doi: 10.1111/j.1365-3121.2006.00719.

The glauconiteFe-illiteFe-smectite problem: a critical review

Alain Meunier and Abderrazak El Albani
HYDRASA UMR CNRS 6532, University of Poitiers, Bat. Sciences Naturelles, 40 avenue Recteur Pineau, 86022 Poitiers Cedex, France

ABSTRACT
Iron silicate minerals are a significant component of sedimen-
tary systems but their modes of formation remain controversial.
Our analysis of published data identifies end-member compo-
sitions and mixtures and allows us to recognize controls of
formation of different mineral species. The compositional fields
of glaucony, Fe-illite, FeAl smectites are determined in the M+/
4Si vs. Fe/Sum of octahedral cations (M+ interlayer charge).
Solid solutions could exist between these phases. The FeAl and
Fe-rich clay minerals form two distinct solid solutions. The
earliest phases to be formed are FeAl smectites or berthierine
depending on the sedimentation rate. Reductive microsystems
appear in the vicinity of organic debris in unconsolidated
sediments. The Fe is incorporated first in pyrite and then in
silicates after oxidation. Potassium ions diffuse from the sea-
watersediment interface. If not interrupted, the diffusion
process is active until reaction completion is reached, i.e.
formation of Fe-illite or glauconite or a mineral assemblage
(berthierinenontronite) according to the available Al ion
amounts in the microsystem. Mixed-layer minerals are formed
when the diffusion process is interrupted because of sedimen-
tation, compaction or cementation. Despite the common belief
of their value as palaeoenvironment indicators, these minerals
can form in a variety of environments and over a period of
millions of years during sediment burial.
Terra Nova, 19, 95104, 2007

Introduction
Clay minerals formed in marine or
hypersaline environments are con-
stantly FeK-rich species: glauconite,
Fe-illite, Fe-smectite, nontronite.
They have been described in contras-
ted sedimentation rate environments
such as big river mouths (Giresse
et al., 1988; Michalopoulos and Aller,
1995; Wiewiora et al., 1999), oceanic
oor (Steinberg et al., 1987), accretion
prisms (Gaudin et al., 2005), marine
hydrothermal vents (Buatier et al.,
1989), continental shelves (Odin,
1988) or evaporitic systems (Pedro
et al., 1978; Baker, 1997; Huggett
and Gale, 1997; El Albani et al.,
2005). Their formation may be very
rapid; a few months for KFeMg
beidellite-type clay minerals in the
Amazon river mouth (Michalopoulos
and Aller, 1995) or very slow, a few
million years for glaucony (Smith
et al., 1998). Most often, these clay
species grow on solid supports (detri-
tal minerals or biogenic debris) from
the sea-watersediment interface to a
variable depth inside the unconsoli-
dated sediments.
Correspondence: Dr Abderrazzak El Albani,
University of Poitiers, UMR 6532, Bat.
Sciences Naturelles, 40, Avenue du Recteur
Pineau, Poitiers Cedex, F-86022, France.
Tel.: +33 5 49 45 39 26; fax: +33 5 49 45 42
41; e-mail: abder.albani@univ-poitiers.fr
In spite (or because) of the huge
literature dedicated to the description
of these KFeMg marine clays, many
points remain controversial or un-
clear. Their formation mechanism is
still an open question. Using pub-
lished data, the purpose of this paper
is to reconsider some of these points.
First, the extension of the solid solu-
tions for each mineral phase is inves-
tigated. Special attention is paid to the
relation between composition domain
overlaps and mixed layering. Such
relationships could indicate a compo-
sitional continuity between the min-
eral species concerned. In a second
step, the mechanism of formation of
these Fe-bearing clay phases is dis-
cussed in order to identify the factors
which determine their species.
Method
Data sources
The data (Table 1) used here have
been selected from published papers
using the following criteria: (1) the
chemical compositions must be coher-
ent with the denition given by AI-
PEA (Bailey, 1980); (2) the structural
formulae must be compatible with a
dioctahedral structure. Celadonite is
not considered here, because it is a
high-temperature phase, typical of
basalt alteration and not of authigen-
esis in sediments. The chemical com-
positions presented in the selected
data have been obtained by wet chem-
ical methods (including the measure-
ments of FeO and Fe2O3 amounts),
electron microprobe or analytical elec-
tron microscopy (AEM).
The M+/4Si vs. Fe/Sum octa.
chemiographic projection
In spite of careful sample preparation
described in the selected papers, the
clay mineral separates, which have
been analysed using wet chemical
methods, were sometimes not totally
puried. Consequently, the calculated
structural formulae suer from experi-
mental errors due to mineral contam-
ination. As the most common source
of contamination for glauconite or Fe-
smectites in sediments is the presence
of quartz, pyrite or calcite, all the
analyses used in the paper were previ-
ously projected in M+4SiR2+
coordinates (Meunier and Velde,
1989). The polluted analyses plot on
mixing lines between the glauconite,
Fe-illite or Fe-smectite domains and
the 4Si, R2+ or M+ poles, respect-
ively. These data have been elimin-
ated. A similar treatment was also
applied to the chemical compositions
obtained using electron microprobe,
because clay minerals are frequently
smaller than the spot size and con-
tamination is always possible. To
solve this problem, Ireland et al.
(1983) and Curtis et al. (1987) pre-
ferred to use AEM. In spite of di-

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The glauconiteFe-illiteFe-smectite problem A. Meunier and A. El Albani Terra Nova, Vol 19, No. 2, 95104
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Table 1 General characteristics of Fe-bearing clay minerals whose chemical compositions are used here. The references are given
for each data source.
Geological data
Formation Sampling depth Stratigraphical age Reference
Glaucony
Miscellaneous Hendrix and Ross (1941)
Miscellaneous Foster (1969)
Miscellaneous Weaver and Pollard (1973)
Miscellaneous Buckley et al. (1978)
Miscellaneous Thompson and Hower (1975)
Miscellaneous Newman and Brown (1987)
Bohemian formations ??? Upper Cretaceous Cimbalnkova (1971)
First Wilcox sandstone 3030 m Eocene Strickler and Ferrell (1990)
Sandstones Outcrop Proterozoic Mendes Guimaraes et al. (2000)
Clayey-siltstoneConglomerate sandstones 435795.5 m AlbianCenomanian Rousset et al. (2004)
Fe-illite
LimestonesCalcareous sandstones Outcrop Middle CambrianLower Berg-Madsen (1983)
Ordovician
Shallow-marine, brackish, lacustrine, hypersaline facies Outcrop Purbeckian Deconninck et al. (1988)
Fluvial litharenites 2258.92266.9 m Early Trias Baker (1997)
Shallow-marine, brackish, lacustrine, hypersaline facies Outcrop Purbeckian El Albani et al. (2005)
Nontronite & Fe-montmorillonite
Galapagos mounds Sea-water interface 3000 m, Recent Buatier et al. (1989)
core 0.133.75 m
Calcareous biogenic sediments Costa Rica margin Sea-water interface 3000 m, Recent Gaudin et al. (2005)
core 0.133.75 m
FeAl beidellite-montmorillonite
Black shales DSDP leg 11 Albian Steinberg et al. (1987)
Sandstones, siltstones 0700 m Miocene to Recent Wiewiora et al. (1999)
Greenalite, Nontronite & Berthierine
Congo River estuary 1216 m Miocene to Recent Wiewiora et al. (1996)

culties in determination of the k nates of celadonite are theoretically:
factors, the AEM analytical precision M+/4Si 1/1; Fe/Sum octa. 1/2.
was roughly similar to that of electron The coordinates discriminate the
microprobe equipped with an energy Fe-bearing clay species (Fe-montmo-
dispersion system. We used the chem- rillonite, nontronite) but not the
ical compositions obtained by Ireland Al-bearing ones (montmorillonite,
et al. (1983) to check the validity of beidellite).
those obtained by wet chemical and The end-member compositions used
electron microprobe methods. here are presented in Table 2. A the-
The presence of other phyllosili- oretical composition of glauconite has
cates such as trioctahedral 1 : 1 or been proposed on the mica model
2 : 1 : 1 phases (sometimes interstrati- (Bailey, 1980) assuming a layer charge
ed) leads to erroneous calculations of of )1 per Si4O10. It is close to that of
the cation proportions in both the
tetrahedral, octahedral and interlayer Table 2 Projection of the compositions of the Fe-bearing clay mineral end-members
sheets. This drawback can be partially in the M+/4Si vs. Fe/Sum octahedral cations diagram.
reduced if ratios are used rather than
End-members Symbol
absolute cation amounts. Indeed, ra-
tios being independent of the oxygen Celadonite Cel
calculation basis, the artefact due to Glauconite (mica) Glm
contamination by 1 : 1 or 2 : 1 : 1 Glauconite (illite) Gli
clay phases is eliminated. As struc- Nontronite (high charge) No Hc
tural formulae are generally calculated Nontronite (low charge) No Lc
for Si4O10, the M+/4Si vs. Fe/Sum Fe-montmorillonite (high charge) FeMo Hc
octahedral cations coordinates were Fe-montmorillonite (low charge) FeMo Lc
Beidellite (high charge) Be Hc
chosen. The M+/4Si ratio corres-
Beidellite (low charge) Be Lc
ponds to the interlayer charge
Al-montmorillonite (high charge) AlMo Hc
(Na + K + 2Ca) divided by Si
Al-montmorillonite (low charge) AlMo Lc
amount/4. For instance, the coordi-
celadonite. However, another compo-
sition has been considered because
glauconite is a low temperature min-
eral which could be considered closer
to illite than to mica (Meunier and
Velde, 2004). Thompson and Hower
(1975) have shown that glauconies
having less than 5% expandable layers
are near 0.75 K per Si4O10. Using this
value, a formula was derived from
that proposed by the AIPEA (Ta-
ble 2). In spite of the fact that berthi-
erine is a trioctahedral species, it will
Structural formulae
[Si4)xAlx]O10(Fe3+Mg)(OH)2K with x < 0.2
3+ 2+
[Si3.67Al0.33]O10(R3 2
1:33 R0:67 (OH)2K, Fe >Al Mg>Fe
[Si3.75Al0.25]O10(R3 R 2
1:50 0:50 (OH) 2K0.75
[Si3.4Al0.6]O10(Fe3
2 (OH)2 M0:6
[Si3.7Al0.3]O10(Fe2 (OH)2 M
3
0:3
Si4O10(Fe31:4 Mg0.6)(OH)2 M0:6
3
Si4O10(Fe1:7 Mg0.3)(OH)2 M0:3
[Si3.4Al0.6]O10(Al2)(OH)2 M
0:6
[Si3.7Al0.3]O10(Al2)(OH)2 M
0:3
Si4O10(Al1.4Mg0.6)(OH)2 M 0:6
Si4O10(Al1.7Mg0.3)(OH)2 M0:3

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Terra Nova, Vol 19, No. 2, 95104 A. Meunier and A. El Albani The glauconiteFe-illiteFe-smectite problem
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be represented here because it is fre-
quently associated with glauconitic
minerals. Its compositional domain
has been determined using data from
Brindley (1982).

Data from the literature

The chemical composition domains of

glauconite, Fe-illite, FeAl smectites
and Fe-smectites
Data from Hendrix and Ross (1941),
Foster (1969), Weaver and Pollard
(1973), Thompson and Hower (1975),
Buckley et al. (1978), Newman and
Brown (1987) and Cimbaln kova
(1971) have been used to determine
the chemical compositional domain of
glaucony. This domain extends from
the glauconite-mica (Glm) and glauc-
onite-illite (Gli) end-members towards
the Al-smectite compositions
(Fig. 1a). The glauconite composition
eld appears to be roughly limited to
Fe/Sum octa. 0.25 on its smectite
side (grey zone in Fig. 1a). The chem-
ical compositions obtained using
AEM (Ireland et al., 1983) plot inside
that eld (Fig. 1b). This means that
the eects of mineral contamination in
the selected data obtained by wet
chemical methods are negligible.
Therefore, these analyses can be used
safely. This allows us to take into
account the FeO and Fe2O3 amounts
which are not measurable using elec-
tron microprobe or AEM analyses.
The composition domain of Fe-
illites (or aluminous glauconites) is
represented in Fig. 1(c). A part of the
compositions published by Berg-Mad-
sen (1983) and Baker (1997) lie in the
glauconite domain. Consequently, the
corresponding Fe-illite cannot be
distinguished from glauconites. On
the contrary, the other compositions Fig. 1 Plots of the chemical compositions of the Fe-bearing clay phases in the M+/4Si
are comparable to those published by vs. Fe/Sum octahedral cations diagram. (a) Glauconies (wet chemical analyses). (b)
Deconninck et al. (1988) and El Alba- Glauconies (AEM). (c) Fe-illite. (d) FeAl smectites.
ni et al. (2005). They plot in a eld
whose limits are: 0.12 Fe/Sum
octa. 0.25 and 0.95 M+/ tites are considered to have ordinary the selected literature show that the
4Si 0.55 (grey zone in Fig. 1c). It is layer charges, i.e. 0.30.6 per Si4O10, elds for each species extend over
to be noticed that data from El Albani their composition domain is bordered several contiguous compositional
et al. (2005) are those of Fe-illite/ as follows: 0.12 Fe/Sum octa. types. Even if we ignore their exact
smectite mixed layer minerals. 0.25 and 0.3 M+/4Si 0.7 (grey extension, one can infer that there is
The compositions of FeAl smec- zone in Fig. 1d). no composition gap between these
tites given by Steinberg et al. (1987) The glaucony, Fe-illite and FeAl three phases. This is not the case for
and Wiewiora et al. (1999) are largely smectite composition domains as they the Fe-rich smectites whose composi-
scattered (Fig. 1d). Part of them lie in are dened here are contiguous. These tions are scattered in a distinct domain
the Fe-illite and glauconite composi- domains dene the type compositions (Fig. 2). Most of the published com-
tion elds. However, if FeAl smec- for each species. However, data from positions lie outside the theoretical

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The glauconiteFe-illiteFe-smectite problem A. Meunier and A. El Albani Terra Nova, Vol 19, No. 2, 95104
.............................................................................................................................................................
the measured composition is acquired
early in the post-sedimentary stage
and does not change during the burial
stage. However, this is a controversial
point as several papers argue that the
glauconitization process is active over
long periods of time. For instance,
Strickler and Ferrell (1990) showed
that the composition of glaucony
grains varies according to the degree
of cementation of the sediment
(Fig. 5). The most mature, i.e.
Fig. 2 Plot of the chemical compositions of the Fe-smectites in the M+/4Si vs. Fe/ Fe-rich, grains are found in the unce-
Sum octahedral cations diagram. mented zones, while the most imma-
ture ones have been observed inside

smectite composition domain limited

by the Nohc, Nolc, FeMohc and
FeMolc end-members. Except for the
Fe-rich smectites analysed by Wiew-
iora et al. (1999), the other composi-
tions (Buatier et al., 1989; Gaudin
et al., 2005) plot in a domain bordered
by the FeMohc and FeMolc end-
members and oriented towards the
berthierine composition eld (grey
zone in Fig. 2).
The iron and potassium contents
of glauconies are not correlated
(Fig. 3a). Iron is present in the two
valency states; the more oxidized one
(Fe3+) predominates. The Fe2+/
Fe3+ ratio is highly variable; it is
obviously not correlated to Si or K
amounts (Fig. 3b,c). This was dis-
cussed by Velde (2003) who consid-
ered that all iron cannot be found
entirely within the sediment included
in proto-glauconite pellets, a part of
it being necessarily introduced from
outside.

The variability of glaucony chemical

compositions
It has been constantly observed that
the composition of glauconies varies
from place to place in a given forma-
tion and from grain to grain in a given
place. Figure 4 shows the dispersion
of two Fe-rich glaucony sample series
from the upper Cretaceous Bohemian
formations (Cimbaln kova, 1971) and
sandstones and siltstones of the Al-
bian-Cenomanian formations of
south-eastern France (Rousset et al.,
2004) and an Al-rich glaucony series Fig. 3 Iron content of glauconies. (a) Total Fe content vs. K. (b) Fe2+/Fe3+ vs. 4Si.
from the Proterozoic sandstones of (c) Fe2+/Fe3+ vs. K.
the Paranoa Group, mid-western Bra-
zil (Mendes Guimaraes et al., 2000). conditions experienced by the glaucony- concretions. The authors estimated
Neither the increasing stratigraphical bearing rocks modify the compositions that the maturation process (incor-
age, nor the intensity of the diagenetic of glaucony grains. This means that poration of Fe3+ cations) is active at

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Terra Nova, Vol 19, No. 2, 95104
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Fig. 4 Variability of the chemical composition of glauconies formed in similar
conditions in dierent geological formations.
Fig. 5 Variation of the composition of glauconies with the degree of cementation of
the Wilcox sandstones, Upper Palaeocene to Lower Eocene (from Strickler and
Ferrell, 1990).
depths from 0.6 to 1.8 km. They
claimed that glauconitization is a
time-dependent process. This is sup-
ported by Smith et al. (1998) who
showed from 40Ar/39Ar ages of glau-
cony grains that glauconitization
could be active over periods of several
million years.
Because of the great importance of
glaucony for the geological time scale,
the time-dependence of the glauconi-
tization process has been investigated
early. Using several sample series,
Odin and Dodson (1982) have shown
that the apparent KAr age decreases
with increasing K2O content of glau-
cony. The apparent KAr ages de-
Fig. 6 Relation between apparent KAr age and the K2O amount in glauconies from
the Gulf of Guinea (from Odin and Dodson, 1982).
 2006 Blackwell Publishing Ltd
A. Meunier and A. El Albani The glauconiteFe-illiteFe-smectite problem
pend on the relative proportions of
detrital vs. authigenic clays in the
analysed samples. The zero age is
obtained by extrapolation of the
detrital component to zero. The
example of the Gulf of Guinea sample
series shows that the amount of detri-
tal clays (det.clay) decreases with
increasing K2O according to an expo-
nential function (Fig 6). Conse-
quently, the detrital clay + K + Fe
glaucony mineral reaction is a rst
order one:
ddet.clay
 kdet.clay
dt
The conditions of formation of the Fe-
and FeAl smectites
Figures 1 and 2 show that the com-
position domains of Fe- and FeAl
smectites do not overlap: no interme-
diate compositions between the FeAl
beidellitemontmorillonite and the
Fe-montmorillonitenontronite com-
position elds. The origin of the com-
position gap between the two smectite
groups is related to the conditions of
formation. The compositions of the
hosting sediments and the sedimenta-
tion rate could be the factors that
control the formation of one or the
other smectite groups.
The Holocene to Miocene deltaic
sediments of the Congo river contain
smectites of the nontronite or FeAl
beidellite group, which form in low or
high sedimentation rate environments,
respectively (Wiewiora et al., 1996,
1999). In both cases, they are associ-
ated with berthierine. Two mineral
reactions may be inferred from these
observations:
1. kaolinite + quartz + goeth-
ite nontronite + Fe-rich 7 A
phase (berthierine).
2. Fe-kaolinite + quartz FeAl
beidellite + Fe-rich 7 A phase (berthi-
erine).
In both cases, kaolinite is destabil-
ized and becomes a source of alumin-
ium for new phases. Aluminium is
consumed rst in berthierine. Non-
tronite is formed instead of FeAl
smectites, because goethite dissolves
and provides large amounts of Fe into
the system. In the absence of goethite,
two aluminium-rich phases are
formed concomitantly: AlFe smectite
and berthierine.
The Albian black shales collected
in the Atlantic ocean (Steinberg
et al., 1987) are aluminium-rich sedi-
ments. The clay fraction is composed
of illite and smectite particles which
exhibit FeAl beidellite or FeAl
montmorillonite overgrowths,
respectively. The neoformation of
these FeAl smectites was considered
to be due to the reaction of detrital
clay particles with pore-water during
early diagenesis. The chemical con-
ditions prevailing during the mineral
reactions could be estimated through
the associated mineral phases. The
presence of clinoptilolite, siderite,
iron sulphide and opal indicate that
the solutions were alkaline, reducing
99
The glauconiteFe-illiteFe-smectite problem A. Meunier and A. El Albani
.............................................................................................................................................................
and saturated with respect to amor-
phous silica.
The sediments overlying the Galap-
agos spreading centre (Buatier et al.,
1989) or the Costa Rica margin (Gau-
din et al., 2005) are both calcareous
sediments mostly composed of pelagic
ooze. Calcite is the predominant min-
eral, but the sediments contain opal
also and siliceous biogenic remains.
No detritals such as clay minerals,
feldspars or mica have been observed.
The sediments are aluminium poor. In
both cases, the green material was
seen to be composed of Fe-rich,
Al-depleted smectites. Lath-shaped
particles observed in the sediments
overlying the Galapagos hydrother-
mal systems were described as glauc-
onite particles because of their high
charge. However, they are far from
the denition given by Bailey (1980)
as total Al varies from 0 to 0.17 per
Si4O10. The Fe-rich smectites are
mostly Fe-montmorillonites but their
compositions are scattered in a large
domain, roughly oriented towards the
berthierine composition (Fig. 2).
Discussion
The numerous published data devoted
to Fe-bearing clay mineral species
formed in marine or hypersaline envir-
onments show that the transition from
expandable phases to non-expandable
ones, if it exists, does not depend on
the age of the hosting formation, nor
on burial depth. This was discussed by
Velde (2003). From the results presen-
ted above, it appears that all these
minerals form in open reductive
microsystems which attract some
chemical components from outside
them by ion diusion in the pore
solutions. The potential relation
between the species of the Fe-clay
mineral which is formed and the local
conditions such as the composition of
the sediment must be investigated
rst. Then, as chemical diusion is
involved in the process, the inuence
of time should be studied.
Relation between Fe-bearing clays,
sediment composition and time
Two groups of Fe-bearing clays
formed in marine or hypersaline envir-
onments can be distinguished: (1) the
FeAl smectiteFe-illiteglauconite
group in which no composition gap
100
separates the dierent phases; (2) the
Fe-montmorillonitenontronitebert-
hierine group in phases are separated
by composition gaps (Fig. 7). The
absence of a composition gap in the
rst group is to be related to the
capacity of glauconite to be inter-
layered with smectite as shown by
Thompson and Hower (1975). The
extension of the glaucony domain
towards the FeAl smectite composi-
tion suggests that the expandable
layers in the mixed layered structures
have FeAl smectite compositions.
This reinforces the assumption of a
complete solid solution between Fe
Al smectites and glauconite. A similar
solid solution may exist between Fe
Al smectites and Fe-illite because
mixed layer minerals have been ob-
served (El Albani et al., 2005). In
other words, a complete glaucony-Fe
illiteFe,Al smectite solid solution
may exist.
The second group does not show
any overlap of the composition do-
mains of Fe-montmorillonite or non-
tronite on the one hand and glaucony
or Fe-illites on the other. Besides,
there is no evidence of mixed-layering
between these phases. On the con-
trary, the fact that mixed-layering has
been observed between 1 : 1 Fe-rich
layers (Wiewiora et al., 1999) could
explain the extension of the Fe-mont-
morillonite composition eld towards
the berthierine type composition
(Fig. 2).
Two factors may control the for-
mation of one or the other Fe-bearing
clay groups: the composition of the
sediment and the conditions of sedi-
mentation. If the inuence of the
composition of the sediment is obvi-
ous for the formation process of the
Fe-montmorillonites, it is not deter-
minative for the other clay species.
Fig. 7 Compositional domains of Fe-bearing clay phases in the M+/4Si vs. Fe/Sum
octa. coordinates. The mixed layer minerals (MLM) which have been identied are
indicated in their compositional elds.
Terra Nova, Vol 19, No. 2, 95104
Indeed, Fe-montmorillonites which
are almost completely Al-depleted
are formed in calcareous biogenic
ooze deposits while glaucony, Fe-illite,
FeAl smectites, crystallize in sedi-
ments containing Al-bearing phases.
However, this is not apparently totally
self-consistent because nontronite and
berthierine are also formed in clay-
bearing sediments (Wiewiora et al.,
1996). Why is a Fe-rich smectite such
as nontronite, which is not very dif-
ferent from Fe-montmorillonites,
formed in spite of abundant alumin-
ium sources in the environment? This
could be due to the fact that berthier-
ine crystallizes rst in the youngest
sediments (upper part of the deposi-
tional column) and then co-precipi-
tates with nontronite in the older ones
(lower part of the column). Berthier-
ine and nontronite are the Al- and
Fe-bearing phases of an authigenic
mineral assemblage. In the absence of
berthierine, FeAl smectites would
form in the place of nontronite. The
presence or absence of berthierine
seems to be the decisive factor which
determines the composition of the
smectite in the green grains.
Considering the geological environ-
ments in the Congo river mouth, the
berthierinenontronite assemblage
and Fe-beidellite are formed in the
low and high sedimentation rate
zones, respectively (Wiewiora et al.,
1996, 1999). A low sedimentation rate
favours the slow chemical exchanges
between pore water and neoformed
clays. This is consistent with the long
maturation time needed for glaucon-
itization (up to 5 Ma according to
Smith et al., 1998). On the contrary, a
high sedimentation rate gives rapid
burial. Consequently, the Fe-beidellite
has to be formed quickly near the sea-
watersediment interface. This was
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Terra Nova, Vol 19, No. 2, 95104
.............................................................................................................................................................
experimentally shown by Michalo-
poulos and Aller (1995) in the
Amazon shelf sediments. These
authors claimed that KFeMg clay
minerals were formed on various solid
substrates after only a few months.
Summarizing, the FeKMg clay
minerals in marine or hypersaline
environments crystallize according to
ve dierent reactions (Fig. 8):
1. FeAl smectites: rapid overgrowth
on detrital phyllosilicates at the
sedimentsea-water interface. The
duration of the reaction is limited
by the high sedimentation rate.
2. Glaucony: the glauconitization pro-
cess (arrow 12 in Fig. 8) is time-
dependent: the shorter it is, the
lower the amount of potassium
incorporated, then the higher the
smectite layer content in the mixed
layer structures. Glauconitization
which is controlled by chemical
diusion, goes to completion only
in low sedimentation-rate environ-
ments. The continuity between the
FeAl smectite and the glaucony
domains suggests that the smectite
forms rst and behaves as a nuc-
leus on which glauconite Glm or
Gli grow.
3. Fe-illite: it forms preferentially in
hypersaline environments where the
sedimentation rate is low (arrow
13 in Fig. 8). Even if its occur-
rences are less well documented
than the glaucony ones, comparable
mixed layered structures have been
described. The Fe-illite and FeAl
smectite composition domains
being overlapping, this suggests
that both are the components of
the MLMs.
4 & 5. Fe-montmorillonite and the
nontronite-berthierine assemblage:
both are formed in low sedimen-
tation-rate environments by a
Fig. 8 Summary of the dierent processes of formation and the corresponding
environment conditions for FeAl smectites (1), glaucony (2), Fe-illite (3), Fe-
montmorillonite (4) and nontronite-berthierine (5).
 2006 Blackwell Publishing Ltd
A. Meunier and A. El Albani The glauconiteFe-illiteFe-smectite problem
chemical diusion process. High
resolution electron microscopy ob-
servations suggest that nontronite
can be interlayered with berthierine.
The reducing microsystem
The formation of green clays in
marine environments, i.e. glaucony
or Fe-rich smectites, is made possible
by the migration of K and Fe ions
from sea-water or surrounding sedi-
ments to a given microsystem
centred on organic debris. The crys-
tallization process at low tempera-
ture inside the microsystem is
facilitated by the presence of Mg2+
ions (Harder, 1978, 1980). Whatever
its shape (pellets, worm burrows,
grain coatings) or its mineral struc-
ture (glauconite, MLM, Fe-smectite),
the green material is frequently
chemically zoned (Parron, 1989;
Gaudin et al., 2005). Both ion migra-
tion and zonation suggest that the
formation of green minerals depends
on chemical diusion. The amount
of K ions is considered as an index
of progression of the mica-forming
process (Thompson and Hower,
1975). The absence of correlation
with Fe amounts (Fig. 3) shows
that K and Fe ions are provided
to the microsystem by independent
processes.
The sources of K and Fe ions are
sea-water and detrital minerals,
respectively (Fig. 9). Most of the iron
contained in detrital minerals is in the
Fe3+ state (oxides, Fe-kaolinite). Iron
must be in the soluble Fe2+ state to
migrate towards the proto-green min-
eral pellet. Thus, the source of iron is
limited to the micro-environment in
which organic debris or bacterial
activity impose reducing conditions.
The Fe is incorporated either in the
silicate or the sulphide phases. Gaudin
et al. (2005) have shown that frambo-
idal pyrite is formed rst in such
microenvironments. The silicate phase
cannot incorporate iron when sul-
phide present. It forms when the
sulphide is oxidized. To crystallize,
Fe-rich smectites and glauconite need
a change in the Redox conditions at
the scale of the microsystem: oxida-
tion occurs as soon as the organic
matter is totally mineralized and the
bacterial activity stops (Gaudin et al.,
2005). This explains why a part of the
Fe2+ ions is oxidized when incorpor-
ated into the green grains. Then,
glauconite form by a nucleation-crys-
tal growth process (Gago-Duport
et al., 2000).
Potassium chemical diffusion and
glauconitization
Odin and Dodson (1982) claimed that
Glauconitization may go to comple-
tion in close contact with the sea-
water. This means that exchanges with
the sea-water must be possible during
the whole process; such exchanges can
only occur in the rst centimetres of a
mud, in the rst decimetres of a sandy
mud and the rst few metres of pure
coarse sand. These observations indi-
cate that the physical characteristics
(porosity, permeability, tortuosity) of
the hosting sediment are decisive in
the glauconitization process. Consid-
ering that glauconitization is con-
trolled by chemical diusion, the
Odin and Dodsons observation sug-
gests that two parameters should be
taken into account: the ux of ion
species per time (f) and the length of
diusion paths (l). The thickness of
the diusion zone being obviously
dependent on the grain size in the
sediments, this means that the tortu-
osity is one of the main parameters to
be considered in the chemical process
involved in glauconitization of mud,
sandy mud and coarse grain sands
(Fig. 10).
According to Odin and Dodson
(1982), one can consider that the
progress of the glauconitization reac-
tion is controlled by the diusion of
K+ ions in the solution from the
sedimentsea-water interface towards
the glaucony grain. The ux of K+
ions can be correctly depicted by the
equation from Holchella and Baneld
(1995):
101
The glauconiteFe-illiteFe-smectite problem A. Meunier and A. El Albani
.............................................................................................................................................................
Fig. 9 Schematic representation of the formation of green materials in a clay-rich
marine sandstone where organic debris are present (black area). Potassium diuses
from sea-water through the sedimentsea-water interface while Fe2+ ions diuse
inside the reductive microenvironment centred on the organic debris.
dq cq T Ci  Ce A
f 1
dt gl
where dq/dt is the ux (f) of species q
per time t; b the geometric constant
taking into account the porosity or
tortuosity; cq the constant that scales
the radius of species q; T the absolute
temperature; Ci and Ce the concen-
tration of species q in the internal
(outer surfaces of glauconite parti-
cles) and external (pore water) parts
of the system, respectively; A the
eective pore area; g the viscosity;
and l is the average length of diu-
sion paths.
Let us take an example: the glaucon-
itization of a given sediment, for
instance a coarse grain sand. The eective
pore area and the pore geometry do not
change much during the whole process.
We can approximate that the b and A
parameters are roughly constant.
Because the glauconitization process
occurs near the sea-watersediment
interface, it can be considered as iso-
thermal, thus T is constant. Isothermal
and iso-saline conditions mean that the
viscosity of sea-water (g) does not
change. The driving force of the diu-
sion is the concentration dierence
Ci ) Ce. This parameter can be consid-
ered as constant because the sea-water
reservoir is innite and the concentra-
tion of the element q at the glaucony
grain is xed by the physico-chemical
102
conditions at surface of the growing
mineral. These considerations allow us
to reduce Eq. (1) to:
dq 1 hundred thousands to 1 Myr. From a
f K
dt l
where K is a constant.
Equation (2) shows that the ux of
species q per time t varies proportion-
ally to the inverse of the average
length of diusion paths. The thick-
ness of the sediment aected by the
glauconitization process depending on
the mud/sand ratio (Odin and
Dodson, 1982) means that there is a
critical value for l (l*). When too long,
the diusion pathways reduce the
ux to a critical value (f*) which
is inecient for the growth of the
glaucony grain under consideration.
Inecient means that the incor-
poration and liberation rates of
the ion species at the surface of
glauconite crystals are equivalent.
Consequently, the glauconitization in
that given microsystem stops. It may
continue in another microsystem for
which l has not reached l*. This
explains the dierent age of grain
populations observed by Smith et al.
(1998).
Why glauconitization may stop
before completion? Thompson and
Hower (1975) have shown that the
per cent of expandable layers in glau-
Terra Nova, Vol 19, No. 2, 95104
cony is inversely related to the amount
of K ions in the crystal structure. The
amount of the diusing ion can be
obtained by integrating the ux f for a
time t. If there is no modication of
the sediment texture during the glau-
conitization process, the diusion
should be active until l* is reached.
Then, the process stops at a time t*
(value of t for f*). The glauconitiza-
tion process goes to completion as it is
in the case of the Gulf of Guinea
(Fig. 6) described by Odin and Dod-
son (1982). However, the process may
stop before completion if the ux
decreases. Any modication of the
porosity during the early diagenetic
stage in cemented sandstones changes
the composition of the glaucony
(Strickler and Ferrell, 1990). Conse-
quently, two phenomena may change
the ux: (1) increasing l* by addition
of sediments (the interface with
sea-water progresses upward), (2)
interruption of the diusion paths
due to compaction or cementation.
According to Odin and Dodson
(1982), the formation of a glaucony
grain having more than 8% of K2O
(highly evolved stage) needs several
2 chemical point of view, this means
that the conditions at the micro-envi-
ronment scale remain stable for those
long periods of time. This is hardly
understandable. Single-grain
40
Ar39Ar analyses reveal that the
glaucony grains in a given sediment
have not been formed simultaneously
(Smith et al., 1998). The glaucony
populations from Cenomanian, Bar-
tonian and Burdigalian sediments
exhibit a wide range of ages which
suggests that glaucony has been
formed in several genetic steps during
a long period of time of up to 5 Myr.
Conclusion
In spite of unavoidable uncertainties
due to Fe-rich nano-inclusions which
could be intercalated between the
layers, the illite and glauconite solid
solution compositions undoubtedly
are extended towards Fe- or Al-rich
end-members, respectively. The distri-
bution of Fe ions in the octahedral
sheets of illite and glauconite has been
investigated through infrared spectr-
oscopy studies and Monte Carlo
simulations (Cuadros et al., 1999;
Sainz-Diaz et al., 2003a,b).
 2006 Blackwell Publishing Ltd
Terra Nova, Vol 19, No. 2, 95104
.............................................................................................................................................................
Fig. 10 Schematic representation of the diusion pathways in dierent sediments: (a)
mud; (b) sandy mud; (c) sand. (d) Relation between the ux of species q (f dq/dt)
with the average length of diusion paths (l). l* and f*: critical value of l and f,
respectively (see text for explanation).
From a mineralogical point of view,
the analyses of the published data
suggest that a continuous solid solution
exists between the FeAl smectite, Fe-
illite and glauconite compositional
end-members. On the contrary, non-
tronite and Fe-montmorillonite com-
position elds are clearly separated
from those of glauconite. Whatever
their composition, the formation of
these minerals is a response to the
change of chemical conditions when
sediments interact with sea-water or
hypersaline solutions. The quickest
response is the overgrowth of FeAl
smectites on detrital clays. When
reductive microsystems are formed in
the unconsolidated sediments around
organic debris, Al-bearing (glauconite,
Fe-illite) or Al-depleted (Fe-montmo-
rillonite, nontronite) species begin to
form according to the sediment compo-
sition. Nucleation and crystal growth
are controlled by chemical diusion of
K+ and Fe2+ ions. If not interrupted,
the diusion process is active until
reaction completion is reached, i.e.
formation of the stable phase (Fe-illite
or glauconite) or mineral assemblage
(berthierinenontronite). Intermediate
steps are observed as mixed-layer min-
erals when the diusion process is
interrupted because of sedimentation
rate, compaction or cementation.
 2006 Blackwell Publishing Ltd
A. Meunier and A. El Albani The glauconiteFe-illiteFe-smectite problem
The mechanism described above
can be activated in sediments what-
ever their depositional environment.
Green minerals have been observed
from coastal to deep sea conditions
and from hypersaline to more diluted
waters. Consequently, these minerals,
and particularly glauconies are not as
good palaeoenvironmental indicators
as commonly thought (Huggett and
Gale, 1997). They can form during
long periods of time (several million
years) as attested by the wide range of
single-grain ages.
Acknowledgements
This study has been supported by the
UMR 6532 CNRS and Alexander von
Humboldt Foundation. The authors
warmly thank the scientic editor, Dr Fritz
and two anonymous referees for their
constructive remarks.
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Received 30 November 2005; revised version
accepted 18 October 2006
 2006 Blackwell Publishing Ltd