to prevent its accumulation in amounts that might be toxic to crop plants. However, in recent years, it has been demonstrated that there are other factors connected with reclamation that are of more importance economically than the mere removal or reduction of the concentration of the undesirable salts. Upon reclamation by the ordinary method of leaching with irrigation water, with- out the use of remedial agents, such as gypsum, practically all alkali soils, except those that contain an excess of a soluble cal- cium salt, tend to become deflocculated and impermeable to water. In Arizona, there are few soils that contain appreciable amounts of calcium sulphate or gypsum, and largely on this account reclamation has been attended with many difficulties. In many cases the soils, after being leached free from alkali, are of less agricultural value than they were before the reclama- tion was begun. Therefore, the farmer has become more inter- ested in the penetration of water and its subsequent removal by drainage, than he is in the toxicity of the alkali salts. In other words, the indirect effect of alkali upon the soil is of more agri- cultural'importance than its direct toxic effect upon the plant. The deflocculation of soils during reclamation, or under con- tinued cultivation, is brought about usually by a change in the colloidal complexes, or zeolites, in the soil. An intelligent inter- pretation of certain soil phenomena is obviously necessary in order to plan and execute practical methods of reclamation. The (37) 38 TECHNICAL BULLETIN No. 26 demand for specific information on the part of the farmer, has caused an extended investigation into the nature and function of soil zeolites, and many methods have been proposed recently for measuring the quantity of these zeolites in the soil, and for de- termining the relation of one zeolite to another. When a single zeolite, or a complex possessing the property of base replacement, occurs in a soil it is a relatively easy matter to treat the soil with a solution that carries another replaceable base, and to measure the degree of base replacement by an analysis of the percolate. However, there are few soils that can be thus treated. Calcium carbonate occurs in nearly all irrigated soils, and this salt, while only slightly soluble in pure water, is much more soluble in the aqueous solutions of all salts that are suitable for base replacement. The presence of calcium car- bonate is responsible for many of the errors that come into base replacement determinations. Many of our western soils contain magnesium carbonate also, and the presence of this salt adds; to the difficulties of base replacement determinations. The presence of relatively large amounts of magnesium zeolite in many soils has been a source of surprise to some investigators. The presence of either calcium or magnesium zeolite in the soil is of great importance. These two zeolites do not hydrolyze readily as do the zeolites of sodium and potassium. They tend to keep the soil flocculated and permeable to water, while sodium and potassium zeolites hydrolyze readily and deflocculate soils. The retention of potassium and other basic plant foods in the soil is often, indirectly, a function of the quantity of the zeolites of calcium and magnesium (1). This bulletin deals with the relation of calcium and magne- sium to each other, and with their relation to other replaceable bases in the soil, and it is hoped that these data will add some- thing to our knowledge of the reactions that take place in the soil, and that it will stimulate the development of practical methods of handling certain soil problems. SOLUBILITIES OF MAGNESIUM AND CALCIUM CARBONATES The source of calcium carbonate, and the fact of its presence in such large amounts in arid soils, has been the subject of much investigation. In the irrigated sections of Arizona it usually runs from a fraction of 1 percent to 6 percent or more, upon MAGNESIUM AND CALCIUM IN ZEOLITIC SOILS 39 the basis of dry soil. Synthetic calcium carbonate is soluble to the extent of only about 10 parts per million in pure water. While requiring a longer time to come to equilibrium, the crys- talline calcium carbonate in the soil has about the same solu- bility as the precipitated salt. In the presence of carbon dioxide, calcium carbonate is converted into the bicarbonate, and is solu- ble to the extent of 1,000, or more, parts per million of that salt. The presence of white alkali, sodium chloride or sodium sulphate, increases the solubility of calcium carbonate in the soil. Many salts of magnesium, and also other salts of calcium, exert a solvent action upon calcium carbonate. Most calcium salts are less soluble than the corresponding salt of magnesium, the hydroxides and crystalline carbonates, however, are exceptions. Calcium hydroxide is soluble about 1,600 parts per million, while magnesium hydroxide is soluble only about 8 or 10 parts per million. Magnesium carbonate in arid soils is derived chiefly from the minerals magnesite and dolomite. In either of these crys- talline forms it is very insoluble. Like calcium carbonate, its solubility ia| increased greatly by the presence of carbon dioxide in solution. It is also soluble in many other salts of magnesium, and in salts of calcium.* Under certain conditions, that are not well understood, cal- cium and magneisum carbonates combine and crystallize out as a double salt, known as dolomite. This salt is very difficult to pre- pare synthetically and, like magnesite, it is very insoluble. With the same conditions under which it was formed the solubility of the mineral dolomite could not have exceeded the solubility of either of its components, hence it is more insoluble than either calcium or magnesium carbonate.
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