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Limonitic jasper manifests itself in many types of supergene iron oxide compounds. For the present, pyrite will be the principal sulfide involved in the discussion. Jaspilite is a variety of massive limontic jasper common in Precambrian rocks.
Limonitic jasper manifests itself in many types of supergene iron oxide compounds. For the present, pyrite will be the principal sulfide involved in the discussion. Jaspilite is a variety of massive limontic jasper common in Precambrian rocks.
Limonitic jasper manifests itself in many types of supergene iron oxide compounds. For the present, pyrite will be the principal sulfide involved in the discussion. Jaspilite is a variety of massive limontic jasper common in Precambrian rocks.
Limonitic jasper manifests itself in many types of supergene iron oxide compounds, but is preeminent only in two: in cellular pseudo morphs, and as massive jasper product. For the present, pyrite will be the principal sulfide which will be involved in the discussion of limonitic jasper, though other sulfides will be mentioned incidentally. A variety of massive limonitic jasper common in Precambrian rocks is jaspilite, in which layers of jasper alternate with layers of chert. Jasper is commonly reddish, but may be yellowish or brownish. Considera- tion of jaspilites will be necessary in order to obtain an understanding of cellular pseudomorphs. In many cases silica has been precipitated as a gel, with iron oxide dispersed through it in particles so small as to make the product appear amorphous. In other cases both silica and the limonitic particles crystallized out distinctly, but so minutely that their crystal forms are recognizable only under high magnification (see table 1, ch. 2). Because of the minute grain size of the iron oxide particles within their glassy matrix, the iron content in the hand specimen frequently has been over- estimated, just as the percentage of coloring matter in glass, or the percentage of ink in a glass of water, usually is overestimated by the uninitiated. This proba- bly explains why the cellular product was not differen- tiated for so long a time from non-cellular limonite. In addition, the minute size of the particles may make difficult the determination of its correct content of iron by routine laboratory methods. The particles frequently are less than 1 micron across. Ordinary pulverizing of the sample therefore may not free or expose all the iron oxide particles from the silica which surrounds them, and such particles may fail to go into solution. More than one analyst has registered complaints upon that score. Among published papers, that by Moore and May- nard (1929), although written for another purpose, has done probably the most to clarify our conception of what limonitic jasper is, and how it is formed as a supergene mineral. Their experiments amplify and carry farther, in several important respects, the earlier work of Lovering and other investigators. The experiments by Moore and Maynard were con- ducted to show the manner of solution, transportation, and precipitation of silica and iron in ground water for areas of moderate to extensive organic decay, essen- tially free of oxidizing sulfides. Such water in many respects contrasts sharply with that originating in min- ing districts of arid and semi-arid regions, where gossans normally are best developed; but much of the informa- tion derived from the experiments is applicable to arid and semi-arid mining regions because many of the con- ditions which govern solution, transportation, and precipitation of silica and iron have universal application. TRUE SOLUTIONS AND COLLOIDAL SOLUTIONS DISTINGUISHED Before considering the results of the Moore-Maynard experiments in detail. it is important to understand the manner in which the essential components of limonitic jaspersilica and ferric oxide or ferric oxide hydrate may exist in ground water. They exist in water either in true (molecular or ionic) solution, or as colloids. Colloidal particles represent aggregates of a limited number of molecules. Though they are so small that they will be kept in suspensin indefinitely by the Brownian movement. provided further coalescence and the resulting agglomeration are prevented, nonethe- less they are large enough to be caught and retained by an animal membrane, parchment paper, or unglazed porcelain filter when the liquid containing them is passed through such a filter. The liquid, together with the colloidal particles dispersed in it, is called a colloidal solution, or sol. The words hydrosol, alcosal, etc. are used to indcate that the dispersing liquid is water, alcohol, etc. From the above descriptions it might be inferred that the only differences between a true solution and a colloidal solution of similar mineral composition is a matter of aggregation or group- molecule size. Some chemists believe, for example, that all dissolved silica (generally known as silicic acid) when freshly derived from a silicate, is in true or molecular solution, but that by aggregation of the molecules colloidal silica results (Freundlich, 1926, p. 421).' Because both true solutions and colloidal solutions of silica and ferric oxide
FORMATION OF LIMONITIC JASPER 17
minerals are nvolved in the formation of limonitic jasper, persons engaged in leached outcrop interpre- tation should grasp firmly the distinctions between the two. A final point should be noted: although particles which pass through or fail to pass through filters of the types specified usually are spoken of. respectively, as being in true or in colloidal solution, the filters conceiv- ably may have tiny holes in them too small to be detected but nevertheless large enough to permit fine colloids to pass through. On the other hand certain sub- stances have single molecules many times larger than those of inorganic origin. Under some conditions filters thus might fail to pass even a single molecule of organic substances with giant molecules. The procedure of filtration as above outlined thus can not always be relied upon to furnish a sharp separa- tion between what at present are referred to as true solutions and colloidal solutions. It does however pro- vide a crude basis for such separation. THE SOLUTION, TRANSPORTATION, AND PRECIPITATION OF SILICA AND IRON Reverting now to the experimental work performed by Moore and Maynard, partial results of the experiments, showing the solution of silica and iron from rock silicates (norite and diabaseigneous rocks) by dis- tilled and several types of ground water, are set forth in table 3, chapter 5. The experiments and other data supplied by them lead to the following conclusions regarding the solution, transportation and precipitation of silica and iron oxide. Silica 1. The average silica content of the earth's river waters is approximately 10 parts per million. The amount tends to diminish as the rivers approach the sea. On the other hand, cise to the source a content of 20 to 30 parts per million is not uncommon. 1
2. Under conditions embraced by the experiments most complete investigations thus far carried out. checking his results by practically every known method. In the last of a series of seven papers, which summarizes the principal results he discussed what he believes were fundamental errors in the work by Kahlenberg and Lincoln, and showed that the reason the previous investigators found only or mainly colloids is because they permitted the crystalloid silica to diffuse through the mem- brane and discarded it, so that only the colloidal silica remained. He concluded from his own work that in extremely dilute solutions of sodium silicate all of the silica is a true solute, and that only as the solutions become more concentrated and the Na30 : SiO. ratio increases beyond 1 : 2 are colloids developed signifi- cantly. Despite Harmon's findings not all geologists and chemists regard the issue as settled (see, for example, Hitchen, 1945). The silica content of streams depends lipn the terrain over which they flow. Invariably, the streams drainng granite and other igneous areas are higher in silica than those draining sedi- mentary and glacial areas (Tarr, 1917, p. 427). that is, in the abscnce of important sulfide oxidation to yield mineral acidscalcium and magnesium bicarbonatos, and the alkali bicarbonates. followed by peat (representative of decaying organic matter) solutions, are the most effective solvents of silica. 3. When in true (molecular or ionic) solution, the silica in natural waters is thought to be carried usually as silicates of the alkalies, notably as sodium silicate. But in time the silica particles gradually coaglate, and colloidal solutions result. :
4. Silica in true solution as sodium silicate, accord- ing to
Harman (1927) in 1925-1927 made what probably are the Moore-Maynard, when not exceeding 25 parts per million, is precipitated most effectively by sea water and calcium bicarbonate, followed much less effectively by potassium sulfate and sodium chloride. The silica comes down as a gel. The effectiveness of all electrolytes increases with concentration of silica in solution, but at ordinary concentrations in natural water, precipitation by any of them is a slow process, and rarely is complete. 5. Silica hydrosols in dilute solution are precipitated most effectively by sodium chloride at the concentration of sea water. Calcium and magnesium bicarbonate, and other electrolytes are on the whole neflicient. 6. At a concentration not exceeding 25 parts per million of silica, magnesium sulfate acts as a stabilizer for silica in true solution and as hydrosols. Above that concentration. and especially when the silica content reaches several hundred parts per million, excess magnesium sulfate precipitates the silica rapidly from solution though not from hydrosols. The silica in this case comes down not as a gel but as magnesium silicate, probably as MgO.SiCX, with excess Si0 2 . In regions such as those to which the Moore-May- nard experiments are applicable, silica in ground water is thus present mainly in small amounts. When fresh, the silica generally is in true solution; but, given time, it usually agglomerates, and is carried as a hydrosol. From a hydrosol it is precipitated effectively only by sea water or sodium chloride. Under all except very special conditions the silica precipitates from true or colloidal solution as a gel. The process is a slow one, extending over many months, and rarely goes to completion. Iron 1. The averageiron content of the earths river waters probably does not greatly exceed 1 or 2 parts per million, but individual streams carry far more. The Amazon and its tributaries, for example, carry 2 to 7 parts per million of ferric oxide; 8 to 10 parts per million frequently are present in regions where bog iron deposits or swamps do not exist, and greater amounts are found in swamps where bog iron deposits are being formed. In a broad way the iron content, in regions other than in the vicinity of oxidizing sulfide bodies, may be accepted as about one-third that of the silica content, though that ratio may not hold for individual streams. 2. In regions of moderate to moderately extensive organic decay (provided sulfides and the resulting mineral acids are not important), carbonated water, followed by peat solution, are the most effective solvents of iron from rocks. This is well shown in table 3, chapter 5. Under some conditions organic acids also are effective solvents. 3. In ground water of such regions iron in dilute concentration probably is present mainly as ferric oxide and/or ferric oxide monohydrate hydrosols, stabilized by organic colloids. The amount of hydrosol varies with the content of organic matter in the water, and with other factors. In general from 2 to 3 parts ferric oxide as hydrosol will be stabilized by 1 part of organic matter. Since the average content of organic matter in stream water is approximately 12 parts per million, it follows that such water may stabilize up to 30 or more parts per million of ferric oxide as hydrosol. When the content exceeds 30 or 40 parts per million, available organic matter in natural waters may be inadequate to stabilize all of it as colloids. In that case the FORMATION OF LIMONITIC JASPER 17
excess iron probably exists in solution as bicarbonate. 4. Most of the electrolytes, when brought in con- tact with ferric oxide hydrosols at a concentration of 10 parts per million ferric oxide, almost immediately bring about the complete precipitation of the hydrosols, but are less effective when a large amount of organic matter is present to stabilize the hydrosols. Most electrolytes likewise are effective precipitants of iron carried in true solution. Unlike the case with silica, the electro- lytes, as a whole, thus are highly efficient precipitants of iron from hydrosols and of iron from true solution, except to the extent that the hydrosols may be stabilized by the organic matter present. 5. Certain bacteria are effective in precipitating iron from bicarbonate solutions, from hydrosols, and from various salts of organic acids, but in general such precipitation probably is only incidental to the iron in ground water. Iron, like silica, thus may be and com- monly is carried as a hydrosol. Some of it is likely to be carried also in true solution, in the main probably as bicarbonate. In either case it is precipitated rapidly and effectively by " ost electrolytes, calcium and magnesium salts beir especially effective in precipitating it from true solution. Mutual Precipitation of Silica and Ferric Oxide in Jaspilites In the absence of electrolytes, as shown above, silica and ferric oxide hydrosols in dilute concentration are separately quite stable in stream water, and the silica on the whole remains stable even in the presence of most electrolytes. But a vital fact brought out by the Moore-Maynard experiments is that, when in dilute concentration in the presence of each other, mutual precipitation of silica and ferric oxide takes place from hydrosols. In the proportion of 30 parts per million of silica and 10 parts per million of ferric oxide, the iron precipitates rapidly. The silica is precipitated more slowly, but over a period of months most of it likewise precipitates. It follows that under moderately stable stream or ground water conditions there thus may be precipitated a layer relatively high in iron and low in silica, followed by a layer high in silica and either low in iron or vir- tually lacking in it. Where seasonal replenishment of silica and iron takes place in a body of water, alternat- ing layers of this type may consequently be deposited. Moore and Maynard regard this as a possible explana- tion for the formation of banded siliceous iron deposits generally referred to as jaspilites, which are so conspic- uous a feature among Precambrian rocks of almost every continent, and with which many of the earths most important iron orebodies are associated. Jaspilites are confined to Precambrian rocks, they have not been seen in process of formation, and geological opinion is not agreed upon their origin beyond the fact that the rhyt'nmic banding is sedimentary. 2 Moore and May- nards contribution to the
2 Smyth (Clements and Smyth, 1899, p. 329-487) was evi- dently the first person to study n detail the silica and jasper n the Lake Superior district. He conceived of jaspilites as being developed by coid waters during the weathering of basic rocks. Van Hise and Leith (1911, p. 513, 516), in an attempt to explain the tremendous amounts of silica and iron involved in the Lake Superior deposits, suggested that the silica and iron-bearing material was derived partly from the weathering of basic rocks, probably, however, predominantly from magmatic springs which poured out their silica and iron content on the sea fioor. They were led to that conclusin chiefly because they could not visualize natural ground water supplying either silica or iron in sufficient amount. This problem lies in establishing that, given time, natural coid ground- water solutions may be competent to supply the necessary silica and iron, and to preciptate them in their banded pattern. Whether or not some or all of the jaspilites '-ver formed in that manner is of no concern in this conaec- tion. What is of direct concern is that, with slight modi- fications to fit conditions existing in areas of oxidizing sulfide bodies. the mechanism set forth by Moore and Maynard is competent to explain formation of the limonitic jasper of cellular pseudomorphs. Modifications of Silica and Iron Reactions in Vicinity of Oxidizing Sulfide Bodies In the arid and semi-arid regions where gossans usually are most conspicuously developed, deca;.ing organic matter is less abundant, carbonated waters are less common (except in limestonej, and the inorganic salts of minerals in ground and stream waters more often are carried in solution as sulfate and chloride. As a consequence electrolytes are likely to be more abundant in stream and other ground waters of such regions. Silica Reactions. To whatever extent they may be present and dominant, the solvents of silica noted by Moore and Maynard are equally effective in arid and semi-arid regions. (Strong organic solutions rarely gradually shifting focus, has tried to bridge the gap between the views of Van Hise and those of Moore by suggesting that hot waters. emanating from igneous intrusions at depth, ha-. e raised the temperature of natural ground waters locally so as :o bring them within the low-to-moderate hydrothermal rar. ;e. The discussions of Tunell and Posnjak (1931) and Durm (1937) are also contributory to an understanding of the problem. Like Van Hise and Leith, Gruner believes that heated wa:e:s are necessary to account for the large amounts of silica and iron taken into solution, but instead of invoking the actior. of hypogene waters, he thinks they may comprise supergene waters heated in the same manner as those involved in geyser and hot spring activity as suggested by Alien and Day (1935. p. 164-231). by Fenner (1936, p. 310-315), and by Day (1939, p. 334). Dunn (1935) had previously proposed the idea to explain the formation of certain jaspilites in India: he concluded (1941) that the Indian jaspilites have been deri-ed both from iron- bearing sediments and from bedded iron-ber- ing tuffs and their derived chloritic phyllites. Moore (1953 i criticized the ideas of Dunn. Alexandrov (1955) suggested that the intermittent banding of silica and hematite in P;e- cambrian formations was due to selective weathering processes whereby the variation of the pH of leaching solutions caused the alternate deposition of silica in warm seasons and irc.n oxide in cool seasons. Obviously, much remains unknown regarding the formation of jaspilites. The fact that in numerous instances the iron oxide minerals occur as bands of crystalline magnetite, hematite, or specularite extending for many miles, makes
view was later reconfirmed by Leith and others (1935, p. 21-23). But this explanation did not satisfy a number of other geologists. They pointed out that if a magmatic origin had been involved, the deposits should exhibit the criteria of metaso- matism and metamorphism associated with the numerous magmatic deposits known elsewhere, which for the most part is not the case with the jaspilites. The view that natural ground waters could supply the necessary silica and iron, and that the precipitation could thus take place rhythmically, was first intro- duced by Moore and Maynard (1929, p. 272-303, 365402, 506-527), who set forth the full mechanism clearly, with every step in the process backed by experimental evidence. They have not proved that all or any of the jaspilites have been thus formed, but have shown that coid water activity, given enough time, may be adequate to accomplish the phenomenon. Geologists of Western Australia formerly regarded jaspilites as shear zones in greenstone, silicified by magmatic waters or by surface hardening; but more recently they have concluded that Western Australian occurrences are sedimentary deposits interbedded with volcanic flows. (For a summary of their views see McKin- stry, 1939, p. 51-65). Among those who have championed the idea of sol sedimentary deposition is Gruner who, with varying degrees of clarity and through a series of papers (1922, 1930, 1937) with FORMATION OF LIMONITIC JASPER 17
it difficult for the student of leached outcrops to conceive of such jaspilites, :r. their present form, as having been produced without deep burial or the occurrence of metamorphic action. The majoriv. of geologists now favor Smyths suggestion of their beir.g developed by coid waters, though they often differ in details. The above mentioned problem however, does not concern the limonitic jaspers involved in the interpretation of leached outcrops; for all geologists agree that the mixed silica-ferr:: oxide hydrate herein referred to as limonitic jasper, may forrr. under strictly supergene conditions. would exist there.) But in areas of oxidizing sulfide bodies. especially pyritic ones, free mineral acid nor- mally predominates; and, as shown by Lovering (1923, p. 525), its solvent action upon rock silicates may sig- nificantly increase the content of silica in ground water of such areas. This is brought out more emphatically by table 2, which presents a portion of the extensive data collected by Emmons, Jarrell, Boswell, and others, with regard to mine waters. Many factors other than the acidity of solutions determine the content of silica carried by mine or ground waters, and no fixed ratio of acidity to silica is shown in table 2. In some cases apparent contradictions exist. Xevertheless the correspondence between high acidity and higher than normal silica content is faf too marked to be explained as coincidence. From the experiments of both Lovering and Moore and Maynard it might be expected, further, that where silica content of the water is high, especially where free mineral acid is present, a variable proportion of silica could exist in true solution. Few statistics have been published upon that phase of the subject, because normally only the total silica content is determined in stream or mine water analyses. Irrespective of whether the silica occurs as hydrosol or in true solution, the data from Emmons, Boswell, and others presented above, leave little doubt that in arid or semi-arid regions which contain oxidizing sulfide bodies, the total content of silica in ground water is likely to be well above the average. To state it another way: conditions which normally bring about the formation of gossans in sulfide areas usually also yield an adequate supply of silica in ground water for formation of limonitic jasper. Iron Reactions. Carbonated waters, and especially waters containing free mineral acid, are noteworthy for their activity in attacking sulfides as well as numerous other iron-yielding minerals. Their effectiveness in dis- solving iron from rocks is well shown in table 2, and in table 3, chapter 5. Where free mineral acid is present, it is generally considered that the dissolved iron is carried in solution rather than as hydrosols, mainly as ferrous or ferric sulfate (Dole, 1909, p. 33). But even in areas of oxidizing sulfides, tests often disclose ferric oxide hydrosols, except at the immediate point of sulfide oxidation. Pre- sumably the hydrosols are stabilized by the small amount of organic matter, or whatever other special stabilizing agent may be present. Precipitation of Silica and Iron. To whatever extent the silica and ferric oxide hydrosols are both present, no reason is apparent why the two products should not in this case experience mutual precipitation in the presence of each other, just as they did in the experiments of Moore and Maynard. The presence of sodium chloride in appreciable amount in ground watera not uncom- mon condition in arid regionsmight accentuate still further the precipitation of the silica hydrosols. 1 The degree to which silica n natural waters is transported in colloidal form is a matter upon which geologists and chemists are not well agreed. For at least half a century prevailing geological opinion has been that most (some writers maintain all) of the silica in solution must be colloidal. Roy (1945) has pointed out that the impression is based largely upon inferences drawn by Kahlenberg and Lincoln (1898) from laboratory experiments performed by them which were not concerned primarily with the status of silica in natural waters; and that the conclusions of those men were accepted at the time without independent check by most geologists, and have been handed down from one writer to another, until they have grown into a geological conviction which rests upon very insecure experimental and investigational data. 3 The Moore and Maynard experiments (1929, p. 401) showed that addition of sea salt in the proportion of 34,400 parts per million to solution containing respectively 25, 49, 98. 781, 1562, 3125 parts per million of silica produced no preciptate in 4 days. At the end of 19 days a preciptate of colloidal silica was clearly evident in the solution containing originally 3125 parts per million of silica and there was a slight preciptate in the silica in the solution originally containing 1562 parts per million of silica. At the end of 200 days precipitates were evident in all the solutions.