Slide 1Types of Metamorphic ReactionsContinuous Reactions Involving Solid Solution PhasesContinuous ReactionsSlide 5Continuous vs. Discontinuous ReactionsSlide 7Slide 8Types of Metamorphic Reactions DevolatilizationReactions and ChemographicsSlide 11Slide 12Slide 13Slide 14Petrogenetic Grids Graphically Portraying Several Reactions in Pressure – Temperature SpacePetrogenetic Grids Multisystems  > C +2Petrogenetic Grids MultisystemsSlide 18GEOL 2312 IGNEOUS AND METAMORPHIC PETROLOGYLecture 26Metamorphic Reactions (cont.)Chemographics and Petrogenetic Grids April 8, 2009TYPES OF METAMORPHIC REACTIONS• Phase Transformations• Exsolution Reactions•Solid-Solid Net Transfer Reactions• Devolatilization Reactions• Continuous Reactions (THIS LECTURE)• Ion Exchange Reactions• Oxidation/Reduction (redox) Reactions•Reactions involving Dissolved SpeciesCONTINUOUS REACTIONSINVOLVING SOLID SOLUTION PHASESWinter (2001) Figure 26-8. The bulk chemistry of each unit is homogeneous, but differs somewhat from the other units in the areaThe garnet-in field isograd varies from unit to unit, occurring at different grades.WHY?An idealized field area of steeply dipping meta-pelitic sediments that strike directly up metamorphic gradeCONTINUOUS REACTIONSTwo possible reasons:1. Each unit has contrasting compositions such that the garnet reaction is differentExample: garnet in some pelites may be created by the (unbalanced) reaction: Chl + Ms + Qtz  Grt + Bt + H2O (26-11)Whereas in more Fe-rich and K-poor pelites, garnet might be generated by an (unbalanced) reaction involving chloritoid: Chl + Cld + Qtz  Grt + H2O (26-12)2. The reaction on which the isograd is based is the same in each unit, but it is a continuous reaction, and its location is sensitive to the composition of the solutions (either solid or fluid) involvedThe offsets this creates in an isograd are usually more subtle than for reason #1, but in some cases they can be substantialLet’s evaluate the second situationCONTINUOUS REACTIONSWinter (2001) Fig. 6-10. Isobaric T-X phase diagram at atmospheric pressure After Bowen and Shairer (1932), Amer. J. Sci. 5th Ser., 24, 177-213““Melt-in” Melt-in” isograd?isograd?Temperature is strongly X-dependentRecall the igneous situation with solid solutionCONTINUOUS VS. DISCONTINUOUS REACTIONS Consider the reaction: Chl + Ms + Qtz  Grt + Bt + H2OF = C –+ 2 = 5 – 4 + 2 = 1 (univariant)But effectively F=0 since T and P are controlled by moving along a geothermalor field gradientTherefore, the reaction occurs at a particular T for a givengradient and would be consideredDISCONTINUOUSCONTINUOUS VS. DISCONTINUOUS REACTIONSThis is a continuous reaction and we expect to find chlorite, muscovite, quartz, biotite, and garnet all together in the same rock over an interval of metamorphic grade above the garnet-in isogradThe composition of solid solution phases will vary across the interval, and the proportions of the minerals will change until one of the reactants disappears with increasing gradeHowever, when considering the solid solution of Mg and Fe in garnet, biotite, and chlorite, the general reaction is (Fe,Mg)Chl + Ms + Qtz  (Fe,Mg)Grt + (Fe,Mg)Bt + H2OCONTINUOUS REACTIONSPerhaps a more realistic way to portray this continuous reaction (minus the K component) is this. Thus, the offsets in the idealized field area may be due to differences in the Mg/Fe ratios of the different rock layers.TYPES OF METAMORPHIC REACTIONSDEVOLATILIZATIONAnother example of a continuous reaction over a range in T due the potential for the fluid composition to changeCLOSED (buffered)Volatiles are trapped in the rock with degassing XCO2 must follow the reaction equibrium curve to the max T.a – degassing of CO2 & H2O drives system to b and increased Tb – Trem, Cal or Qtz must be consumed before T can increase c – degassing of CO2 causes system to move along reaction curve toward XCO2 = 1 Fluid composition is controlled (buffered) by the progress of the reactionREACTIONS AND CHEMOGRAPHICSWe can use chemographics to infer reactions. Consider the 2-component system MgO-SiO2 MgO SiO2Per Fo En QtzAny two phases in a binary system can react to from a phase between themFo + Qtz = En Mg2SiO4 + SiO2 = Mg2Si2O6En + Per = Fo Mg2Si2O6 + 2 MgO = 2 Mg2SiO4Per + Qtz = Fo or EnIf we know the chemographics we can determine that a reaction is possible (and can dispense with balancing it)However, thermodynamics determines whether such a reaction is probableREACTIONS AND CHEMOGRAPHICSFor a ternary system, any phase that is coplanar with three other phases can be related by a chemical reaction2A + B + C = XAgain, whether this reaction is probable under natural conditions of P & T depends on Thermodynamics.If the diagram represents a projection from another phase or component, then that phase is implied in the reaction.For component D, the reaction might be: 2A + B + C + #D = XHowever, the amount of D in the reaction would have to be figured out by balancing the reaction.REACTIONS AND CHEMOGRAPHICSAt P/T Conditions AAt P/T Conditions B2A + B + C = XX-inIsogradREACTIONS AND CHEMOGRAPHICSAnother Possibility If phase X can be defined by two different reactions:2A+B+C = X D+E = X Then, the reaction: 2A+B+C = D+E is also trueREACTIONS AND CHEMOGRAPHICSA + B = C + DA Tie-line Flip - results in new groupings in the next metamorphic zoneBecause A+B and C+ D share a common tie-line, they can be related by the reaction: Increasing GradeBelow the Isograd At the Isograd Above the IsogradPETROGENETIC GRIDSGRAPHICALLY PORTRAYING SEVERAL REACTIONS IN PRESSURE – TEMPERATURE SPACEUnivariant Curves can be labelled by Absent PhaseMetastableExtensionsSimple One Component SystemSimple One Component SystemPETROGENETIC GRIDSMULTISYSTEMS > C +2One-Component SystemFour Phases (ABDE)Four invariant points(labelled by the absent phase)Seven univariant lines(labelled by the absent phases)Four divariant fields(labelled by stable phase)PETROGENETIC GRIDSMULTISYSTEMS Theoretically Possible vs. Geologically ProbableMany Petrogenetic Grids will overlay grids of multiplecomponent systems that pertain to a specific protolith typeWinter (2001) Fig. 26-19. Simplified petrogenetic grid for metamorphosed mafic rocks showing the location of several determined univariant reactions in the CaO-MgO-Al2O3-SiO2-H2O-(Na2O) system (“C(N)MASH”). PETROGENETIC GRIDSMULTISYSTEMS