Isotope Geochemistry

Measuring Isotopes While different, isotopes of the same element exist in certain fractions corresponding to their natural abundance (adjusted by fractionation) We measure isotopes as a ratio of the isotope vs. a standard material (per mille ‰) Where Ra is the ratio of heavy/light isotope and a is the fractionation factor ‰

Fractionation A reaction or process which selects for one of the stable isotopes of a particular element If the process selects for the heavier isotope, the reaction product is ‘heavy’, the reactant remaining is ‘light’ Isotope fractionation occurs for isotopic exchange reactions and mass-dependent differences in the rates of chemical reactions and physical processes

Temperature effects on fractionation The fractionation factors, a, are affected by T (recall that this affects EA) and defined empirically: Then, As T increases, D decreases – at high T D goes to zero Where A and B are constants determined for particular reactions and T is temp. in Kelvins

Equilibrium vs. Kinetic fractionation Fractionation is a reaction, but one in which the free energy differences are on the order of 1000x smaller than other types of chemical reactions Just like other chemical reactions, we can describe the proportion of reactants and products as an equilibrium or as a kinetic function

FRACTIONATION DURING PHYSICAL PROCESSES Mass differences also give rise to fractionation during physical processes (diffusion, evaporation, freezing, etc.). Fractionation during physical process is a result of differences in the velocities of isotopic molecules of the same compound. Consider molecules in a gas. All molecules have the same average kinetic energy, which is a function of temperature.

Because the kinetic energy for heavy and light isotopes is the same, we can write: In the case of 12C16O and 13C16O we have: Regardless of the temperature, the velocity of 12C16O is 1.0177 times that of 13C16O, so the lighter molecule will diffuse faster and evaporate faster.

Equilibrium Fractionation For an exchange reaction: ½ C16O2 + H218O ↔ ½ C18O2 + H216O Write the equilibrium: Where activity coefficients effectively cancel out For isotope reactions, K is always small, usually 1.0xx (this K is 1.047 for example)

WHY IS K DIFFERENT FROM 1.0? Because 18O forms a stronger covalent bond with C than does 16O. The vibrational energy of a molecule is given by the equations: Thus, the frequency of vibration depends on the mass of the atoms, so the energy of a molecule depends on its mass.

The heavy isotope forms a lower energy bond; it does not vibrate as violently. Therefore, it forms a stronger bond in the compound. The Rule of Bigeleisen (1965) - The heavy isotope goes preferentially into the compound with the strongest bonds.

Equilibrium Fractionation II For a mass-dependent reaction: Ca2+ + C18O32-  CaC18O3 Ca2+ + C16O32-  CaC16O3 Measure d18O in calcite (d18Occ) and water (d18Osw) Assumes 18O/16O between H2O and CO32- at some equilibrium T ºC = 16.998 - 4.52 (d18Occ - d18Osw) + 0.028 (d18Occ-d18Osw)2

Empirical Relationship between Temp Empirical Relationship between Temp. & Oxygen Isotope Ratios in Carbonates At lower temperatures, calcite crystallization tends to incorporate a relatively larger proportion of 18O because the energy level (vibration) of ions containing this heavier isotope decreases by a greater amount than ions containing 16O. As temperatures drop, the energy level of 18O declines progressively by an amount that this disproportionately greater than that of the lighter 16O. Consider from here what the value of alpha is (essentially the y-axis)

Distillation 2 varieties, Batch and Rayleigh distillation dependent on if the products stay in contact and re-equilibrate with the reactants Batch Distillation: df = di – (1 – F) 103lnaCO2-Rock where the isotope of the rock (di) depends on it’s initial value (df) and the fractionation factor Rayleigh Distillation df - di =103(F(a – 1) – 1)

RAYLEIGH DISTILLATION Isotopic fractionation that occurs during condensation in a moist air mass can be described by Rayleigh Distillation. The equation governing this process is: where Rv = isotope ratio of remaining vapor, Rv° = isotope ratio in initial vapor, ƒ = the fraction of vapor remaining and a = the isotopic fractionation factor

Effect of Rayleigh distillation on the 18O value of water vapor remaining in the air mass and of meteoric precipitation falling from it at a constant temperature of 25°C. Complications: 1) Re-evaporation 2) Temperature dependency of 

Using isotopes to get information on physical and chemical processes Fractionation is due to some reaction, different isotopes can have different fractionation for the same reaction, and different reactions have different fractionations, as well as being different at different temperatures and pressures Use this to understand physical-chemical processes, mass transfer, temperature changes, and other things…

Volatilization calcite + quartz = wollastonite + carbon dioxide CaCO3 + SiO2 = CaSiO3 + CO2 As the CO2 is produced, it is likely to be expelled Batch vs. Rayleigh Fractionation – In batch fractionation the CO2 stays in the system and continues to re-equilibrate while in Rayleigh factionation the CO2 is separated and does not re-eqiulibrate

Other volatilization reaction examples…

Alta Ski Area – Tertiary pluton intruding paleozoic sedimentary rocks, including quartz-bearing dolomites – this material metamorphosed, look at role of isotopes in deciphering that the rocks were metamorphosed by not only a large amount of heat and associated volatilization reactions, but also by a significant flux of hydrothermal waters. The interpretation is that because the petrology indicates fluid-rich conditions nearestthe contact that the water was primarily magmatic – I am not sure about that though, the volume of fluid needed seems pretty high for that…

Data shows that the mineral assemblages found in the area grade into higher T closer to the contact – the periclase formed at the contact reqires H2O (The x-axis is H2O vs. CO2 fluid compositional space!)

Indicates the isotopic fractionation is not just from the devolatilization reactions – if they were the isotope values should fall into the field from the Raleigh equation…

Suggestion that there may be some sort of mass loss from the interaction of meteoric water

Model results indicating there needed to be significant water flow (200-800 m3/m2)

ISOTOPE FRACTIONATION IN THE HYDROSPHERE Evaporation of surface water in equatorial regions causes formation of air masses with H2O vapor depleted in 18O and D compared to seawater. This moist air is forced into more northerly, cooler air in the northern hemisphere, where water condenses, and this condensate is enriched in 18O and D compared to the remaining vapor. The relationship between the isotopic composition of liquid and vapor is:

Assuming that 18Ov = -13.1‰ and vl(O) = 1.0092 at 25°C, then and assuming Dv = -94.8‰ and vl(H) = 1.074 at 25°C, then These equations give the isotopic composition of the first bit of precipitation. As 18O and D are removed from the vapor, the remaining vapor becomes more and more depleted. Thus, 18O and D values become increasingly negative with increasing geographic latititude (and altitude.

Map of North America showing contours of the approximate average D values of meteoric surface waters.

Because both H and O occur together in water, 18O and D are highly correlated, yielding the meteoric water line (MWL): D  818O + 10

Deviation from MWL Any additional fractionation process which affects O and D differently, or one to the exclusion of the other will skew a water away from the MWL plot These effects include: Elevation effects - (dD -8‰/1000m, -4‰/ºC) Temperature (a different!) Evapotranspiration and steam loss Water/rock interaction (little H in most rocks)

Kinetic Fractionation lighter isotopes form weaker bonds in compounds, so they are more easily broken and hence react faster. Thus, in reactions governed by kinetics, the light isotopes are concentrated in the products. Again, isotope reactions can be exchange reactions or mass-dependent chemical or physical reactions – kinetic factors may affect any of these!

Kinetic fractionation I – SO42- reduction SO42- + CH4 + 2 H+  H2S + CO2 + 2 H2O This reaction is chemically slow at low T, bacteria utilize this for E in anoxic settings Isotope fractionation of S in sulfide generated by microbes from this process generates some of the biggest fractionations in the environment (-120‰ for S) THEN we need to think about exchange reactions with H2S or FeS(aq) as it may continue to interact with other S species

S isotopes and microbes The fractionation of H2S formed from bacterial sulfate reduction (BSR) is affected by several processes: Recycling and physical differentiation yields excessively depleted H2S Open systems – H2S loss removes 34S Limited sulfate – governed by Rayleigh process, enriching 34S Different organisms and different organic substrates yield very different experimental d34S Ends up as a poor indicator of BSR vs. TSR

Iron Isotopes Earth’s Oceans 3 Ga had no oxygen and lots of Fe2+, cyanobacteria evolved, produced O2 which oxidized the iron to form BIFs – in time the Fe2+ was more depleted and the oceans were stratified, then later become oxic as they are today This interpretation is largely based on iron isotopes in iron oxides and sulfide minerals deposited at those times (Rouxel et al., 2005) No one has yet bothered to measure how iron isotopes change when iron sulfide minerals precipitate – that’s where we come in…

Mass-independent fractionation Mass effects for 3 stable isotopes (such as 18O, 17O, and 16O) should have a mass-dependent relationship between each for any process Deviation from this is mass-independent and thought to be indicative of a nuclear process (radiogenic, nucleosynthetic, spallation) as opposed to a physico-chemical process Found mainly associated with atmospheric chemistry, effect can be preserved as many geochemical reactions in water and rock are mass-dependent

S-isotopic evidence of Archaen atmosphere Farquar et al., 2001; Mojzsis et al., 2003 found MIF signal in S isotopes (32S, 33S, 34S) preserved in archaen pyrites precipitated before 2.45 Ga Interpreted to be signal from the photolysis of SO2 in that atmosphere – the reaction occurs at 190-220nm light, indicating low O2 and O3 (which very effficiently absorb that wavelength)