EXTENSION MODULE 4.1 Bowen’s Reaction Series This module illustrates the reactions observed to occur between minerals and magma, and the order of these reactions during magma crystallization that was described by Norman Bowen in the 1920s. A. The Reaction Principle Olivine Order of crystallization Amphibole Na-rich plagioclase feldspar Biotite Potassium feldspar Muscovite Quartz Late ▲ Figure EM4.1-1 A diagram of the reaction series. Bowen used this diagram in 1928 to illustrate two different mineral series that result from reactions between early crystallized minerals and magma. Arrows show the chemical reactions that produce new minerals (discontinuous series) and gradual changing composition within the plagioclase feldspars (continuous series) during crystallization of a silicate magma. feldspars. Relatively calcium-rich (Ca) plagioclase feldspar crystallizes first in a cooling magma. As temperature decreases during crystallization, plagioclase feldspar reacts with the remaining liquid to become progressively more sodium rich (Na), as illustrated schematically in Figure EM4.1-2. The sodium-rich Initial crystal is calcium-rich Calcium-rich Plagioclase crystal C. Understanding Each Series Magma Crystal becomes more sodium-rich as it grows The two sides of the reaction series diagram (EM4.11) depict two different types of reactions between minerals and melt. Bowen named these reactions the continuous and discontinuous series. The continuous series involves only the plagioclase EM4.1-1 Smith/Pun How Does Earth Work? Second Edition, Pearson Prentice Hall © 2010 Sodium-rich Figure EM4.1-2 Visualizing the continuous series. The first plagioclase feldspar crystals to form in a cooling magma are relatively rich in calcium. As the magma cools, the feldspar crystals react with the melt and become more sodium rich as they continue to grow. If crystallization takes a sufficiently long time, then the reactions will homogenize the crystal into a single composition. Otherwise, the center of each crystal remains more calcium rich while the edges are more sodium rich. ▲ Why should a mineral, once it crystallizes from magma, then react with the magma? The key thing to remember is that the crystallizing minerals do not have the exact same composition as the magma. For example, quartz consists entirely of silica, but no magma is 100 percent silica. Another example is olivine, which commonly crystallizes first in cooling mafic magma. Olivine contains less silica and more magnesium than mafic magma. As more and more olivine crystals form, the remaining liquid contains progressively more silica and less magnesium than before the olivine crystallized. Eventually, the magma is sufficiently silica rich and magnesium poor that the olivine crystals are no longer stable and these crystals react with the magma to form pyroxene, which contains less magnesium and more silica than the original olivine. Discontinuous series Ca-rich plagioclase feldspar Composition of plagioclase feldspar B. Why Reactions Happen Continuous series Pyroxene Decreasing temperature During crystallization of silicate magmas, reactions take place between crystallized minerals and the remaining molten liquid. These reactions change the compositions of the minerals or consume one mineral while producing a new mineral. As a result of these reactions, minerals appear and disappear in a specific order as crystallization and reactions progress. This reaction principle, which explains the minerals found in igneous rocks, is based on both laboratory experiments and evidence of mineral reactions preserved in real rocks. Norman L. Bowen presented the principle in 1928, and his research was supported by nearly two decades of research at the Carnegie Institution of Washington. Figure EM4.1-1 diagrammatically illustrates the mineral reactions. In continuous reactions, the mineral composition changes gradually as crystallization occurs. In discontinuous reactions, one mineral reacts with the liquid to produce a new mineral at the expense of the first one. Early Olivine crystal Magma Olivine reacts with magma to form pyroxene Olivine Figure EM4.1-3 Visualizing the discontinuous series. Olivine crystallizes early in mafic magma. As crystallization proceeds with decreasing temperature, the olivine reacts with the magma to form calcium-poor pyroxene. The temperature does not change until the reaction is completed. After the reaction consumes all of the olivine, the temperature continues to decrease and pyroxene continues to crystallize. ▲ Olivine crystallizes from cooling magma Decreasing temperature feldspar also contains more silica and less aluminum than the calcium-rich feldspar. The descriptive term “continuous” emphasizes that the reactions are ongoing and modify the composition within single crystals of plagioclase feldspar. The discontinuous series describes reactions between the common Fe-Mg silicate minerals— olivine, pyroxene, amphibole, and biotite. After crystallization of each mineral, reaction with the remaining liquid causes that mineral to dissolve and be replaced by the next mineral shown beneath it on the diagram (EM4.1-1). Figure EM4.1-3 schematically illustrates how olivine and magma react to form pyroxene. The term “discontinuous” applies to reactions in which one mineral is consumed and a new mineral formed, unlike the continuous series where compositional change happens continuously within a single mineral group. Pyroxene Pyroxene crystal D. Illustrations in Real Rocks Bowen realized that reactions like those produced in laboratory experiments were observed in many volcanic rocks. Rapid cooling of lava flows and nearsurface magma intrusions can prevent the reactions from being completed. Therefore, Ca-rich plagioclase can be surrounded by more Na-rich plagioclase (continuous series) and Fe-Mg silicates that formed early can be surrounded by those that formed by later reaction (discontinuous series). Figure EM4.14 illustrates these reactions in real rocks. Plagioclase crystal has a calciumrich center surrounded by more sodium-rich zones. This plagioclase feldspar in this andesite has distinct zones. Analyses show that the interior of the crystal is calcium rich and the outer zones are sodium rich. these zones reflect the reactions of the continuous series. E. Relationship of the Reaction Series to Rock Composition Where crystallization begins and ends on Bowen’s diagram depends on the initial composition of the magma and whether or not fractional crystallization occurs (see Section 4.7 of text). A mafic magma may begin with crystallization of olivine and Ca-plagioclase and be completely crystallized by the time pyroxene and slightly more sodium-rich plagioclase form. Quartz, potassium feldspar, and muscovite typically crystallize if the magma has not completely solidified after formation of sodium-rich feldspar and biotite (see Figure EM4.1-1). These minerals do not form as a result of chemical reactions but simply crystallize from the remaining magma, which typically is very rich in silica, potassium, and aluminum. These three minerals are not, therefore, part of either the continuous or discontinuous series. 2 mm The olivine crystals in this gabbro have rims of pyroxene, documenting the reaction of the olivine with the magma to produce pyroxene at the time crystallization of the rock ended. Olivine reacted with magma to form a rim of pyroxene. ▲ Figure EM4.1-4 Reactions observed in rocks. These microscope photographs show evidence for reactions in igneous rocks. (Source: Aurora Pun) EM4.1-2 Smith/Pun How Does Earth Work? Second Edition, Pearson Prentice Hall © 2010 Early Putting It Together ■ ■ ■ Continuous series Discontinuous series Ca-rich plagioclase feldspar Olivine Bowen’s reaction series diagrammatically illustrates the minerals that commonly occur together in rocks in accordance with rock and laboratory studies that show early minerals to react with magmas during crystallization. In the continuous series, reactions produce gradual changes in the composition of plagioclase feldspar during magma crystallization. In the discontinuous series, an earlier formed magnesium-rich (and calcium-poor) silicate mineral is consumed by a reaction that produces a different magnesium-rich silicate. Rock composition Mafic Intermediate plagioclase feldspar Felsic Biotite Late Potassium feldspar Muscovite Quartz EM4.1-3 Smith/Pun How Does Earth Work? Second Edition, Pearson Prentice Hall © 2010 Figure EM4.1-5 Relating Bowen’s reaction series to rock composition. The broad horizontal bands on the diagram show the ranges of approximate boundaries between the mineral compositions of mafic, intermediate, and felsic rocks. The types of minerals found in each rock type, also illustrated in text Figure 4.3, result from mineral reactions. Olivine, typical of mafic rocks, does not occur with quartz, typical of felsic rocks, because these two minerals form at different stages in magma crystallization. ▲ Figure EM4.1-5 illustrates how the reaction series explains why mineral associations are different for each compositional group. Minerals widely separated on the diagram (e.g., Mg-rich olivine and quartz) are not expected to be found together because they do not form at the same stage of magma crystallization or in magmas of comparable composition. Typically, only adjacent minerals on the diagram are found together. Bowen used an analogy to a childhood game that was popular in his time to explain the mineral associations: “Suffice it to say here that those minerals that belong to the same general period of crystallization tend to be associated and those belonging to remote periods ordinarily fail to associate. The controlling factors are thus analogous to those which determine that little girls ordinarily play ‘London Bridge’ with other little girls, occasionally with their mothers, seldom with their grandmothers and never with their great grandmothers.”