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Redox Zonation

Chapter · July 2011

DOI: 10.1007/978-3-642-11274-4_1139

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 Redox Zonation R 1441

Biology References and Further Reading

Virtually all reactions employed in catabolism, and many Atkins PW (1990) Physical chemistry, 4th edn. WH Freeman and Com-
reactions employed in metabolism more generally, involve pany, New York, see Chapter 10, “Equilibrium Electrochemistry”
Madigan MT, Martinko JM, Parker J (2000) Brock biology of microor-
transfer of electrons. Extensive use is made of redox poten-
ganisms, 9th edn. Prentice-Hall, New Jersey, see Section 4.6,
tials in characterizing such processes. Because reactions in “Oxidation-Reduction”
cell cytoplasm typically occur at near-neutral pH, Stumm W, Morgan JJ (1996) Aquatic chemistry: chemical equilibria and
a convention in biology is to work with a modified stan- rates in natural waters, 3rd edn. Wiley-Interscience, New York, see
dard reduction potential, E˚˜΄ (or Eo΄), that specifies the Chapter 8, “Oxidation and Reduction; Equilibria and Microbial
Mediation”
zero-current potential for a given half reaction at pH = 7
(where standard reduction potential is expressed for unit
H+ activity, or pH = 0). For reactions that include protons
as products or reactants, E˚˜΄ differs from E˚˜, but the two
can be related through equation (2) above (by setting {H+}
= 107 in the Q term). In both biology and geochemistry, Redox Zonation
the quantity pε is sometimes also used as a measure of
redox potential. In analogy to pH (=log{H+}), pε is DANIELE L. PINTI
a measure of the solution activity of hypothetical free GEOTOP & Department of Earth and Atmospheric
electrons, pε = log{e}, and is related to E via: Sciences, Université du Québec à Montréal, Montréal,
QC, Canada
pe ¼ ðF=2:3RTÞ E ð3Þ

Geochemistry
Synonyms
Geochemical systems are frequently also characterized
Chemical zones; Metabolic zones; Redox zones
with reference to redox potential. In addition to the mea-
sures above, the overall redox potential of a system may be
described in terms of hypothetical activities or fugacities Keywords
of H2 or O2 (e.g., aH2 or fH2). Such expressions can be Anoxic, geochemical environments, oxic, oxygen levels,
related to E via equation (2), above (by specifying the non- redox potential, sedimentary environments, suboxic
unit activity or fugacity of H2 or O2 in the reaction quo-
tient (“Q”) term). Oxygen fugacity, fO2 (and, therefore, Definition
redox potential), is sometimes also specified by reference Redox zonation is the subdivision of natural environ-
to mineral “redox buffers.” These buffers, constituting the ments (geochemical, ecological, or sedimentary) based
reduced and oxidized mineral species in a reaction involv- on the availability of O2 to be consumed to completion
ing oxygen, specify a unique fO2 for a given set of physi- by biological respiration and inorganic chemical reactions.
cochemical conditions. Thus, for example, “QFM” Traditional classification scheme for sedimentary environ- R
specifies fO2 (for a given temperature) at equilibrium in ments in oxic and anoxic is based on the amount of
the oxidation of fayalite (F) to magnetite (M) and quartz measurable dissolved O2 and dissolved sulfide in sedi-
(Q), 3 Fe2SiO4(F) + O2 ! 2Fe3O4(M) + 3SiO2(Q), when ments at the time of authigenic mineral precipitation
all three mineral species are present. Mineral redox buffers (Berner 1981). Classification schemes for oceanographic
are a convenient way to describe changing redox condi- and ecological studies propose five principal redox zones
tions over wide-ranging temperatures, and to understand (oxic, nitric, sulfatic, carbonic, and nitronic) based on the
real-world effects on redox chemistry within the solid sequential thermodynamic availability of electron accep-
Earth. tors to oxidize marine planktonic organic matter (organic
See also matter mineralization).
▶ Bioenergetics
▶ Electron Acceptor Overview
▶ Electron Donor Redox zonations are common in natural systems espe-
▶ Energy Sources cially where mixing is limited and oxygen is consumed
▶ Redox Zonation by biological respiration and inorganic chemical reactions
▶ Reducing Agent (Canfield and Thamdrup 2009). Geochemical environ-
▶ Reduction ments where sedimentary rocks formed are characterized
1442 R Redox Zones

in terms of hydrogen ion activity (pH) and the References and Further Reading
oxidation-reduction potential (Eh). But these parame- Berner RA (1981) A new geochemical classification of sedimentary envi-
ters are not useful in a practical sense, pH being quite ronments. J Sed Petrol 51:359–365
Canfield DE, Thamdrup B (2009) Towards a consistent classification
uniform for marine and nonmarine subaqueous sedi-
scheme for geochemical environments, or, why we wish the term
ments (pH = 6–8) and Eh not practically measurable “suboxic” would go away. Geobiology 7:385–392
(Berner 1981). Indeed, many of the species involved in Murray JW, Jannasch HW, Honjo S, Anderson RF, Reeburgh WS, Top Z,
sedimentary oxidation–reduction reactions, such as SO4 Friederich GE, Codispoti LA, Izdar E (1989) Unexpected changes in
or NH4+, are not electroactive, that is, they do not readily the oxic/anoxic interface in the Black Sea. Nature 338:411–413
accept or release electrons from the gold and platinum
electrodes used for measuring the Eh. The common
classification defined by Berner (1981) was based on
the amount of dissolved O2 and total sulfide (H2S plus
Redox Zones
HS-) measurable in a specific environment and the
▶ Redox Zonation
presence or absence of characteristic mineral phases sen-
sitive to the occurrence of O2 and H2S in the environment.
The term “oxic” was then identified as a zone containing
O2 with concentrations higher than 1 mmol/L and occur- Redshift
rence of ▶ hematite, ▶ goethite, manganese-bearing
oxides but no organic matter. The term “anoxic” was Definition
then assigned to a zone where O2 concentration is less The redshift is a quantity, generally noted z, that measures
than 1 mmol/L. This anoxic zone is then subdivided the Doppler effect of a celestial object which is going away
into “sulfidic” (H2S concentration higher than 1 mmol/L from the observer, thus whose light exhibits an apparent
and occurrence of pyrite, marcasite, and organic matter) shift toward a longer wavelength. The term is especially
and “non-sulfidic” (H2S concentration less than suited for distant objects in the expanding Universe (gal-
1 mmol/L). The “non-sulfidic” zone is in turn divided axies, quasars, clusters of galaxies), since it supposes that
into “post-oxic” (presence of glauconite and iron silicates; the change of wavelength is positive (the apparent longer
no sulfide minerals and minor organic matter) and wavelength makes the object redder than it is in its
“methanic” (presence of siderite, sulfide minerals, and restframe). The term blueshift is sometimes used for the
organic matter). The most important addition to this reverse situation of an object which is approaching
simple scheme was the discovery of the so-called the observer. The redshift gives a direct information on
“suboxic” zone at the oxic–anoxic interface, which is the recession velocity v of the object. For a velocity which
defined as the region where concentrations of oxygen is much lower than the speed of light c, the Galilean
and sulfide are both extremely low and had no perceptible approximation z = v/c is valid. For velocity approaching
gradients (Murray et al. 1989). The redox zonations, trans- the speed of light, a relativistic formulation must be used.
lated to the open ocean, are based on the sequential ther- Note that there is also a redshift, i.e., a positive change in
modynamic availability of electron acceptors to oxidize wavelength, that could be due to a very strong gravita-
organic matter during respiration processes. These tional field; in that case one speaks of gravitational
so-called metabolic zones have names depending on the redshift.
electron acceptor available and subdivided into “oxic/
▶ aerobic respiration” (electron acceptor being O2), See also
nitrate reduction (NO2, NO3), manganese reduction ▶ Doppler Shift
(MnO2), iron reduction (FeOOH), sulfate reduction ▶ Galaxy
(SO42), and ▶ methanogenesis (CO2). ▶ Spectroscopy

See also
▶ Aerobic Respiration Reducing Agent
▶ Goethite
▶ Hematite Definition
▶ Methanogens A reducing agent is a compound that facilitates the
▶ Siderite ▶ reduction of an oxidized compound by a coupled

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