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1. Introduction to zoning in crystals 2. Diffusion equation 3. Diffusion coefficient 4. Modeling natural crystals: isothermal case * Initial conditions * Boundary conditions 5. Problems, pitfalls and uncertainities

1. Zoning in crystals

X-ray distribution map of olivine from lava lake in Hawaii Moore & Evans (1967)

Development of electron microprobe 1960’, first traverses and X-ray Maps

Among the first applications to obtain time scales those related to cooling histories of meteorites (e.g. Goldstein and Short, 1967)

SIMS.Increasingly easier to measure gradients with good precision and spatial resolution (LA-ICP-MS.Major elements. Zoning in crystals . and isotopes . e-probe. NanoSIMS. micro-FTIR) . FIB-ATEM.1. trace elements.

Major and trace element zoning in Plag .

(2008) .Stable isotope zoning 18O in zircon from Yellowstone magmas Bindeman et al.

Sr isotope zoning in plagioclase Tepley et al. (2000) .

.

Compositional Zoning in Grt Lower part of Grt-zone Sample. 575±50 oC . WAH Peak P-T: 8.1±0.9 kbar.

Compositional Zoning in Grt Upper Part of Grt-zone Sample. 580±65 oC . WAH Peak P-T: 8.1±0.5 kbar.

580±65 oC . WAH Peak P-T: 8.1±0.Compositional Zoning in Grt Upper Part of Grt-zone Sample.5 kbar.

3±0.Compositional Zoning in Grt Ky-zone Sample. WAH Peak P-T: 8.6 kbar. 595±65 oC .

6 kbar.Compositional Zoning in Grt Ky-zone Sample. WAH Peak P-T: 8.3±0. 595±65 oC .

WAH Peak P-T: 8.Compositional Zoning in Grt Ky-migmatite zone Sample.8 kbar. 675±35 oC .6±0.

WAH Peak P-T: >7 kbar. 795±55 oC .Compositional Zoning in Grt Kfs-Ky-Kfs Migmatite zone Sample.

795±55 oC .Compositional Zoning in Grt Kfs-Ky-Kfs Migmatite zone Sample. WAH Peak P-T: >7 kbar.

Garnet Zoning Garnet: use of elements of contrasting D for initial conditions Garnet: effect of crystal size Sc Mn Spear & Kohn (1996). GMR 1 . Geology 24 Spear & Daniel (1998).

Compositional Zoning in Garnet Due to Garnet Growth .

Stability of Grt-bearing assemblages in Different Metamorphic Grades .

T. or composition t0. X0 tt. Tt. Zoning in crystals Diffusion driven by a change in P. T0. P0. Xt distance distance . Pt.1.

1. Zoning in crystals .Because D is Exp dependent on T and Ds in geological materials are slow. minerals record high T events (as opposed to room T) distance .The compositional zoning will reequilibrate at a rate governed by the chemical diffusion (Fick’s laws) .

1. Zoning in crystals Crystals record the changes in variables and environments: gradients are a combined record of crystal growth and diffusion .

Deformation. No measurable diffusion Stage 2: An intermediate branch. Radioactive Decay . Atomic Ordering. Compositionally zoned mineral Stage 3: A long-time branch. R=f(t). Compositionally Homogeneous mineral Time recorder: Diffusion.MEASURING TIMESCALES: THE CHARACTERISTICS OF CLOCKS Stage 1: A short-time branch. R~0%. System frozen. System at equilibrium. Chemical Reaction. R~100%. Measurable diffusion. Diffusion complete.

2. The diffusion equation .

flux. 1945) (2) It occurs in all materials at all times at temperatures above the absolute zero (3) The existence of a driving force or concentration gradient is not necessary for diffusion . Diffusion.2. and Fick’s law Diffusion: (1) motion of one or more particles of a system relative to other particles (Onsager.

and Fick’s law GAS LIQUID SOLID . flux. Diffusion.2.

NOT the cause of diffusion Fick’s first law Flux has units of ‘mass or moles or volume * distance/time’ Diffusion coefficient has units of ‘distance2/time’ .2. Diffusion. flux. and Fick’s law Random motion leads to a net mass flux when the concentration is not uniform: equalizing concentration is a consequence.

Fick‟s Law of Diffusion: General Features .

Diffusion Equation: Application of Continuity Relation where moles/cc .

Diffusion Coefficients: Different Types Tracer diffusion coefficient Self diffusion coefficient Chemical diffusion coefficient Interdiffusion coefficient .

it can be shown that the interdiffusion is effectively the same as the isotopic or tracer diffusion.Tracer diffusion coefficient A tracer diffusion coefficient is defined as the diffusion coefficient of a tracer isotope of an element that describes its flux in response to the specific isotopic concentration gradient in a medium that is homogeneous with respect to the concentration of the chemical elements. As long as the diffusing isotope is very dilute so that its thermodynamic behavior is within the Henry‟s law limit. In practice. A tracer diffusion coefficient of an element will be designated by the symbol D(*i) here the superscript „*‟ indicates the isotope and i stands for the element. in which case one deals with the problem of interdiffusion. . Such a medium is referred to as a chemically homogeneous medium. However. this exchange mechanism may not always hold as an isotope of an element may exchange position with an isotope of a different element. this can be ensured only when an isotope of an element diffuses by exchanging position with another isotope of the same element.

. A tracer diffusion coefficient of an element is the same as its self diffusion coefficient when all the isotopes of the element have the same diffusivity. A self diffusion coefficient of an element i is denoted by the symbol D(i). In this work.Self diffusion coefficient A self diffusion coefficient is the one that describes the flux of an element solely in response to its own concentration gradient and under condition that its thermodynamic interaction with the matrix is independent of the change of its own concentration. the self and tracer diffusion coefficients Will be treated as effectively the same quantity.

. If the molar volume of the medium remains constant. where Xi is the mole fraction of the component i. respectively. the activity coefficient and concentration (moles per unit volume) of the component i. then the ∂lnCi = ∂lnXi.Chemical diffusion coefficient A chemical diffusion coefficient of an element (i) represents a product of its self diffusion coefficient and a thermodynamic factor (TF) that is given by the quantity (1 + ∂lnγi/∂lnCi) where γi and Ci are.

denoted by D(i-j).Interdiffusion coefficient An interdiffusion coefficient of two elements. represents a product of the weighted average of the two self diffusion coefficients. For the special case of interdiffusion of two equally charged species in a medium of fixed molar volume. and the thermodynamic factor. it is given by . D(i) and D(j).

where Q: activation energy of diffusion. where p= pressure in bar. 2. Temperature: D = Do exp(-Q/RT).Factors Controlling Diffusion Coefficient 1. fO2: Qp= Q1bar + (p-1) * ∆V+. generally expressed at 1 bar Do= Pre-exponential factor. ∆V+ = activation coefficient of diffusion in cc . Pressure: 3.

couples annealed at high P-T conditions within graphite capsules. Mn and Ca determined by modeling multicomponent diffusion profiles in diffusion. respectively. Solid and dashed lines: Arrehenius relations to the data obtained from AlmPrp (Ganguly et al. .Diffusion Coefficient and Arrehenius Relation Summary of self-diffusion data of Fe. All data are normalized to a pressure of 10 kb. Mg. 1998b) and Alm-Sps (Chakraborty and Ganguly 1992) diffusion couples.

Arreheneus Relation: Calculate Q1bar P=10 kbar .

Multicomponent diffusion .

here DCa .Multicomponent Garnet Diffusion Grt D Matrix Mg Mg Fe Mn DMgMg DFeMg DMnMg Fe DMgFe DFeFe DMnFe Mn DMgMn DFeMn DMnMn nth component is the dependent component.

Multicomponent Garnet Diffusion DMgMg= D*Mg-[(D*MgXMg)/(D*MgXMg+ D*FeXFe+ D*MnXMn + D*Ca*XCa)] (D*MgD*Ca) DMgMn= -[(D*MnXMn)/(D*MgXMg+ D*FeXFe+ D*MnXMn + D*Ca*XCa)] (D*Mg-D*Ca) .

ΔCi.t) = concentration at any point (x) within the crystal at time t. Two semi-infinite media with a common interface and initial homogeneous but contrasting compositions where Ci(o)= lower of the two initial concentrations.Analytical Solution of Diffusion Equation: 1.o =Diff in initial concentrations of the species i at the interface. D(i-j)= binary inter-diffusion coefficient between the species i and j . The constant source solution for constant D: where Cs = Surface concentration. C∞=initial concentration in the crystal. C(x. T=time 2. D=Diffusion coefficient. .

Numerical Solution of Diffusion Equation: Finite Difference Method

2

Courant condition, r=DΔt /(Δx)2 ≤0.5.

**Advantages and Limitations of the Numerical Methods
**

1. If an explicit method is to be used, we cannot choose D, Δx and Δt arbitrarily. As D and Δx are usually specified by the problem at hand, the choice of Δt is limited by the Courant condition. 2. Inspection of the formula above shows the necessity to have the two boundary conditions and one initial condition. Boundary condition: Knowledge of compositions at the 1st (i-1 th) and last point (i+1 th point). Concentrations held constant or there is no flux etc 3. As these calculations proceed by explicitly determining the concentrations at each position at each time step, it is easy to add variations in the model. For example, to start off a calculation we need to define the concentrations at each grid point (the initial condition). Because each concentration is specified individually, it is irrelevant whether the concentration profile is homogeneous, has a regular geometric form, or is of an arbitrary shape. Similarly, if we wish to change the boundary conditions subject to which diffusion occurs after, say, the 20th time step, we can directly do so. This is where the flexibility of the numerical method noted in the text comes from.

Outline-I

**1. Application to isothermal problems
**

(a) boundary and initial conditions (b) effect of geometry and multiple dimensions

2. Application to problems with cooling history (a) approach of Lasaga and co-workers

boundary conditions) 4. Uncertainties (a) in model parameters (e.g. Examples of applications (a) olivine in magmatic rocks (c) garnet in metamorphic rocks .g..II 3.Outline.. T) (b) in the modeling approach (e.

Xt Ci Ci (Di ) t x x Boundary ? Initial ? distance distance D does not depend on t but can depend on C or other variables . Isothermal diffusion problem t0. X0 tt.1.

may also include the effects of: (a) crystal growth or (b) dissolution .Boundary conditions I. (a) open or (b) closed to flux with the environment II.

Boundary conditions Example of Fe/Mg diffusion in garnet O O What are the effects of boundary conditions for calculated times ? Fe/Mg C Garnet O O C C Florence & Spear (1995) EPSL 134 .

.Boundary conditions Closed boundary Open boundary distance Conc. Conc.

Boundary conditions: effects on time scales Equilibration in the closed system occurred much faster Incorrectly applying a no flux condition to an open system can lead to underestimation of time by factors as large as an order of magnitude (this has happened in the literature!) .

.Boundary conditions: effects of crystal growth or dissolution (a) Neglecting crystal growth tends to overestimate time scales (b) Neglecting crystal dissolution tends to underestimate time scales (e. shortening of diffusion profiles) t1 t2 distance distance .g.

Initial conditions tt. Compare profiles of elements with extremely different diffusivities. vary depending on the problem at hand. Xt Boundary OK Initial ? distance Need to be evaluated using geological criteria. and also the zoning profile of crystals of different sizes . At least 4 end-member possibilities 1.

.Diffusivity of anorthite is ~ 10^7 slower than Mg DMg~ 100 x DSr ~ 100.Small (Pl4) crystal more equilibrated than larger ones (Pl7) Costa et al (2003). GCA 67 .000x DNaSi-CaAl Different elements can record different aspects of the thermal history experienced by a plagioclase crystal.Initial conditions Plagioclase . Modeling the differing degrees of modification of Compositional zoning of various elements in one crystal provides a unique tool to constrain timescales of processes in a Magma chamber.

Initial conditions Garnet: use of elements of contrasting D for initial conditions Garnet: effect of crystal size Sc Mn Spear & Kohn (1996). Geology 24 Spear & Daniel (1998). GMR 1 .

e. maximum permissible duration of a thermal event without diffusive modification). EJM 16 . can be used as a time constraint (i. Elimination of smaller wavelengths by diffusion Preservation of sharp compositional gradients in igneous garnet. (a) Using arbitrary maximum initial concentration range in natural samples (this provides maximum time estimates). Trepmann et al (2004). (b) Some times possible to use an oscillatory zoned model. if the cation diffusion coefficients are known and if “sharpness” can be quantified.Initial conditions 2. unmodified by diffusion.

g.Initial conditions 3. e.. Model of Spear et al (1990). Homogenous initial profiles has proved a good approach when dealing with minerals that have experienced high-T episodes prior to the event that finally drove diffusion. Fe-Mg in garnet or olivine (e.. Costa & Dungan. Chakraborty & Ganguly. 1991. Initial concentrations are constrained by thermodynamic equilibria + mass balance to establish the initial zoning of garnet during growth 4. 2005) What are the effects of initial profiles in calculated time scales? .g.

Initial conditions 100 Equil % 0 time distance Conc. . Conc.

5 Thus.Initial conditions: effects on time scales Despite the difference in shapes of the initial profiles the maximum difference on calculated time scales is a factor of ~1. although the initial profile that we assume controls the time that we obtain. the error can be evaluated and is typically not very large .

one can create unnecessary and artificial 2D effects Not OK OK Neglecting multidimensional effects tends to overestimate time scales .Effects of geometry and multiple dimensions These are important depending on the type. shape. and size of the crystal that we are studying and on the diffusion time Careful with the orientation of the diffusion front with respect to the traverse.

t = 225 y 800 700 600 500 ini Mg ppm 400 300 200 100 calc equi 0 50 100 microns 150 200 Costa et al (2003).Effects of geometry and multiple dimensions Example of plagioclase 1D. GCA 67 0 .

Effects of geometry and multiple dimensions ini 800 700 600 500 400 300 200 100 0 calc Mg ppm 800 700 600 500 400 300 200 100 0 Mg ppm 1D. t = 225 y ------> 2D. t = 60 y almost a factor of 4! .

Fe-Mg zoning in olivine: diffusion anisotropy and 2 dimensional effects Mg zoning Model Initial c b Fo zoning 150 µm .

analytical work and detailed modeling is necessary for obtaining reliable time estimates from diffusion modeling Next step:cooling history .Isothermal diffusion problem summary A clear understanding of the initial and boundary conditions plus the effects of multiple dimensions in the natural system is very important because it can have large effects on the calculated time scales Careful petrographic observations.

T0 G B tt.The effect of a slow cooling history Important for metamorphic and some igneous rocks (plutons and dikes) t0. Tt G B t0. Tt G K0 distance G B distance Kt B . T0 tt.

The effect of a slow cooling history The driving force for diffusion is related to the T dependence on K. T(t) ---> K(t) tt. Tt G K(t) B distance G B Fe# Fe# K(t) Ko e [ Q ] RT(t) .

Tt G K(t) D(t) Do B distance [ e E ] RT(t) C D(t) t C 2 x 2 .The effect of a slow cooling history But because of T(t) ----> D(t) tt.

s= cooling rate 1 (s t/To) Next step. G Fe# B Fe# K(t) Ko [ E ] RT(t) [ e Q ] RT(t) 2.linear cooling. 2C x 2 To ~ T(t) To s t Near. D(t) Do e 3.The effect of a slow cooling history 1. find analytical or numerical solution . C D(t) t T(t) 4.

.The effect of a slow cooling history Approach of Lasaga et al. t ' D( ) d 0 t Diffusion equation becomes C 2 C 2 t' x . (1983) for analytical solution Create a new variable t’ (“compressed time scale “). (1977) and Lasaga.

the initial conditions are the same as with t.. analytical . This requires the mathematical work shown in Lasaga et al. but the boundary conditions are not.The effect of a slow cooling history C 2 C 2 t' x With this new time variable t’. (1977) and Lasaga (1983) Jaoul & Sautter (1999) and Jaoul & Bejina (2005) basically the same approach.

95 Tpeak . Tch~ 0.The effect of a slow cooling history Chakraborty & Ganguly (1992) reduce the nonisothermal problem to an isothermal one by defining a ‘characteristic diffusion coefficient’ Dch Dch t D( ) 0 t d Total amount of diffusion can be obtained by calculating at a given Tch at which D=Dch.

there is the possibility of constructing finitedifference algorithms. These are extremely flexible and rather simple to implement What are the effect of cooling history on time scales and shapes of diffusion profiles ? .The effect of a slow cooling history Finally.

The effect of a slow cooling history Blindly modeling a profile with a cooling history at a single T underestimates the time by orders of magnitude .

The effect of a slow cooling history Shapes of profiles are quite different when one incorporates K(t) .

The effect of a slow cooling history Neglecting K(t) largely underestimated the time .

1995) .The effect of a slow cooling history A cooling history oscillating around a trend is indistinguishable from that of the simpler trend (Jiang & Lasaga.

g.Errors and uncertainties associated with time determinations One can distinguish two types: (a) those associated with the parameters used in the model (e.. D). and (b) those associated with how well we understand and reproduce the natural physical conditions (e.. multiple dimension etc) .g. T.

One can expect overall uncertainties on calculated times s of a factor of 2 to 4. e.Errors and uncertainties associated with time determinations 1. Typically much smaller 4. T uncertainties from geothermometers are ~ 50 oC E (kJ/mol) Uncer. Uncertainties in other variables that D depends on.Factor 500 4 200-300 2 100 1. pressure.3 2. Experimental D determination at a given T: within a factor of 2 3..20 years . e. oxygen fugacity.g. 10 years might mean between 5 .g.

and modeling work one can diminish these uncertainties to almost null. by careful petrographical. boundary conditions or multidimensional effects are very variably and can be very large. it just takes work! . analytical.Errors and uncertainties associated with time determinations Uncertainties related to initial. more than 1 order of magnitude However.

2004) . Garnet zoning in metamorphic rocks. Exhumation rates of metamorphic core complexes (Spear.Examples of applications I. 2005). Olivine zoning in lavas from Chilean volcano (Costa & Dungan. Time scales between assimilation of mafic crust by ascending basalts and eruption II.

Example of cooling and exhumation rates of metamorphic core complex using Fe-Mg zoning in garnet .

Basic Geology Valhalla metamorphic core complex part of the Shuswap terrane of British Colombia (Cretaceous) High grade migmatitic paragneisses. with 820 oC and 8 kbar as peak metamorphic conditions .

Mn and also Ca and Cr Ca Fe-Mg Mn Cr Ca and Cr diffuse very slowly through garnet: they record the growth history (high T) .Mineral zoning Garnets show Fe-Mg .

the Fe-Mg and Mn zoning at the garnet rims and record the cooling history of the complex .Mineral zoning In contrast.

Modeling of zoning Diffusion model constructed using only Fe-Mg (it could have been multicomponent in garnet) First attempt using a single T did not reproduce the zoning. so a model with a cooling history was constructed (using the explicit methods) .

Modeling of zoning Best fits when an initial fast cooling (> 200 oC/ Ma) period followed by a longer and slower one (~ 25 oC/ Ma) .

Age dating F. Spear not convinced. We understand everything and Ds are correct! . so in-situ Th/Pb dating of different generations of Monazite supposed to have crystallized at different Ts Agreement between radiometric and diffusion times.

Thermal modeling How to produce such fast cooling rates? By simple erosion is too slow. and in part by tectonic denudation Thrust ramp onto a cooler footwall does the work .

Thermal modeling

Thermal model fits well with diffusion and radiogeneic dating.

Summary geospeedometry

- It’s a method based on thermodynamic and kinetic laws that can access the time scales and rates of geological processes spanning more than 15 orders of magnitude, from seconds to millions of years - Such a wide applicability is unrivaled by any other geochronometric method - The precision and accuracy of the results varies depending on how well we know T, but also Ds .

Summary geospeedometry

- In the case of metamorphic rocks there seems to be a quite good agreement between diffusion data, radiogenic data and thermal modeling

- In the case of magmatic rocks this is much less so. - There is a lot of room for doing new and interesting work related to geospeedometry and diffusion: experiments, modeling, interpretations. It’s a good field to invest one’s future time and energy

Core compositionally homogeneous. These diffusion closure temperatures tend to be ∼500 °C or even lower. retrograde zoning near rim. Grt core no longer suitable for retrieval of TMax. What to be done? . Use of rim compositions of garnet for thermobarometric purpose would yield P–T conditions at which diffusion effectively ceased in the garnet grains. Granulite facies Condition: Growth zoning obliterated due to volume diffusion at high T. Strategy: Grt core composition reflects possible preservation of its peak metamorphic T. Problem in Granulite facies Grt: For very HT metamorphism. Strategy: Grt rim composition reflects its peak metamorphic T.Grt Diffusion: Application in Geothermobarometry Greenschist to Lower Amphibolite facies Condition: Growth zoning preserved and not significantly modified by diffusion. Grt Core may be affected by diffusion during cooling.

Peak T from HT Granulite Facies Grt Choice of Grt Grain Size: Large enough for Grt cope to escape diffusive modification.1 if Tp≤1000 °C. R =gas constant. E =activation energy of binary diffusion. . where. Ganguly and Tirone (1999) showed that there is no significant resetting of garnet core composition for M≤0. This can be predicted by using the equation below. M= dimensionless parameter. D(Tp) =diffusion coefficient at the peak temperature (Tp). dT/dt =cooling rate at T and ℜ =radius of the garnet crystal.

Peak T from HT Granulite Facies Grt Minimum grain size of spherical of garnet crystal surrounded by biotite (or homogeneous infinite matrix) that is required to preserve the peak metamorphic composition at the grain center. . The numbers beside the curves indicate cooling rates (°C per Myr). Tp stands for the peak temperature.

Equilibrium Composition for Estimation of Pressure A thin section map of a metapelite granulite showing internal and external Grt decomposition. .

Pressure-Controlled Reaction Textures .

Grt Compositional zoning .

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