Chapter 7 M.D. Barton, R.P. Ilchik & M.A. Marikos METASOMATISM INTRODUCTION Metasomatism = changes in the bulk composition of rocks in the solid state - occurs to some degree in virtually all contact metamorphic environments, although the types, scales, and causes are varied. Most contact metamorphism is isochemical except for volatiles, Metasomatism is prominent around many intrusions, It is best developed in the upper crust, but metasomatic changes occur around intrusions even in the upper mantle. Changes in rock composition and mineral assemblages near intrusions have been of interest, and controversial since the dawn of geology (¢.g., see Skinner, 1979}. In the late 19th and early 20th centuries, there was increasing recognition that many mineral deposits and related rocks were intimately related to the emplacement of magmas (e.g., Lindgren, 1933). Many of these careful early observations remain among the best descriptions of metamorphism although they have been complemented in recent years by continuing work (see reviews by Einaudi et al., 1981; Meyer and Hemley, 1967; Rose and Burt, 1979). ‘The two end-member processes for metasomatic transfer, diffusion and infiltration, are promoted by different aspects of the igneous environment. Diffusion metasomatism (bimetasomatism) is driven by differences in chemical potential and promoted by high temperatures and prolonged times. Bimetasomatism will only be touched on here because itis generally less extensive and less well described in contact metamorphic environments (Einaudi et al,, 1981; Barton et al., Chapter 14). The interested reader is referred to papers by Brady (1975, 1977), Joesten and Fisher (1988), and Frantz and Mao (1976, 1979). Infiltration dominates the vast majority of contact metasomatism, particularly in the upper crust where circulation of external and magmatic fluids is promoted by high permeabilities. Infiltration metasomatism is occurs to some degree around most intrusions in the upper cou an many deeper intrusions, although its character, abundance, and distribution vary widely. In this paper we briefly review several aspects of infiltration metasomatism in and around intrusions including: (1) mineralogical and chemical characterization, (2) meta- somatic types, (3) environment and distribution, and (4) some general models and interpretations. Discussion of metasomatism begins with mineralogical and cherical characterization, which is simple in concept, but can be challenging in application. Metasomatic features have been described in many ways, here we emphasize the chemical types and their distribution in space. We conclude with an overview of ideas about the origin of these features. ‘Theoretical approaches to metasomatism derive from transport theory, the basic approaches summarized here emphasize simple but useful results. CHARACTERIZATION Characterization of metasomatism includes mineralogical, chemical, temporal and spatial aspects. The simplest characterizations are those that can be identified petro- graphically. These form the basis for most classifications of metasomatism and are used Tater in the paper. Symbols used in this paper are given in Table 1. Modal changes. (Changes in modes (minerals and volumes) commonly define metasomatism. These changes may be obvious as where one set of minerals replaces others, where porosity is generated or filled, or where volume clearly changes (c.g., widths of sedimentary beds decrease). They can also be subtle, such as exchange reactions which may have little322 Table 1. Symbols and abbreviations used in the text_, figure captions, and_tables Mineral abbreviations noted below are in addition to shase in Kretz, 1983 Afs alkali feldspar Alu alunite Amp amphibole, undifferentiaved ‘Ano anortheclase Csi calesilicate, undifferentiated Da —datolite Fid feldspar, undifferentiated Foid _feldspathoid, undifferentiated Px pyroxene, undifferentiated Zoo zeolite, undifferentiated viarion FE felsic igneous rocks IN intermediate igneous rocks MA mafic racks, igneous or metamorphic PE _pelite or peltie rocks QF quartzofeldspathic rocks UM ultramafic rocks Symbols used in formulas i ——_aetivity of component i ‘equilibrium tTuid concentration oF . 7 - ‘component i Cif’ initial Muid concentration of component § final (reaction complete) rock concentration of component i Cir initial rock concentration of component i ‘conceniration in the phase p Cp final concentration in the phase p initial concentration in the phase p Keg equilibrium constant final muss of component i mi” initial mass of component i volume of magma chamber stoichiomenic coefficient of componentiin pf final densit % Goa p y Phost hosttock density Pmag ‘msm density ma e initial density yi final volume Mi ‘volume of mineral i in reaction v initial volume WR water to rock ratio & reaction progress with respect to reaction i Xf inital weight fraction of component i Xj" final weight fraction of component i Xy weight fraction of water fi fugacity of component i AGE ses inconcentration of component iin ACjr —_ change in concentration of component iin the fluid the rock Amj change in mass of component i AP change in pressure, in bars aT change in temperature, in “C AN change in volume obvious effect on the mode or volume. Mineral modes are of great qualitative use (distinguishing alteration types, defining mass transfer) and have been used quantitatively to determine mass transfer (Brimhall, 1979) and progress of other reactions (see Ferry, Chapter 8). However, only when carefully determined modes are combined with mineral analyses can tnineralogical approaches quantify metasomatic changes. Even then, the bulk composition is typically better evaluated by whole rock analyses. Mineralogy, in conjunction with the phase mule, can also be used to evaluate if a system was open or closed with respect to external components (Thompson, 1959). Mineral assemblages with low degrees of freedom are less likely to be metasomatic, although care must be taken to determine which minerals are inequilibrium, and what may represent Superposition, For example among calcsilicate rocks, skarns (metasomatic) typically have high variance, whereas skarnoids (non- or sparingly metasomatic) may have similar 323 compositions but exhibit lower variance (Einaudi et al., 1981). A complication arises from disequilibrium along sharp infiltration fronts (Hofmann, 1972) which can lower the apparent variance. Chemical changes. The essence of metasomatism is that bulk compositional changes take place during metamorphism. Multiple approaches have been taken to determining gains and losses of components, most of which are based on the need to relate the initial state of the system to the final state. In terms of masses, this can be expressed by: [mni"] + (Am) = Ef), Q) where mj is the the mass of the ith species, the superscripts and refer to the initial and final states, and Am is the change in mass. Although (1) reflects what actually happens in a rock, typically only have chemical analyses are avialable, thus the operative relationship is: Lay [Xj] + [Ami] = Emi [Xi] , Q) or, because we can arbitrarily set our initial mass (say to 100 gm): [Xi] + [Am)/Emi = ComiX. @) The problem in solving for Amj comes in determining Imjf, it is a problem of determining an appropriate reference frame for mass euane (¢.g., Brady, 1975), This can be done if we know specifically how some aspect of the system changed during the process. Commonly, the mass of some component (¢.g., Alz03) is assumed to be Constant, thus the change in the total mass can be determined from a relationship such as: Xaigo3" Lmi" = XaigogZmjf or Emi/Em;" Many other considerations are equally valid. For example, if volume is conserved or if itis known to change by a.certain amount, then: Vip’ = Em‘, Vif = Emit, thus Emmy" = Wiplyv'p* @) If volume is constant, Emj/Em;" = pp’, if not, the ratio V/V" is a measure of the strain during mass transfer (cf. Brimhall and Dietrich, 1987). ‘Thus measurement of strain (e.g., from changes in bedding thickness) can yield a normalizing factor, Xaiz03' anos’ @) What is conserved? As a practical matter then, one needs to decide what is conserved, and hence provide the reference for mass transfer. Early approaches emphasized constant volumes (é.g., Lindgren, 1925) or fixed numbers of anions (e.g.. Barth, 1948), To some degree these two are related, as minerals have similar densities per oxygen atom (Carmichael, 1987). These approaches may be justified on the basis of field evidence, but offer poor approximations when net transfer reactions are significant. Altematively one can assume that a component is conserved or that volume varies in a known way (Gresens, 1967; Brimhall and Dietrich, 1987). A conserved component can be chosen on geological or experimental evidence for minimum mobility under the conditions of interest. Grant (1986) describes a simple approach to this where aliered compositions are plotted against fresh compositions. On this type of diagram, components that are conserved fall on a line passing through the origin, Colinearity (= constant enrichment or depletion) is no guarantee of conservation of mass, thus independent evidence is desiteable. Alz03, TiOz, and high-field-strength trace elements commonly appear to be immobile, although uncritical application is inappropriate. They clearly move in some324 aureoles (e.g, Barton, 1987; Gieré, 1990) and moderate solu ies are indicated by experiment (e.g. Pascal and Anderson, 1989). Variable protolith compositions. If protolith compositions vary, as they commonly do in igneous and sedimentary suites, then one or more additional degrees of freedom are introduced. It is no longer sufficient to know how one variable changed during metasomatism, rather several must be characterized. For example, if a suite of rocks has ‘one degree of compositional freedom (e.g...a simple igneous fractionation sequence), and if the ratio of two immobile components varies monotonically, then the appropriate original composition can be obtained by relating the ratio of the two back to the original composition. TiQ2 and Alz03 could be used because they are fairly immobile and they behave systematically, but differently, during fractionation in granitic rocks (TiO decreases strongly, AlO3 decreases slightly). Thus in a simple fractionation sequence TiOz/Al205 will indicate the position in the fraction sequence independent of the degree of metasomatism. Such an approach can be readily generalized to systems with more than one degree of freedom, but it will be limited by the number of well-measured immobile components, Reactions Enovieiee ‘of chemical and mineralogical changes allows specific identification of reactions and evaluation of reaction progress. This ean easily be done where textural evidence is unambiguous, for example the replacement of plagioclase by K-feldspar or sericite, It can also be accomplished algrebraically given compositional data, Not only are these changes useful for determination of the reactions, but they may also be useful for inferences about the flow path. Reaction progress (&)) is used here as the linear measure from no reaction to complete reaction (cf, Helgeson, 1979): {Sy Cp") 8) (Cpt - Cp") where Cp!, Cp” and Cp are the final (equilibrium), intial, and intermediate concentrati some product, p. The units of concetration are arbitrary, provided that they are consi Common units of measure include moles, volume, and mass. If, for example, C, moles, then the relationship between the compositional change (Am) and an independent set of reactions j with reaction progress §j and stoichiometric coefficients of transported component i (vy) is: 6) j where mw; is the molecular weight of i, This amounts to a matrix equation relating the compositional change vector to a different basis set of vectors that correspond to the reactions. Given one or more samples and a plausible set of reactions, this is just a simple mixing problem that can be solved by least squares in a way analogous to applications in igneous petrology (Bryan et al., 1969; Wright and Doherty, 1970). What Tori isa cet of values &j that may be useful nrg oF modeling the path of compositional change (see Discussion). Ttis important to remember that the compositional vector [Ami] represents the entire change in composition, thus if the path from the initial to final states is not linear, inferences drawn must be treated with caution, Any set of linearly independent reactions can be chosen, the trick is to find those that most closely represent the acutal variations, To take a simple example, hydrolytic alteration in granitoids leads to abundant sericite and quartz; it is commonly portrayed by the reaction: 2 Ht +3 KAISi30g = KAI2[AISi30i9|(OH)2 +6 SiOz +2 K* . Cc) 325 Gain-loss calculations indicate that K is commonly little changed (e.g., Meyer and Hemley, 1967), but CaGENa) is lost, indicating the following reaction is more representative: KAISi30g + CaAl2Si203 + 2 Ht = KAI[AISi300/(OH)2 +2 Si02+Ca2* (8) Among these reactions, it is convenient to distinguish between exchange reactions and net transfer reactions (cf. Thompson, 1982). Simple exchange reactions leave the number of moles and mineralogy unchanged, but alter the composition and the mass. Volume changes associated with these reactions tend to be small. Examples include Na-K exchange in feldspars and micas. Complex exchange-type reactions, such as (7) and (8), may result in changes in modal mineralogy, and may or may not conserve the number of moles (Carmichael, 1987). Net transfer reactions change the total number of moles in the system, although many of them typically have an exchange component, Volume changes are usually substantial. Examples include precipitation of quartz, hydration of olivine, and conversion of anorthite to clinozoisite with addition of calcium. TYPES Many factors control the development of comtact metasomatism, but the majority of types reflect combinations of interaction between magmas and their environment. ‘The types of metasomatism share many mineralogical and compositional characteristics (Fig. 1), but distinctions reflect meaningful differences in process and environment. Itis convenient to divide types between aluminum-rich and aluminum-poor rocks. The predominance of aluminum and silicon with variable, but lesser amounts of alkalies, alkaline earths and iron, make alteration in igneous and clastic rocks rather similar. Chemical changes predominantly involve exchange of alkalies, alkaline earths and hydrogen. In contrast, alteration is carbonate and ultramafic rocks is dominated by addition of silica, alumina and metals, and by loss of volatile components. Igneous and clastic host rocks Igneous and clastic rocks share moderate to high silica and alumina contents and respond in fundamentally similar ways to metasomatism (Table 2). As a generalization, three types of reactions take place: (1) exchange of alkalis and alkaline earths with each other and with hydrogen ion, (2) addition or loss of silica, and (3) addition or loss of volatile components. The principal mineralogical and chemcial charateristics are sum- marized in Table 2. Differences in alteration in response to similar fluids reflect variations in bulk composition thus modal mineralogy (Fig. 1B). Many investigators have described the systematics of alteration types in aluminous rocks, This summary generally follows the classification outlined by Meyer and Hemley (1967, also see Rose and Burt, 1979). Fenites are reviewed by Heinrich (1980). Recent thorough descriptions of marine alteration include papers in Barrett and Fox (1988) and Se Harper (1988), plus the paper by Alt et al. (1986) and the review by Franklin etal, (1981). -Mg-Cas] . Magnesian, sodic(-ealcic), calcie, and potassic metasomatism are characeterized by significant changes in the relative contents of Na, Ca, K, Mg, and Fe, predominantly by complex exchange reactions. Mafic and felsic minerals are both typically affected. Significant changes in volatile and Si contents may accompany these reactions, but do not characterize them. H* exchange is of secondary importance. Mg metasomatism. Magnesian metasomatism results from exchange of Mg for Fe and Ca accompanied by hydration. Itis typically expressed as chloritization of shallow marine mafic rocks, Oxidation, silica loss, and K gains are associated with this type of alteration (Bloch and Hofmann, 1978; Alt et al., 1986). In the process, the basalts are altered to low-326 Als, Ms, Pri, Kin, Alu Figure 1. ACF projection of minerals and generalized rock compositions commonly involved in metasomatic aureoles. A. Mineral compositions. B. Generalized fresh rock compositions and schematic regions for metasomatic grade assemblages by destruction of mafic minerals and feldspar, magnetite is oxidized to hematite and goethite. Mg metasomatism is distinguished from other types of chloritization by addition of magnesium to the rock in an exchange-type reactions rather than leaching of other components (Bloch and Hofmann, 1978). Na{-Ca) metasomatism, Sodie and sodic-calcic metasomatism are primarily charac- terized by Na for Ca or K exchange, and secondarily by Ca for Fe and Mg exchange (Fig. 2). They grade into calcic alteration. These types are well described in seafloor hydro- thermal systems where they afect mafic to intemmediate composition rocks Seyfried el. 1988; Harper et al., 1988; Nehlig and Juteau, 1988). Similar alteration occurs in dioritic to quartz monzonitic arc intrusions, where it may be associated with magmatic or external hydrothermal systems (e.g., Carten, 1986; Hollister, 1975}. Characteristic mineralogical changes include replacement of igneous plagioclase by sodic plagioclase (rarely analeime or scapolite) and mafic minerals by chlorite and actinolitic amphibole (Table 2). In the more calcic varieties epidote ts prominent, Volatile addition is ubiquitous. These assemblages are typically greenschist grade, less commonly lower grade. Rosenbauer et al. (1988) also 327 suggest that excess silica, high Na/Ca ratio, and low Mg content in the fluid are required to form these types during deep cireulation of seawater. A distinctive variety of Na metasomatism occurs. with strongly raluminous granitoids where Ca, K and Si are removed (Fig. 2; Charoy and Pollard, . Albite and muscovite form at the expense of plagioclase and K-feldspar. Al is apparently mobile in many of these greisen-related systems. of Types of Metasomatic Changes, ical Minevalogi ‘ypical Chemical intrasto ‘Changes ranges Component sources Alkali and Alkaline Earth Mexasomation Magnesian (Mg) Mafie min, to Chl Mg for Fe, Car+Hp0,0 ——Inmru: Marine voleanicm Comp. seawater Sodic (Sodie-calcic) Px, HI, Biot Chl, Act. Ep Na for Ca, Kr 4420.0: some Inaru.: mafic to intermediate Nota) Fid wo Czo, Ab, Sep, Ant a for Fe, Mg Comp: extemal saline; ‘magmatic Calle (Cad FW, mafic minerals t0 Ep, Chl, Ca for Mg, Na, H's +120, 0° Int: Marine voleanisan ‘Qtz: lim to Spa, Mag Comp: moshified seawater Potassie (K) Mafic min. to Bio K for Na.Ca: +Si02. +H20, Intra: felsic to-mafic (K-rieh) Pi to Kis, Ms 3,0 ‘Comp._usually magmatic Sericitic ‘Mafic min, 10 Chl, Ep, Py HY forCa, Na(,X)+H0, Inn: felsic to intermediate Fid to Ms, (Chi, Clays) £8102 ‘Comp, external or (magmatic) Iniermediste ‘Mafic min. 10 Ch, Py H* focCa,Na,K:+H0, Intru: felsic toimermediste ‘ili Pio Ms or Clays 18102) ‘Comp; extemal ¢ magmatic Geisonizaion Matic min, 10 Micas. Ch, Sulf, 14° for Ca, K,=Mg. Fe, Nav Intnt.s felsic peraluminous ‘Fld to Ms, Quz, Taz, (Ab) +H20. F.(S,B): 2(Si. Al) Comp. magmatic ‘Advanced rgillic Mafic min, to Py HY for Ca,Na, K, Mg. Fe: Intra. felsic vo intermedine Fld w Pri, And, Alu +0, S4Si03, AO;) Comp: catcmat and magmatic ve fons ropylitizat Mafic min, 10 Chl, Ep, Act, PY + H2Q. 002, S:= H*for Ca, Inirus Felsic 10 mafic Fd and Fotds to Zoo, #Clay,Cal_ Na; More intense in mafic rx Comp> external and magmatic Zeolitzation _—-Mafic min. t0 ei. le. +0. CO Ist. mainty mafic Fig and Foids to 200 Comp.: external Eenitization Feritizaion and Mafic mia. to NP, Na-Amp. Aluminous host: Na. K: Intra: ‘Nepheline spe ewbonatitzation Bio; Removal of Qtz 3C0;.Ca, Fe. Mg:- SiOz carbonatie, rue kimbesite Fld and Ms to Afs, Folds, Carb Carb, host: +Na. K. (Mg. Fe) _Comp.:_ magmatic (+ meteoric) Carhohate-hosted mpes Anhydrous Skam Cal ioanhyd. Caksilicates (Gri, - COz, (H2O); = Ca, Mgi +Si, tnurus Felsic and intermediate, px. CaP, etc) Fe, Al-(meials) redox state, ave with male and alkaline Dol woarhyd, Mg-Caksiticates metals. afdelemental ritios Comp: magmatic (Fo, Di, Mii, Mag etc.) vary with magna types Hiydrous Skarn Ca skarn & Cal to Ep.Chi, Act, Ca, Mg: * C03. $. Al, Int: Felsie and imtermediate (Qu. sulfide et metals: + $i, H2O fare with mate (Mg skam & Dol to Th, Srp. Bre Comps magmatic and extemal ie ete, RReplacementand Calcsilicates or Carb to Qtz other + 51,5. H+.H20,(COz), nina; esis and intermediate Silicification Carb, clay, and sulfides metals Comp.: extemal and magmatic Endoskam Als to Ca-PI, Ep. Ca-Grt #003. HO. C2: intrusions ra: felsic 1 matie Matic min 10 Cox form host ‘Comp: magmatic and external Uirramafic-hosted mpes Blackwall Formation of Chl, Amp, Tle, SiQ2_Al203. 170 ¢ Fe, min Felsic and intermediate (cat) ‘Mg: # #20, (C03) Comp: magmatic Steatiization & — Low-Si uluamafic silicates to + SiOz 120, (CO2) Ther. Variable Serpentnization The, Srp. Mag. Amp. Car ‘Comp.: external or magmatic328 Ca metasomatism. Ca metasomatism (calcic alteration) in seafloor rocks results in epidosites by addition and exchange of Ca for Mg, K, and Na (Schiffman and Smith, 1988). Calcic plagioclase and mafic minerals are converted to epidote, alkali feldspars to zeolites and illmenite to sphene and magnetite. The excess Ca appears to result in some hydrolytic alteration as well through reactions such as (Seyfried et al., 1988); 3 CaAlpSiz0g + Ca2* +220 = 2 CapAlz(SiO4)3(OH) +2 H*. @) Na-Ca metasomatism Na KA 10 SYMBOLS TS, = ‘open = fresh 0.01 Normalized to Al slased = altored Gat F Na K Ca Fe Mg Si Zvol Josephine —/ basalt Harper et al. (1988) ‘Yerington granite / Qtz moncodiorite te caren (1986) estas qu-s« Yorington granite) granite Figure 2. Chemical changes for some examples of Caren (1986) sodic(-calcic) metasomatism in marine-and arc rocks. Kyushu granadiorite shale ‘Shown are standard AFC projections, molar propor- —"“*""— Oba (1968) tions of Na, Ca, and K, and compositions of altered —_g4___ Karmutsendiorte/mafie wit rocks normalized to fresh rocks. Compositions of Kuniyoshi d Liou (1978) intrusions and host rocks are indicated along with the ca espp ++ Emuford granite / psammite data sources. (Charoy & Pollard (1989) K metasomatism Na KA 10 SYMBOLS| open = fresh closed = altered “Ca O41 F Na K Ga Fe Mg Si Evol Bingham granite / granite Moore (1978) a. — Yettington ganite (Qt monzonite Figure 3. Chemical changes for some examples of Carten (1986) potassic alteration, Shown are standard AFC pro- Kywshu granodiarite/shale jections, molar proportions of Na, Ca, and K, and ~ ” ha (96H) ‘compositions of altered rocks normalized to fresh rocks. Compositions of intrusions and host rocks are Land's End granite / dolerite indicated along with the data sources. Mitrapaulos (19825 1984) 329 Similar calcie alteration involving garnet and clinopyroxene has been reported in arc rocks (Battles, 1990). The high Ca coment of the fluids may result from the combined effects of Mg and Na-Ca metasomatism along earlier portions of the fluid path. K metasomatism. K metasomatism (potassic alteration) is characterized by replacement of sodie and calcie phases by potassic phases (Fig. 3). Exchange of K for Na and Ca may be accompanied by silication, addition of metals, and hydration. Typical reactions include replacment of mafic minerals by biotite and plagioclase by potassium feldspar + muscovite (Table 2). In igneous host rocks, the pseudomorphous replacement of pyroxene or amphi- bole grains by "shreddy" biotite is ‘Eaguosie ‘of K metasomatism. K-metasomatism in pelitic rocks around granites is rarely described (e.g., Oba, 1968; Brammall and Harwood, 1932) may take place both by exchange reactions and conversion of micas to feldspars (Table 2; ef. fenitizaiton). Formation of muscovite and biotite alone is not diagnostic as they may form by other reactions involving other K-rich minerals already present. Also, low-temperature K-feldspar flooding in some environments may be related to contact metamorphism (e.g., Hanson et al., 1991), but its origin is often ambiguous. Hydrogen-ion metasomatism. Hydrogen-ion metasomatism (hydrolytic alteration) is characterized by exchange of hydrogen ion for other cations, typically Na, K, and Ca. HO, COp, and § ate commonly added. Hydrolytic alteration destroys feldspars resulting in silica release and deposition (e.g., Eqn. 8), although total silica may increase or decrease (Fig. 4), For similar integrated fluid fluxes, the intensity and extent of the alteration depends on the acidity of the fluid and the neutralizing power of the minerals in the rock. Therefore, a wide range of effects are observed from minor removal of Ca and Na to complete leaching of Na, K, and Ca. At shallow to moderate depths, the most abundant types are include sericitic, argillic, chloritic, and advanced argillic alteration, Hydrolytic Na KA 10 O41 0.01 aes 0.001 Neenalzed tol closed = altered Cg F Na K Ca Fe Mg Si Vol Neer Kentucky granite /granite ‘Vernon etal. (1987) Lands End granite /dolerites Mitropowlos (1982; 1984) Renison-Bell granite / granite Paterson et al. (1981) Bruce Mine —/ andesite Larson (1984) Josephine — / basalt Zierenberg et al. (1988) Land's End granite / pelites Miropoulos (1982; 1984) Figure 4. Chemical changes for same examples of hydrolytic alteration, Shown are standard AFC projections, molar proportions of Na, Ca, and K, and compositions of altered rocks normalized to fresh rocks. Compositions of intrusions and host rocks arc indicated along with the data sources.330 Sericitic alteration. Sericitic alteration is characterized by conversion of K-feldspar and plagioclase to sericite (tclay) minerals (Meyer and Hemley, 1967; Table 2). Mafic con- stituents are reconsituted as chlorite, epidote or sulfides. At higher temperatures and(or) where fluids contain appreciable fluorine, hydrolytic alteration may be expressed as greisenization (Shcherba, 1968), Coarse-grained muscovite is typical (but not required) as are F-bearing minerals including F-micas, topaz, and fluorite which form at the expense of feldspars. Mafics go to Li-Fe-micas, chlorite, sulfides, and oxides. Mass changes typically include loss of Ca and Na, gain or loss of K and Si, and gain of volatiles including F and $ (Fig. 4). The equivalent in higher pressure and higher temperature rocks may be formation of an AlpSiOs polymorph (e.g., Vernon et al., 1987). In mafic host rocks, the paucity of K and the abundance of Mg and Fe lead to the development of chlorite as the strongly peraluminous mineral in place of or in addition to Sericite during hydrolytic alteration. Chloritic alteration is seen in many intermediate composition systems (Seedorff, 1991) and marine volcanic systems (Franklin et al., 1981) where it has been confused with propylitic alteration. Ca and Na are lost while Mg and Fe may increase or decrease (¢.g., Bruce Mine and Josephine data, Fig. 4). Intermediate argillic alteration. These two types reflect varying degrees of lower temperature acid metasomatism. Intermediate argillic alteration is characterized by destruc- tion of plagioclase to form sheet silicates, but without destruction of K-feldspar. Mafic minerals are commonly converted to chlorite. Mass changes are apparently smaller than for other types of hydrolytic alteration (Meyer and Hemley, 1967), This type is the weakest of all and results from the least acid solutions (Montoya and Hemley, 1975). Advanced argillic alteration, Advanced argillic represents essentially complete leaching of Ca, Na, K, and Mg from original rocks (Meyer and Hemley, 1967). Some Fe may be retained (as pyrite) and aluminum may be mobile. The result is that mafics are destroyed, sulfides formed, and feldspars and micas are converted to pyrophyllite, andalusite or other aluminosilicates. The fluid may be magmatic or external, but argillic alteration generally indicates a high fluid flux and low K/H and Na/H ratios, Advanced argillic alteration results in the complete conversion of feldspars and muscovite to clay minerals, pyrophyllite, and alunite, and complete destruction of mafic phases with attendant pyrite deposition. Advanced argillic alteration may form by the action of acidic magmatic fluids. AlpSiOs minerals in higher pressure rocks do not reflect advanced argllic alteration where they occur with K-feldspar (e.g., Vernon et al., 1987). Volatile addition and silication. These alteration types are characterized by addition of components such as HzO, CO3, S, and SiOz, but may also involve exchange reactions. Because these are neutral species, no exchange is required to maintain charge balance. Volatile addition. Volatile addition (proplytic alteration, zeolitic alteration, retrograde hydration) is the most widespread of chemical changes in aureoles. Volatile-poor igneous and high-grade metamorphic rocks are particular susceptible, to retrograde volatile addition accompanying fluid inclux. Volatile addition commonly grades into alkali-exchange and hydrolytic types. Whereas some destruction of mafic components and feldspars may be necessary to propylitization, the net effect is not dominated by H* for Na, K. Ca, Fe, and Mg exchange. Other volatilization reactions include serpentinization and zeolitization. In both cases, HoO 4 CO2 are added to the mafic and felsic components, respectively, to form serpentine and zeolite minerals + carbonates. These reactions occur within and commonly extend well beyond contacts. Most commonly these alterations involve external water. Silication. Silication is net addition of SiO, commonly as quartz but alse as more silica-rich minerals, particularly in quartz undersaturated rocks (see below’). Unlike other types, it is not usually coupled with exchange or hydration reactions. Silication can only be: Proven when properly normalized mass-balance calculations show a net increase in SiO. Na KA SYMBOLS Normalized to Al ‘open = fresh closed = altered Ca F Na K Ca Fe Mg Si EVol Brent Crater carbonate / granite Curie (1971) gp — Monehique syenite/ plite A Rock (1976) wees eq... Monchique syenite /psammite Rock (1976) Figure 5. Chemical changes for some examples of ___.—_—Pollen carbonate mafic curmulate fonitization. Shown are standard AFC projections, Robins & Tysscland (1983) molar proportions of Na, Ca, and K, and compo- ___ gq Soklicathonatse/ granite ntiss sitions of altered racks normalized to fresh rocks. Vartiainen & Woolley (1976) ‘Compositions of intrusions and host rocks are Sok carbonatite/ schist indicated along with the data sources. HE Vartisinen d& Woolley (1976) In alurninous rocks, silication results from cooling or decompression and thus commonly forms a part of other alteration types such as potassic alteration. Fenitziation Fenites comprise an intense: and distinctive reaction set of metasomatic rocks developed in the aureoles around alkaline intrusions, Fenitization is characterized by addition of Na, K and CO and removal of $iQ2 from quartzofeldspathic, pelitic, and mafic rocks with variable redistribution of Ca, Fe, Mg, and AlO3 (Heinrich, 1980; Currie and Ferguson, 1971; Kresten and Morogan, 1986; Morogan, 1986; Vartiainen and Woolley, 1976; Fig. 5). Mafic constituents are reconstituted as sodic pyroxenes or amphiboles, or phlogopite, feldspars and muscovite go to alkali feldspar or feldspathoids, quartz is removed, and carbonates may be added to the rock. Syenitic intrusions generate dominantly sodic fenites that are rarely quartz undersaturated , while carbonatites generate sodic and potassic fenites that may be quartz undersaturated (Heinrich, 1980; Rock, 1976). Kimberlites and other ultrapotassic intrusions generate limited potassic fenites (Ferguson et al., 1973), ‘The extent and intensity of fenitization is greater in quartzofeldspathic than pelitic rocks, For carbonatitic intrusions, quartzofeldspathic rocks make silica- undersaturated fenites while pelitic rocks rarely become undersaturated with respect to silica (Rock, 1976). Carbonatization, the reconstitution of felsic and some mafic components as ‘carbonates, is often associated with fenites around carbonatites and kimberlites, Carbonate and ultramafic host rocks Carbonate and ultramafic rocks are particularly susceptible to contact metasomatism because they are generally far from equilibrium with magmas and magmatic fluids. Consequently compositional changes are typically larger than in aluminous rocks. . Metasomatism is particularly well developed in carbonate rocks, Mineralogical variations systematically reflect intrusion types and host. This summary is based mainly on the on extensive reviews published elsewhere (Burt, 1977; Einaudi et al.,332 Na KA 100 7 10 ot Sree Normalized to mass. ‘open = fresh 0.01 slosed = aterad Cd Fo"lNa Al Ga Fe Mg Si Evol Ely Quz monzosite | limestone James (1971) Ely Qtz monzonite/ limestone Ae james (197 seuengeveee Bishop granite /Timestone fr cman (1965) Figure 6. Chemical changes for some skams. ____..__ king Island granite / limestone Shown are standard AFC projections, molar Kwak (1978) propartions of Na, Ca, and K, and compositions of Mina granite Flimesione altered rocks normalized to fresh rocks. Composi- BE owak & Askins (198) tions of intrusions and host rocks arc indicated along |. |p |, Moina granite / limestone with the data sources, Kwak & Askins (1981) 1981; Binaudi, 1982a,b; Einaudi and Burt, 1982; Kwak, 1987; Zharikov, 1970). It is evident in many cases that nothing is conserved in carbonate rocks, although there are commonly empirical arguments for approximate conservation of volume (Lindgren, 1925). Metasomatism in carbonates is broken into three overlapping types in approximate relation to temperature of formation: anhydrous skarns, hydrous skains, and replacement bodies (Table 2). Low-Fe calesilcate assemblages (skarnoids) are also common in these systems. These typically represent local exchange of components between calcareous and aluminous rocks (bimetasomatic skams) or simply prograde reactions in impure carbonates. They generally predate formation of infiltration skams, and are distinguished by their distribution and lack of exotic components (Einaudi et al., 1981). Endoskam is the analogaus, calcium-rich alteration of intrusions along contacts with carbonate rocks, Endoskarn may reflect infiltration of fluids from the host rocks as well as diffusional exchange. Anhydrous skarns. The highest temperature metasomatic alteration typically results in predominantly anhydrous calcsilicate assemblages formed by infiltration of magmatic fluids. Chemical changes are dominated by the addition of silica with abundant iron and alumina, and large losses of volatile elements (Fig. 6, Table 2). Variable amounts of magnesium, alkalies, and rare element are also commonly added. These assemblages typically contain combinations of Ca-Fe-Al gamet, pyroxene, pyroxenoids, and idocrase in calcic (limestone) hosts, and forsterite, diopside, monticellite, magnetite, tremolite and chlorite in magnesian (dolomite) hosts (Einaudi et al., 1981; Zharikov, 1970), Within these broad groups, the proportion and identity of phases reflects the composition and oxidation state of the magmas (Einaudi et al., 1981). Oxidized skarns are characterized 3+, typically in andraditic garnet and oxides; pyroxenes are typically Fe-poor. Conversely, reduced skams are typified by grossularitic and sub-calcic gamets (almandine, spessartine) and Fe-rich clinopyroxenes. 333 Hydrous skarn and replacement, Hydrous (or retrograde) skarns are characterized by hydrous calc-silicates, and commonly have abundant accessory minerals such as oxides and sulfides (Table 2). Lower-temperature replacement assemblages are characterized by the lack of calesilicates (excepting zeolites and clays) and an abundance of quartz, secondary carbonates and accessory minerals such as sulfides. Chemical changes in both types can be broadly similar to anhydrous skams where hydrous skars replace carbonate. Beside differences in volatile contents, a wide-range of exotic components may be added as will as significantly different proportions of Fe and Al (Einaudi et al., 1981; Kwak, 1987). Where hydrous skarn and replacement assemblages are superimposed on anhydrous skarns, the high-temperature phases are typically partly to completely replaced by lower temperature equilivalents, In some situations where hydrolytic alteration is prominent in igneous rocks, extensive hydrolytic alteration in skarms results in formation of silica-pyrite- clay rich replacement zones (Einaudi, 1982a). Ultamafic rocks Emplacement of felsic magmas into ultramafic rocks forms blackwall alteration (Arai, 1975; Table 2) similar to that observed from bimetasomatic reactions between ultramafic and siliceous rocks during regional metamorphism (Sanford, 1982). At the contact, diffusion of SiQ3 from the intrusion, and FetMg from the ultramafic rocks forms intermediate zones of chloritetbiotite. Farther into the host, hydration and silication reactions may result in additional zones of amphiboles, talc, and serpentine group minerals. Desilication of intrusion margins as a result can result in corundum bearing rocks (Vlasov, 1968; Rossovskiy et al., 1981). Most of the literature on blackwall occurrences are written from a regional metamorphic context (e.g., Sanford, 1982; Mathes and Olesch, 1986) or interpreted to be the result of ultramafic rocks tectonically emplaced against aluminous rocks (e.g., Green , 1964). At the small scales typical of most blackwall zones, distinction of diffusional and infiltration, and indeed igneous origins may be difficult to establish (e.g., Grundman and Morteani, 1989). ENVIRONMENTS AND DISTRIBUTION, ‘The various factors that influence metasomatic style are interrelated by their mutual dependence upon environmental factors. To a large extent, environment governs magma type, availability of external fluids, thermal structure, and the types and grades of host rocks that may be intruded, These systematics allow generalizations to be made about the processes and reactions that occur, and hence the effects of metasomatism. The descriptions below are summarized in Table 3. Depth. Contact metasomatic features are strongly concentrated in the upper crust where their development reflects the strong chemical and physical constrasts, the ubiquitious presence of external fluids including seawater, and abundant brittle structures offering high permeabilities (cf. Barton et al., Chapter 14). With depth, infiloration metasomatism is generally subdued and restricted to the vicinity of intrusive contacts; ductile beha’ subdued physical contrasts, and the paucity of extemal fluids limit the metasomatic varieties to less extreme examples of shallower types. Sources of Companents. Igneous and external sources of metasomatic components are both prominent. This evidence has been extensively reviewed elsewhere, and is noted where appropriate below. A strong magmatic component in many types of proximal and high-temperature alteration is clear from combined field, isotopic, and petrological data (e.g., Taylor, 1979; Ohmoto, 1986; Finaudi et al,, 1981; Burnham, 1979). This is supported by the close association of many types of metasomatism with magmas that release fluids and the scarcity of strong metasomatic alteration in non-maring volatile-poor magmas. External fluids cause the bulk of metasomatism that typically overprints more localized magmatic alteration, Seawater involvement in marine volcanic systems is clear from isotopic, chemical, and field evidence (c.g., Muehlenbachs, 1986; Franklin ct al., 1981; Seyfried et al., 1988). In terrestrial systems, similar evidence demonstrates meteoric334 water involvement in nearly all shallow systems and many deeper ones (¢.g., Criss and Taylor, 1986; Valley, 1986). ‘Matic intmsive suites Metasomatism in and around mafic intrusions is largely due to the circulation of external fluids. Minor metasomatic effects arc due to magmaiic fluids, notably in layered intrusions (Hopson et al., 1981; Schiffries and Rye, 1989; Bird et al, 1988). In marine environments zoning is well developed and retrograde effects are widespread duc to extensive scawater circulation (Alt et al., 1986). By contrast, metasomatism is subdued around most mafic terrestrial intrusions. In both cases, alteration is dominated by volatile addition with common sodic and mafic types, but with relatively little hydrolytic alteration. Marine environments. Marine mafic sytems are unique in the scale of hydrothermal circulation, because of the essentially unlimited supply of seawater and continuous supply of new magma. Several recent papers (Schiffman and Smith, 1988; Harper et al., 1988: Nehlig and Juteau, 1988; and Zierenberg et al., 1988, Alt etal, 1986) present detailed descriptions of the hydrothermal systems that exist in ridge environment. Metasomatism in ridge environments consists of a zoned sequence downwards of generally pervasive and increasingly higher temperature assemblages. This sequence is shallow Mg-metasomatism, then deeper Na and Na(-Ca) types. Superimposed on these pervasive assemblages are localized intensely altered zones that represent areas of upflow, characterized by Ca alteration (epidosites) and shallow hydrolytic alteration, which can be overlain by syn- genetic massive sulfides. The zonation represents sequential alteration along parts of seawater hydrothermal circulation cell. Mg metasomatism forms over large areas away from the where seawater enters and begins to react. With increasing depth, extensive somatism represents subsequent alteration by Mg-depleted seawater. Magnesium removal is apparently necessary before significant albitization of seafloor basalts can proceed (Rosenbauer et al., 1988). The Mg for Ca and Fe exchange, and the subsequent, deeper Na for Ca exchange of Na-Ca metasomatism increase the Ca content of the modified seawater so that Ca metasomatism ean occur in the upwelling zones ef the system (Seyfried et al., 1988). Conversion of plagioclase to zoisite during Ca metasomatism may be the source of hydrogen ion that transports metals to the vent sites and causes the hydrolytic alteration seen directly below the vent sites (Zierenberg et al., 1988). Old upwelling zones, after they have moved a sufficient distance off of the ridge axis, may be altered by Mg and or Na-Ca metasomatism from recharging seawater (Alt et al., 1986). Terrestrial environments, Metasomatic effects are severely limited in most terrestrial mafic systems, due to the lack of saline waters for transport ef components. Characteristic alteration in these systems is localized at the contacts where limited Si versus Fe and Mg exchange takes place, However, hydrothermal zeolitization and isotopic exchange may extend kilometers from the contact (e.g., Ferry et al., 1987; Taylor and Forester, 1979; Norton and Taylor, 1979; Bird et al., 1988; Manning and Bird, 1991 }, Oxidized, Fe-rich skarns occur locally at contacts with carbonates, particularly where external fluids have circulated (¢.g., Cornwall, Pennsylvania type, Rose ct al., 1985). Tntermediate intrusive suites Intermediate composition intrusive suites (dioritic 10 granodioritic) are associated with a variety of alteration types. In some cases these are clearly associated with magmatic fluids, in others with seawater, in many cases fluid sources are mixed or uncertain. Typical alteration types include abundant sodic(-calcic) alteration, common hydrolytic and potassic alteration, and less common, but locally extensive skams, Seawater-dominated environments. Metasomatism of marine intermediate to felsic systems can be quite extensive due to the ready availability of saline waters for transport of 335 components. As in marine mafic systems, diffuse recharge and concentrated discharge zones are characteristic. The diffuse recharge zones are characterized by hydrous (zeolitic) alteration near the water/rock interface with Na-Ca metasomatism increasing at depth. In the discharge zones, strong hydrolytic alteration occurs, depleting Na and Ca. Fe and Mg are commonly added so that the resulting rock is characterized by chlorite and quartz with lesser amounts of sericite (Fig. 4; Larson, 1984; Franklin et al., 1981; Urabe et al., 1983). Other environments. Intermediate composition metaluminous intrusions in transitional are-related environments have variable alteration: sodic, sodic-calcic, commonly potassic (typically biotitizs without secondary K-feldspar), variable hydrolytic, bur extensive volatile addition. Fe-rich, oxidized skars are widespread, but somewhat sparse perhaps due to scarcity of limestone (Einaudi et al., 1981). In arc environments, the intrusions may have access to seawater or connate brines, however, magmatic waters from more mafic (dioritic) intrusions may form sodic in place of potassic alteration. Sodic alteration is commonly quite widespread, particularly in mafic systems and in marine arcs (Drewes et al, 1961; Speed, 1976; Bookstrom, 1977), Deeper examples of sodic alteration are unusual, but do seem to be associated with intermediate composition intrusions (Oba, 1968; Fig. 2). Where present, potassic alteration metasomatism is generally followed by one or more episodes of Na-Ca metasomatism and followed by less abundant or shallower hydrolytic alteration (Carten, 1986). intrusive suit Felsic rock types include metaluiminous and peraluminous granitoids, Marine occur- rences are rare, but as noted above are important causes of arc-related volcanogenic massive sulfide deposits (Franklin et al., 1981). Potassic and hydrolytic alteration types are particularly common, as is volatile addition, although is perhaps less abundant than for other intrusion types. Sodium metasomatism is sparse, except with some strongly peraluminous granitoids (Charoy and Pollard, 1989). Metaluminous granitoids. Shallow terrestrial intermediate to felsic plutons can release considerable saline magmatic water during crystallization (Burnham, 1979). Intense K metasomatism, associated with magmatic witers, commonly occurs near the apex of cupolas, overprinted by mild to intense hydrolytic alteration associated with both magmatic and external waters (Titley and Beane, 1981). Oxidized (Fe+-rich) skarns and replace- ‘ment deposits at contacts and occur in carbonates along structures hundred meters from the intrusions (Einaudi, 1982a). Extensive propylitic alteration generally surrounds and overlies the intrusion in quartzofeldspathie rocks, as a manifestation of hydrothermal circulation. Sericitic, argillic and advanced argillic alteration follow the earlier types. Notable examples include El Salvador, Chile (Gustafson and Hunt, 1975) and Bingham, Utah (Atkinson and Einaudi, 1978). Deeper seated examples, such as that described by Vernon et al. (1987) in the Kentucky area of New South Wales, Australia, show more subtle hydrolytic alteration. In pelitic rocks, granites locally cause potassic alteration (Oba, 1968; Fig. 4). Intermediate to felsic intrusions into alpine peridotites often show well developed blackwall formation as near Erbendorf, Oberpfalz, Bavaria (Mathes and Olesch, 1986). Extensive retrograde hydration, local migmatization, and possible potassic alteration have been described around some deeper intrusions (e.g., Pattison and Harte, 1988). Decp skarns are typically small, restricted to contacts, W-rich, and reduced (Newberry and Einaudi, 1981). Strongly peraluminous granitoids. Alteration in and around felsic peraluminous intrusions is typified by early greisenization with significant amounts of potassic and sodic alteration, Potassic alteration generally exceeds greisen in extent and is typically interior to and earlier than the latter (Shcherba, 1968). In some cases albitization occurs, closely associated with greisenization (Shcherba, 1968; Charay and Pollard, 1989), and differs from normal Na{-Ca) metasomatism (Fig. 2). Skarns are typically more reduced and336 strongly enriched in Al, F and B (Kwak , 1987). In contrast to F-poor skarns, these are rypically stockworks of veins (Barton, 1987; Dobson, 1982). Greisens may form in felsic, pelitic, or mafic host rocks. ‘The Cornwall, England region contains well described examples of many types of alteration UJaekson et al, 1982; Brammall and Harwood, 1932; Mitroupolous, 1982, 1984). Other examples for which data are shown in Figures 2-6 include Moina, Tasmania; Emuford, Northeast Queenland, and Rennison-Bell, Western Tasmania. ‘Strongly alkaline suites Alkalic rocks are common to continental rift zones, and therefore most commonly intrude quartzofeldspathic and pelitic rocks. Fenites, the most prevalent metasomatic rocks, form abundantly with carbonatites and less extensively with syenites (Rock, 1976). Carbonatites may produce undersaturated peralkaline fenites, whereas syenites rarely produce peralkaline chemistries, and do not produce undersaturated fenites, Fenitization is both more intense and more extensive quartzofeldspathic rocks than in pelitic rocks (Rock, 1976). Aureoles in quartzofeldspathic rocks are commonly several hundred meters in extent (Kresten and Morogan, 1986; Morogan, 1989). Only locally and at depth do kimberlitic intrusions produce K fenites and carbonatization (Ferguson et al., 1973). Fenites typically show multiple stages of development, associated with fluid release from several intrusive phases and usually precede intrusion of the carbonatite ot syenite (Heinrich, 1980), Mafic fenites (ijolites) are generally deeper and proximal (Garson and Smith, 1958). Although most fenites are characteristically peralkaline, late fenites may be locally peraluminous and dominated by carbonate (Heinrich, 1980), and involve meteoric waters (e.g., Andersen, 1984). Where the magmas retain or vent their alkalies, as in recent eruptions of Oldoinyo Lengai volcano, fenitization is apparently minimal (Heinrich, 1980; Dawson, 1962). DISCUSSION ‘The systematic composition, distribution and timing of metasomatic features can be attributed to the contrasts in materials and the nature of transport processes in around intusions, The theory of energy and mass transport around intrusions have been reviewed elsewhere (e,g,, see Bredehoeft and Norton, 1990, and Chapter 10 for recent summaries). The compositions of metasomatic features vary with chemical contrast between magmas and host and with the flow path (¢.g., AT and AP). The scale of systems depends on a number of factors including energy balance, abundance of fluids, distribution of permeability. Here, we draw on some of these approaches to rationalize the compositional variations and scales of metasomatism in and around intrusions. Intrusion compositions Many of the broad variations in silica, alkalies and alkaline carths, hydrogen-alkali exchange, oxidation state, and metals in aurcoles can be rationalized in terms of the compositional (chemical potential) differences among different intrusion-host rock combinations. These interpretations are straightforward where the host and intrusion are at the same temperature and pressure. Changes in pressure and temperature can be of equal or greater importance and are discussed in a following section, Silica. The high solubility of silica in hot aqueous fluids is reflected in its prominent redistribution in contact metamorphic environments (e.g., Walther and Helgeson, 1977; Fournier, 1985). Neglecting for the moment the considerable effect of changing temperature and pressure on silica solubility, the effect of magma composition is clearly seen in the differences among aureoles associated around intrusions of differing sili saturation (Fig. 7). The addition of silica to aureoles associated with many interme felsic intrusions follows from the high silica activity in these magmas (Table 2). 337 0.20 é a 3 -0.40 lg 3 -0.60 6.00 5.00 4,00 “3.00 “2.00 1,00 0.00 Log acm Figure 7. Calculated activiry diagram for ilustrating the range of the activities of quartz and corundum over thc range of common igneous rocks. Also shown arc contours of log(aNa+/aH+) for the reaction 2 NaAlSi30g + 2 H* = 6 Si0p + Alp03 +2 Nav. | ‘This diagram rationalizes pattems in silication, hydrolysis reactions, metal tansport as a function of composition Calculated using data in SUPCRT (Helgeson et al., 1978). For a similar presentation in terms.of fluid components, see Burt (1981). 1 SiO) ., = 5i02.9, , == CaCO, + SiO}, = CaSiO; + CO, 4 +— CaCO) + SiOz g, = CaSiO5 + CO,] T T T T 300 400 500 600 700 T’e Figure 8, Calculated concentration of aqueous silica in equilibrium with quartz, wollastonite + calcite, and nephcline + albite for three pressures as a function of temperature, The effect of the reduced activity of ‘water on the stability of ageous species has been neglected (see text).338 Around undersaturated magmas (olivine gabbros, nepheline syenites, carbonatites), the gain or loss of silica reflects the difference between silica activity in the host rock and the intrusion. Quartz-saturated host rocks commonly lose silica, prominently so in the case of many fenites (Heinrich, 1980). This can be seen from the difference in concentrations of SiOdaq) in equilibrium with quartz and nepheline+albite (Figs. 7 and 8, above), Fluids at or near magmatic temperatures and equilibrated with strongly undersaturated magmas can dissolve several grams of quartz per kilogram of water at pressures on the order of 0.5 to 2 kbar. Diminished magmatic agio2 may also be reflected in the scarcity of skarns with mafic alkaline and tholeiitic magmas, although the paucity of fluids and carbonate host rocks is probably be the dominant effect. Extensive skarns are locally abundant adjacent to some mafic intrusions where flow has been abundant (e.g., Rose et al., 1985). Typically though, these skarns and high-temperature magnesian skarns associated with mafic rocks are relatively poor in silica (Reverdatto, 1973). For example, a fluid at 600°C and 1 kbar nephelinesalbite is only slightly oversaturated in silica with respect to calcite+wollastonite (-0.2 gm SiOz per kg Hg0 at Xcqp = 0.1; Fig. 8), thus a small amount of wollastonite could form. In contrast, infiltration of a quartz-saturated fluid at the same conditions will precipitate about ten times as much silica (~2 gm/kg) in the form of wollastonite. Although the effect of changing T and P is large (Fig. 8), the net result is similar — strongly undersaturated magmas precipitate much less silica even in silica-free host rocks. Alkalies and alkaline earths. Na, Ca, K, and Mg changes generally correlate with magma composition and contrasts with hast rock (Figs. 2, 3), The correlation of alkali ratios with magma composition follows the distribution of potassic phases in the magma. Potassic alteration in intrusions and host rocks is best developed with granitic compositions (Lowell and Guilbert, 1970; Oba, 1968), whereas sodic alteration is predominant with mafic and some intermediate magmas (Hollister, 1975; Carten, 1986; Fox and Miller, 1990). Even in seafloor systems, where compositional changes are mainly governed by the high (Na+Mg)-contents of seawater, the alkali ratio in the igneous rocks is reflected by lack of K-bearing alteration in mafic systems and the common presence of sericite in intermediate and felsic marine hydrothermal systems (¢.g., Franklin et al., 1981). An apparent exception to this rule is sodic alteration associated with some greisen type systems. In this case, the effect appears to be primarily one of temperature combined with original saturation in both Na and K feldspar. Where these systems interact with more ‘ic materials, the alteration appears to show consistent K enrichment (e.g., in the Land's End aureole, Mitropoulous, 1984). Acid (hydrogen) and alkaline (fenitic) metasomatism: The development of acid and alkaline metasomatistn is largely interpretable in terms of igneous compositions, although temperature is also important, Hydrogen metasomatism is strong mainly in metaluminous to peraluminous granitoids, and locally in marine-hydrothermal systems (Table 3), Conversely, peralkaline intrusions typically have fenitic alkaline alteration. Two compo- sitional factors are important: (1) the acidity of the magma, and (2) the sulfur content. The extent of this type of alteration depends on the abudance of fluids and their overall concentration. The first control is magma “acidity,” which is conveniently considered in terms of alumina saturation (Shand, 1943) by reactions such as: NaAISizOg + H* = 3 S102 + [AlzO3] + Nat ; Keg = S8i028(AR2031¢Na+ 4°" AHMINSAISIOS In this reaction [Al203] indicates an aluminum oxide component (e-g., corundum) that is not physically present, Consequently, if 441303 of asiq2 decrease in the magma at constant total salinity (¢.g., Nat + H+), then the acidity must also decrease, The activities of SiO2 Metasomatic Environments. Table 3. Metasomatie types 5 g f=] Marine Bruce: 5 arolytie Ser Upwelling zones Bingharn Kentucky. Kyusta, Pine Crock 3 = 8 z 3 4 Deep systems: weak Land's End, Moina, 5, patassie rigmalization Gi sams £ replscer z= g K hydro Iminosas K, Hydroly = Febsic| ‘Alkali Syenites “Monchique, Petugal atic Sy |Skams} Naand K feni 1 Sok Polk typically, Synmagerat localized K ‘Carbonatization Cat 2 i 4 8 3. syumagmatie and Laer evespeint 4 8 i & ee 5 Kimbestites / 39and Al2Q3 can be estimated from igneous mineral assemblages (e.g., cf. Carmichael et al., 1974) including Al2O3 buffers such as: KAI[AISi3019](OH)2 = KAISi3x0g + [AlO3] + H20 for a strongly peraluminous rock and, 4 NaAlSi30g + 2 FeyOq = 4 NaFeSig0¢ + 4 [Al203] +Fe2SiO4 + 3 SiO2 for a peralkaline rock. As can be seen in Figure 7, pH shifts by several log units in going from quartz-saturated peraluminous rocks to quartz-undersaturated peralkaline rocks, ‘The rarity of hydrolytic alteration in mafic systems follows from their intermediate aai203 and common undersaturation in quartz (¢.g., olivine tholeiites). Hydrolytic altera- tion with intermediate intrusions is variably developed (e.g., diorite-type porphyry systems, Hollister, 1975). Weakly to strongly peraluminous granitic systems have better developed and typically high-temperature hydrolytic alteration, In strongly peraluminous systems this is often among highest-temperature associations (greisens; Shcherba, 1968). An additional factor in the development of hydrolytic alteration with oxidized, sulfur-rich systems is due to hydrolysis of $02 or oxidation of HS (Burnham and Ohmoto, 1980): 4802 +4H20 = H2S + 3 SOg™+6H* , In contrast to metaluminous and peraluminous systems, hydrolytic alteration is virtually absent in peralkaline systems, Where it occurs, hydrolytic alteration is generally associated with sparse metaluminous to weakly peraluminous biotite granites (e.g., Nigerian rift, Kinnaird, 1985). On the other hand, peralkaline alteration assemblages (fenites) are restricted to aureoles around carbonatite centers and some syenite complexes, These are well-developed and convert metaluminous phases such as biotite to peralkaline phases such as alkali pyroxenes and amphiboles. In pelitic rocks, the peraluminous phases are converted to feldspars (Rock, 1976). Other Aspects. The metal contents and oxidation states of aureoles also follow intrusion compositions (¢.g., Einaudi et al., 1981; Ishihara, 1981; Burnham and Ohmioto, 1980; Candela, 1989a,b), Metal concentrations in part reflect the inventory of metals in the magma (ic., high-iron metasomatic rocks are typically associated with mafic and intermediate intrusions), but also depends on other aspects of magma composition including acidity, redox state, and minor element mineralogy. Base metals, which are predominantly transported as chloride complexes or ions (Brimhall and Crerar, 1987; Barnes, 1979), will follow acidity (Urabe, 1985) by reactions such as Mt++ H3S = MS +2 H* and 2Mt + HyS =M2$+2Ht ; thus metal solubility increases with increasing acidity. Comparison with Figure 7, then, is consistent with the lack of base metal occurrences (and indeed transport of other uncomplexed or chloride-complexed cations) in alkaline systems. Oxidation state of aureoles and the types of associated metals parallel one another and these typically reflect the oxidation state of the magmas. Oxidized skarns typically occur with oxidized, commonly sulfur-rich magmatic systems (Einaudi, 1982b; Burnham and Ohmoto, 1980), In deeper aureoles around intermediate composition intrusions, oxidation as evidenced by removal reduced carbon and oxidation of Fe-bearing phases (Yardley and Long, 1981; Speer, 1981; Todd, 1990) may reflect similar effects. Metasomatic aurcales associated with reduced strongly peraluminous and some metaluminous granites (ilmenite series, Ishihara, 1981) are characterized by low Fe3+/Fe2+, with mineral assemblages requiring reduced conditions (¢.g., Bumham and Ohmoto, 1980; Einaudi et al., 1981). 341 In addition to igneous chemical control, the type and distribution of metasomatic features reflects the relative efficiency at which metasomatic changes are propagated with fluid flow along various paths, Metasomatic and related transport theory have extensively developed and reviewed elsewhere (e.g., see books by Helgeson, 1987; Kerzhinskii, 1970; Bredehoeft and Norton, 1990; also, Furlong et al., Chapter 10). Accurate modeling of complex aureoles usually requires numerical models (e.g., Norton and Taylor, 1979; Salemink and Schuiling, 1987), but many useful insights can be drawn from simple mass balance considerations and continuum models (c.g., Hofmann, 1972; Frantz and Weisbrod, 1974; Baumgartner and Rumble, 1988; Bickle and McKenzie, 1987; see also Ferry, Chapter 8; Nabelek, Chapter 9), Transport in the real world takes 1-3 spatial dimensions and time to treat accurately, however, in practice, considerable insight can be obtained from simpler treatments, These usually involve reduction of spatial dimensions to one-dimensional continuum models or zero-dimensional box models. For simple situations, analytical solutions can combine diffusion and infiltration (Bickle and McKenzie, 1987). These models typically assume local equilibrium, although it is not required if appropriate kinetic information is available (e.g., Baumgartner and Rumble, 1988). Constraints from simple mass and heat balance. The simplest approach to interpreting the size and intensity of metasomatic features is consider elementary mass and energy balance. These calculations arc useful because they provide a limit on the amount of material that must be transferred in order to achieve an observed change. Where formalized and expressed in terms of equilibrium between fluid and rock, models of this general type are known as box models. ‘They have been widely applied, particularly in stable isotope studies (e.g., Taylor, 1979). Mass balance calculations have also been applied in many situations, for example to compare metal inventories between intrusions and ore deposits (e.g.. Dilles, 1987). They are, however, fundamentally limited by lack of consideration of jal and temporal variations (see Baumgartner and Rumble, 1988). Consider two simple cases of incremental imeraction. In the first case, a net transfer reaction takes place, such that the fluid composition drops from its initial value to a fixed equilibrium value, All fluid leaves the rock at the same concentration until the rock has. completely reacted. In this situation, reaction progress (cf. Reaction (5) as a function f the water-rock ratio (W/R) is given by: . (10) ie! - where Ci! and Cig’ are equilibrium and initial fluid concentrations, and Cir! and Cj;" are the final (reaction complete) and initial concentrations in the rock. As before, concentration terms can be arbitrary provided that they are consistent. In the second case, an exchange reaction takes place and the composition of the departing fluid varies with the degree of reaction. Figure 9 (below) shows these relationships for several types of transfer based on representative values for ACjr = Ci! - Ciy" and ACir = Cx! - Cie". The sequence qualitatively matches what is seen in most aureoles: hydrogen isotope exchange and volatile-addition are the mast widely distributed effects, followed by oxygen isotope exchange and evidence for heating (purely thermal effects and reactions driven by fluid flow — Ferry, Chapter 8), and, most restricted, transfer of major elements. Mass and energy balance also imply that the size of metasomatic aureoles should be proportional to intrusion size. To the extent that aureoles can be considered single "boxes" into which fluids enter, equilibrate, and leave, relationship (9) will govern the fraction of that volume (E;) which reacts for some W/R. Equation (9) applies even for exchange342 reactions if the volume is chosen large enough. Consider then a magma chamber of volume N containing X weight fraction water. ‘The maximum mass of magmatic water that can be given off is ~NeXw*pmagma. Likewise, an approximate limit on the amount of external waters that ean be heated to the contact temperature is 30% of the mass of the intrusion, or ~N+0.3+pmagma; given heat capacities for rock and water. Thus, for some ACifdCig (mass basis) the maximum volumes of metasomatism caused by magmatic and external fluids will be Aci Prnagma ACir 7 ~-NeXqePMROMBE and ~-0,3eNePMMBMA TN | respectively. wt Psa ant AC pe 7: =. Phost ot Avrepresentative value for ACS10209)_ in the case of skams formed from magmatic fluids, SiO 2rock) is ~0.01 (cE. Fig. 8), Pmagma/Phost ~ 0.8, and Xw ~ 0.05, Thus, massive ska formed by infiltration of magmatic fluids only should be ~0.05% the volume of the intrusions. For intrusions on the order of 10 km dimension, this amounts to an evenly distributed aureole of only a few meters. If, as is typical, flow is concentrated or reactive beds comprise only a fraction of the aureole, skarns will extend 10s or 100s of meters. Although highly irregular in distribution and thickness (Einaudi et al., 1981), sizes in this range are typical (Barton et al., Chapter 14), Apart from irregularities in fluid distribution, variations in ACjs/ACj, contribute to large differences in aureole sizes. ACig/ACir depends strongly on fluid composition (e.g., total chloride, total sulfur), the chemical contrast between rock types (as noted above), and the changes in temperature and pressure along the fluid flow path. For example, the marked difference in extents of metasomatism in marine and terrestrial mafic systems reflects the large difference in total chloride available in circulated fluids. Likewise, the large differ- ence in hydrolytic alteration around shallow felsic intrusions appears to reflect the relative oxidized sulfur contents of magmatic fluids (Burnham and Ohmoto, 1980). Thus mass balance relationships are qualitively useful for rationalizing the general extent of metasomatism, however they can not predict the spatial distributions or the sequence of events, Development of zoning. The sequence and distribution of mineral assemblages in aureoles reflects lithologic and pressure-temperature changes along flow paths. Processes such as fluid immiscibility (e.g., boiling) and fluid mixing can also be significant (e.g., Henley and McNabb, 1978). ‘The ultimate distribution of metasomatic features reflects the combined effects of evolving fluid interactions along flow paths and sequential changes in the same place due to changes in fluids and P-T conditions with time (cf. Lichtner et al., 1987), In aluminous host rocks, the broad similarity in composition to intrusions leads to spatially extensive aureoles where the primary controls on zoning are changes in temperature and pressure. At stnaller-scales, well-developed zoning (e.g., around veins) generally reflects large differences between vein-forming fluids and the local host (Meyer and Hemley, 1967). This is reflected, for example, in the subdued nature or absence of envelopes around potassic veins in granitic host rocks, whereas lower-temperature sericitic veins typically have prominent envelopes (¢.g., Gustafson and Hunt, 1975). The sequence of alteration in aluminous rocks can be rationalized in terms of temperature and pressure changes along flow paths, with differences reflecting the composition of the intrusions and external fluids (e.g., Burnham, 1979; Hemley et al., 1986; Seyfried et al., 1988). In granitoids, the predominant pattern of internal potassic alteration grading out to hydrolytic and propylitic alteration is cosistent with cooling of fluids equilibrated with the igneous rocks at near magmatic temperatures. Potassic alteration forms at high-temperature in response to cooling of fluids in equilibrium with nwo feldspars (path 1, Fig. 10A). As temperature decreases, fluids of fixed DH/3(K+Na+Ca) progres- sively react with plagioclase, K-feldspar, and micas producing hydrolytic assemblages 343 418 08 02 9.02 AC,,/AC,, -3.0 -2.0 =L.0 0.0 1.0 2.0 3.0 10g, LM yoic/Moael Figure 9, Reaction progress as a function of ‘W/R for several simple representative reactions. See text for discussion, 700 600 500 ° z 400 2 alkali feldspars, 2 kb- 300 ster | ter Kin Orvite (1963) | Montoya & Hemley (1975) 200 15 20, 25 2 3a 48 6 Ka Log (K*HKCI) gg (NaT+NaC) mol percent (Ht+HCP) {H*+HCr) Figure 10. Reactions in aluminous rocks. A. Alkali exchange in feldspars, &. Hydralytie alteration reactions. See text for discussion344 (path 2. Fig. 10B). For strongly peraluminous rocks, the path may begin with high DH/E(K+Na+Ca) and thus cause hydrolytic (greisen-type) alteration at higher temperatures (path 3, Fig, 10B; cf. Fig. 7). In potassium-poor rocks, similar relations may obtain, except that the principal high-temperature exchange is Na for Ca in the feldspars (Caren, 1986; Hemley et al,, 1971). Where fluids flow into the intrusion and up temperature (and possibly pressure) gradients the reverse should hold, as has been suggested for sodic alteration in some systems (e.g., Carten, 1986; cf. path 4 in Fig. 10A), In marine hydrothermal systems, broadly similar relationships hold, differing primavily by the involvement of seawater. Reaction of rocks with Na-Mg-rich seawater drives hydrothermal fluids on the heating path to higher Ca contents, and is reflected in the development of Ca-rich metasomatism that precedes hydrolytic alteration in upwelling zones (Rosenbauer et al., 1988; Seyfried et al., 1988). In carbonate rocks, the strong chemical contrast leads to more restricted metasomatic features than in aluminous rocks, although large scale spatial variations occur where fluids are channelized (e.g., Einaudi ct al., 1981). Consequently, mineralogical zoning in skarns is best summarized in terms of chemical potential diagrams (e.g., see Burt, 1974; Einaudi et al., 1981; Korzhinskii, 1970). Broadly, compositional uends toward the carbonate Show progressive decrease in the less soluble igncous components such as AlsO3 (e.g,, the common sequence: intrusion-gamet-clinopyroxene-wollasonite-marble). Generalization is difficult because mobilities vary greatly in different environments and the relative advance of different metasomatic fronts depends on their relative compositional changes between the fluids and rocks (ACif/ACir for a sharp front; Hofmann, 1973), Superposition of alteration assemblages is typical of most aureoles. In some eases, this represents the advance of interior fronts over exterior fronts. For example, gamet zones encroach along veins and fronts on pyroxene zone. assemblages in skarns (Einaudi et al., 1981), and sericitic alteration commonly replaces outer zones of intermediate argillic alteration in granitoids (Meyer and Hemley, 1967). In other cases, superposition is caused by collapse of hydrothermal systems back on the intrusions during cooling, Hydrous skams overprint anhydrous skarns, and hydrolytic alteration is superimposed on alkalic alteration in many granitoids (e.g, Lowell and Guilbert, 1970). Lastly, superposition of metasomatic effects may reflects successive influx of distinctive fluids produced by multiple magmatic events associated with single centers (e.g., Seedorff, 1984; Barton and Trim, 1991) or separate centers (e.g., Hanson et al., 1991). Two additional factors, rheology and reaction volumes. appear to be important in governing the relative extent and style of aureoles. First, brittle behavior al shallow depths fosters fracture control and thus wide distribution of alteration, At greater depths, restricted aureoles may reflect the more ductile behavior of host racks and subdued release of volatiles from the magma (Burham and Ohmoto, 1980; Barton et al., Chapter 14). The ductility of carbonate rocks may contribute to the relative restriction of carbonate aureoles even at shallow levels. Second, volume changes due to alteration reactions should also influence distributions. Negative volumes of reaction are associated with some spatially extensive types of alteration, such as hydrolysis and fenitization reactions ix quartzofeldpathic racks (e.g., Yatusegon/Vaksp -0.18 for sericitic; SiOz dissolution for Eranite-hosted fenites), Extensive fluid flow in carbonate rocks is commonly localized by decarbonation reactions (e.g., Vwol/Vcal+Qe = -0.33; cf. Nabelek et al,, 1984) and ska. forming reactions with negative volumes (¢.g.. Vi/Vcai = -0.34; ef. Barton, 1987). Conversely, limited aureoles in some rocks, such as fenites in pelitic hosts (Rock, 1976) and many calcic skarns may reflect filling and self-sealing of open space (e.2., Vaksp/V mtustage = +0.18 for fenite; Viyo/Vcai = +0.08 for silication), 345 ACKNOWLEDGMENTS We appreciate discussions with J.-M. Staude, M. Davis, B. 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