Green Clay Minerals

Color is a problem for scientific study. One aspect is the vocabulary one used to describe color. Mint green, bottle green, and Kelly green are nice names but not of great utility in that people's physical perception of color is not always the same. In some industries, such as colored fabric manufacture, current use is to send a set of standard colors which are matched by the producer. This is similar to the use of the Munsell color charts in geology. None of these processes makes use of physical optical spectral studies. The reason is that they are difficult to obtain and interpret. For a geologist, color is very important but we rarely have the possibility to standardize the method of our color perception. One reason is that color is both a reflective and transmission phenomenon. The thickness of the sample is critical to any transmission characteristics. Hence, a field color determination is different from one made by using a petrographic microscope. Green glauconite in a hand specimen is not the same color in 30 μm thick thin section seen with a microscope using transmitted light.A second problem is that color in a spectral identification is the result of several absorption emissions,with overlapping signal, forming a complicated spectrum. Interpretation depends very greatly on the spectrum of the light source and the conditions of transmission-reflection of the sample. As a result, for this text, we will not attempt to analyze the physical aspect of green in green clays. In the discussion which follows, reference is made concerning color, to thin section microscopic perception.Very briefly, green clay minerals are green, because they contain iron. This is perhaps not a great revelation to mineralogists, but it is the key to understanding the origin and stability of green clay minerals. In fact, iron can color minerals either red or green or in various shades of orange and brown. The color most likely depends upon the relative abundance of the iron ion valence in the silicate (clay mineral in our case) structure, the specific bonding of these ions, and other factors. In fact, the reasons for coloration are not known completely, but it is certain that a combination of Fe2+ and Fe3+ ions is necessary to give a nice green color to clays. In the green clay minerals discussed here, the colors vary greatly as seen under the optical microscope (not always the same as the one seen in hand specimen). Yellow to blue-green hues can be found. However, for the moment, no clear relation between iron content, iron valence ratio, or other factors such as minor transition element concentrations can be found to explain the greenness of green clay minerals. The fact that a clay is green just indicates a combination of the two oxidation states of iron. The color, however, indicates the key to the formation in nature of green clay minerals.Green clay minerals are in general the product of "mixed valence" conditions of formation, most often in a situation where some iron is reduced from Fe3+ and enters into a silicate mineral structure. In general, iron would rather be an oxide when it is in the trivalent state. The moment iron is reduced to a divalent state under surface or near-surface conditions, it looks for a silicate, sulfide, or carbonate to hide in. The reverse is also true, of course. When a silicate is oxidized, Fe2+ becoming Fe3+, the iron begins to group together in oxide clumps and eventually exits the silicate structure. This is seen in thin section in altered rocks (weathering or hydrothermal action). The production of trivalent, oxidized iron usually results in a brownish or orange mineral.If the geology of the formation of green silicate minerals is relatively well defined, especially at near surface or surface conditions, the question remains how much of the iron is in a reduced oxidation state and how? In the case of reduction of iron in surface environments: if most of the iron goes to Fe2+, one mineral is formed; if only part of it is reduced, another is formed. This is the fundamental geochemical aspect of the genesis of green clay minerals; they contain iron in both oxidation states.Unfortunately modern methods of mineral analysis on a microscopic scale, electron microbeam and others, do not allow the determination of the different oxidation states of iron especially for nonstoichiometric minerals. One can use Mössbauer spectral analysis, but the scales of observations are not the same (Mössbauer needing more material); one method used for observations on a microscale, the other on a macroscale. Given the problems of micro- and macroscale observations, oxidation state information is almost excluded from data gathered since the 1980s or so, and hence information concerning the relations of iron reduction and clay genesis must be taken from older studies. A second, much greater problem is that little X-ray diffraction (XRD) work is done on samples which are analyzed chemically by electron microbeam studies. In the past both types of information, structural and chemical, were available for the same sample. Hence not only do we have no precise chemical data for many samples (oxidation state of iron), but there is a rarity of mineral structural information to go along with the incomplete chemistry. This is critical for the study of clay minerals, because slight chemical changes in a clay mineral are frequently accompanied by changes in its structure, especially when one deals with interstratified clay minerals (mica/smectites for example). In fact, the tendency to obtain more and more precision (analysis of a smaller and smaller sized sample) has led to a total loss of mineralogical data. The Heisenberg principle is unwittingly verified by geologists. We know more about a small part of a sample, but we know less about its whole. As a result, the following discussion is based largely upon old data, those which combine iron oxidation states and XRD information.