I just love it when Philip talks dirty.

An equivalent measure of redox potential is pE. Just as pH is the negative log of the hydrion activity, pE is the negative log of electron activity (source). Soil pE and soil pH are equally important to predicting charge state of metals and nutrients. However, because measuring pH is relatively easier by far, and because knowing pH tells us volumes about expected pE, soil pE is a less discussed subject. It is important to bioremediation, industrial chemistry, and wetland science. Not a household term.

These two are more than a mirror pair, although mirroring is their most notable characteristic. When pH changes, pE must also change in response. The reverse is true also. In soil, that response departs from simple mirroring. So much so that it can seem to be two separate dances.

Soil pH and pE have different causes of change and different effective buffering agents. The term 'buffering' is replaced in a pE context - it is called poise. A stabilized soil pE system is referred to as a well poised system, differences in soil buffering versus soil poise account for the departure from 1:1 mirroring.

My emphasis. Redox potential and electron activity have just become my new dirty obsession. I'd flirted with it a bit in the past, but now I'm infatuated. As time permits I'll spill about it. . . or at least leak a bit.

Now for the exciting stuff. To many of us, what makes soil different than geologic material is that it is in an excited state, excited mostly by solar energy as facilitated by living processes. Unlike soil pH, soil pE is directly influenced by these energy fluxes.

The most influential cause of changes in soil pE is metabolic respiration aka oxidation. Oxidation doesn't necessarily involve oxygen. Oxidation does necessarily involve shedding an electron. Thus, respiring living systems lower the pE of a soil system, and with pE in the dance lead, pH must follow. . .

A well recognized soil buffering agent is lime . . . The major agent of soil poise is iron. . . [S]oil manganese, although far less abundant than iron, plays a more important, more dynamic role in most soil systems.

One soil scientist, Richmond Bartlett, . . . goes on to describe the role of manganese in terms that nearly describe a catalyst. Mn is not consumed, and the capacity for metabolic respiration increases in its presence.

This is sheer speculation on my part: from my view through the knothole, the nearly catalytic nature of traces of Mn is a finessing touch that makes bio-char the wonderful soil reef it is. It is a fine point, and one hardly worth mentioning considering the much more important issues that need working out in our pursuit of Wim Sombroek's vision for terra preta nova.

One of the components of the dark earth sites in the Amazon is pottery shards, most often cited as evidence that hearth refuse including organic scraps, ashes and charcoal, and broken cookware were disposed of in such soils. Manganese compounds are used by potters, so I wonder if there is some connection here that matters?