<p>First let me start by saying that redox buffers are a made-up thing. All these QFM (actually FMQ) or NNO or other abbreviations don't exist in nature. They were developed as a way to "cheat" in experiments to get the desired Fe(II)/Fe(III) ratio, and later extended for more uses. High temperature and pressure experiments are permeable to hydrogen: it just goes through the experimental capsule. Depending on the direction of diffusion, it can either oxidise or reduce the contents of the capsule, changing the desired Fe(II)/Fe(III) ratio. Buffers "force" a certain oxygen fugacity. In reality, redox (or not) is buffered by a variety of reactions that we may not even know exist.</p>

<blockquote>
  <p>partial pressure (fugacity) of an element such as oxygen </p>
</blockquote>

<p>In the deep Earth, there is no free O<sub>2</sub> gas phase, so it doesn't make sense anymore to talk about the "partial pressure". But the oxygen fugacity controls the reactions involved electron transfer (i.e. buffers).</p>

<blockquote>
  <p>how oxygen fugacity influences mineral crystallization</p>
</blockquote>

<p>In general, higher oxygen fugacity means there's a higher ratio of Fe<sup>3+</sup> to Fe<sup>2+</sup>. This is particularly true in melts. So a melt with lots of Fe<sup>3+</sup> will crystallise magnetite (for example) whereas a reduced melt with little Fe<sup>3+</sup> will not. This is one of the differences between tholeiitic and calc-alkaline differentiation trends. Calc-alkaline melts are oxidised, so they crystallise magnetite early. Therefore, they never reach high Fe contents. Tholeiitic melts re reduced, and magnetite does not crystallise until very late, so it is possible for them to reach high Fe contents.</p>

<p>This is also important for sulfur. Will a volcano erupt SO<sub>2</sub> or H<sub>2</sub>S? It all depends on the oxygen fugacity of the system.</p>

<p>I will also add that the bulk amount of Fe<sup>3+</sup> and Fe<sup>2+</sup> does not directly tell you where a rock is oxidised or not (with respect to oxygen fugacity). For example, a rock with 1% hematite, 98% enstatite and 1% magnetite will have more bulk Fe<sup>2+</sup> than a rock with 50% magnetite, 49% quartz and 1% fayalite. But, the former is at the HM buffer while the latter is at the FMQ buffer (reduced).</p>

<p>I highly recommend reading this (preferably more than once):</p>

<p>Frost, B. R. (1991). "Introduction to oxygen fugacity and its petrologic importance." Reviews in Mineralogy and Geochemistry 25: 1-10.</p>

CC BY-SA 3.0
2018-03-12T11:21:43.250Z
Thank you for this lucid explanation. After reading your comment, the material in my textbook makes much more sense. I feel I now have a better context in which to understand this.
Steven
CC BY-SA 3.0
2018-03-16T08:29:19.020Z
@Steven great - make sure you tick the V next to the upvote button to mark this answer as accepted
Gimelist
CC BY-SA 3.0
2018-03-11T07:23:26.383Z
2018-03-11T07:23:26.383Z
Gimelist
<p>I'm trying to gain a firmer conceptual understanding of how redox buffers work in petrology, specifically how oxygen fugacity influences mineral crystallization. </p>

<p>While I understand the mathematical and thermodynamic principles underlying these concepts, I'm not seeing how changes in the partial pressure (fugacity) of an element such as oxygen can impact what minerals crystallize.</p>

<geochemistry><petrology><thermodynamics>
Please help in understanding redox buffers
Steven
# Please help in understanding redox buffers

(Asked by: username_0 on 2018-03-10)

I'm trying to gain a firmer conceptual understanding of how redox buffers work in petrology, specifically how oxygen fugacity influences mineral crystallization.

While I understand the mathematical and thermodynamic principles underlying these concepts, I'm not seeing how changes in the partial pressure (fugacity) of an element such as oxygen can impact what minerals crystallize.

**Tags:** geochemistry, petrology, thermodynamics


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## 1 answers

### Answer by username_1 on 2018-03-11. Score: 5

First let me start by saying that redox buffers are a made-up thing. All these QFM (actually FMQ) or NNO or other abbreviations don't exist in nature. They were developed as a way to "cheat" in experiments to get the desired Fe(II)/Fe(III) ratio, and later extended for more uses. High temperature and pressure experiments are permeable to hydrogen: it just goes through the experimental capsule. Depending on the direction of diffusion, it can either oxidise or reduce the contents of the capsule, changing the desired Fe(II)/Fe(III) ratio. Buffers "force" a certain oxygen fugacity. In reality, redox (or not) is buffered by a variety of reactions that we may not even know exist.

> partial pressure (fugacity) of an element such as oxygen

In the deep Earth, there is no free O2 gas phase, so it doesn't make sense anymore to talk about the "partial pressure". But the oxygen fugacity controls the reactions involved electron transfer (i.e. buffers).

> how oxygen fugacity influences mineral crystallization

In general, higher oxygen fugacity means there's a higher ratio of Fe3+ to Fe2+. This is particularly true in melts. So a melt with lots of Fe3+ will crystallise magnetite (for example) whereas a reduced melt with little Fe3+ will not. This is one of the differences between tholeiitic and calc-alkaline differentiation trends. Calc-alkaline melts are oxidised, so they crystallise magnetite early. Therefore, they never reach high Fe contents. Tholeiitic melts re reduced, and magnetite does not crystallise until very late, so it is possible for them to reach high Fe contents.

This is also important for sulfur. Will a volcano erupt SO2 or H2S? It all depends on the oxygen fugacity of the system.

I will also add that the bulk amount of Fe3+ and Fe2+ does not directly tell you where a rock is oxidised or not (with respect to oxygen fugacity). For example, a rock with 1% hematite, 98% enstatite and 1% magnetite will have more bulk Fe2+ than a rock with 50% magnetite, 49% quartz and 1% fayalite. But, the former is at the HM buffer while the latter is at the FMQ buffer (reduced).

I highly recommend reading this (preferably more than once):

Frost, B. R. (1991). "Introduction to oxygen fugacity and its petrologic importance." Reviews in Mineralogy and Geochemistry 25: 1-10.

> **Comments:**
> **username_0**: Thank you for this lucid explanation. After reading your comment, the material in my textbook makes much more sense. I feel I now have a better context in which to understand this.  
> **username_1**: @username_0 great - make sure you tick the V next to the upvote button to mark this answer as accepted  

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