spe515-03 1st pgs page 49

The Geological Society of America

Special Paper 515
2015

Authigenic clay minerals in lacustrine mudstones

Daniel M. Deocampo*
Department of Geosciences, Georgia State University, 24 Peachtree Center Ave NE, Atlanta, Georgia 30303, USA

ABSTRACT

Substantial amounts of authigenic clay minerals can accumulate in terrestrial

mudstones where the following conditions are met: surface or pore waters are alka-
line, aqueous silica activity is high, at least some dissolved magnesium (Mg) is pres-
ent, and detrital input is relatively low. Availability of Al- or Fe-rich detrital clays
likely leads to Mg-rich smectite formation, whereas sepiolite or kerolite is favored in
environments with no detrital substrates. Surface waters of the Ngorongoro Crater,
Tanzania, provide a good example of alteration of incoming detrital clay minerals into
authigenic sediments with strong partitioning of Mg into silicate rather than carbon-
ate phases. Quaternary deposits of Olduvai Gorge (Tanzania) and the Olorgesailie
Basin (Kenya) provide end members for comparing processes in highly saline and
alkaline settings (Olduvai) versus those in diatomaceous fresher water environments
(Olorgesailie). Authigenic clays from around the world suggest that illitization and
octahedral alterations are decoupled, and therefore indicative of different process-
es, emphasizing the need to supplement basal layer X-ray diffraction analyses with
analyses of hkl reflections and geochemistry of purified phases. In general, authigenic
clay minerals are more common in underfilled lake basins, usually associated with
evaporitic basins with siliceous input from volcaniclastics or hydrothermal discharge.

INTRODUCTION mudstones. The thermodynamic stability of most clay minerals

Clay minerals belong to the phyllosilicate group of crystal-
line silicates. They generally have a very fine grain size, rarely
greater than 1 or 2 µm. The clay size fraction (<2.0 µm) com-
monly contains more than one phase, which often includes clay
minerals, but also may include non-clay minerals such as quartz,
carbonates, and others (Moore and Reynolds, 1997). Clay miner-
als are generally associated with Earth surface processes (e.g.,
soil formation, sedimentation), or relatively shallow processes
in the upper crust of the Earth (e.g., hydrothermal alteration,
sedimentary diagenesis; Meunier, 2005). They are therefore
important components of many sediments, including continental
generally limits their environments of formation to near-surface
environments, although some clay minerals may precipitate in
contact with igneous minerals in postcrystallization environ-
ments (Manuella et al., 2012). Because of the relatively low
thermal stability of clay minerals formed at the Earth’s surface,
transformations associated with burial diagenesis have been used
as important indicators of postdepositional processes, including
those associated with thermal maturation of petroleum hydrocar-
bons (Elliott and Haynes, 2002; Stroker et al., 2013).
The clay mineralogy of terrestrial sedimentary environments
differs from that of marine sediments in several key respects.
The sediment sources are generally very close, so clay mineral

*deocampo@gsu.edu

Deocampo, D.M., 2015, Authigenic clay minerals in lacustrine mudstones, in Larsen, D., Egenhoff, S.O, and Fishman, N.S., eds., Paying Attention to Mudrocks:
Priceless!: Geological Society of America Special Paper 515, p. 49–64, doi:10.1130/2015.2515(03). For permission to copy, contact editing@geosociety.org. ©
2015 The Geological Society of America. All rights reserved.

49

50 Deocampo
assemblages in terrestrial basins typically closely reflect the min-
eralogy of proximal sediment sources. Whereas the geochemis-
try of marine sedimentary pore waters is dominated by seawater
(except for marine hydrothermal systems), the geochemistry of
terrestrial surface water and groundwater is much more diverse.
Particularly in evaporative systems, water chemistry differences
in sedimentary systems can have major implications for the pri-
mary depositional and early diagenetic mineral assemblages
(Deocampo and Jones, 2014).
The importance of basic identification of detrital clays in
lake sediments is well accepted for the purpose of reconstructing
sedimentary provenance in basins where detrital clay mineralogy
varies between watershed inputs. For example, Yuretich and Ervin
(2002) showed the importance of the geology and weathering
regimes of catchments contributing to Lake Malawi (southeastern
Africa). In the north area of the lake, intense weathering delivers
kaolinitic clays to the lake, whereas in the south the climate is
more arid, so incoming stream sediments are richer in smectites.
These lateral variations in input are more significant in large lake
systems fed by multiple geological terrains or climate zones.
AUTHIGENIC CLAY MINERALS IN
LAKE SEDIMENTS
In many lake basins, authigenic clay minerals and other sili-
cates represent a significant component of the sediment, and in a
few cases they dominate the assemblage. In Pliocene deposits of
paleolake Olduvai, northern Tanzania, most of the basin-center
deposits are authigenic precipitates or alteration products (Hay,
1976; Hover and Ashley, 2003; Deocampo et al., 2009; Ashley
et al., 2014). In many other basins, authigenic silicates are major
sediment components, at least for certain stratigraphic intervals,
such as the Pliocene–Pleistocene Lake Tecopa beds (California,
USA; Starkey and Blackmon, 1979; Larsen, 2008), the Miocene
Barstow Formation (California; Sheppard and Gude, 1969; Park,
1995), the Eocene Green River Formation (western USA; Brad-
ley and Fahey, 1962; Dyni, 1976), the Pleistocene Magadi Beds
and Humbu Formation (southern Kenya; Eugster, 1967; Deo-
campo, 2004a), and others.
The importance of magnesium (Mg) silicates was recog-
nized in the work of Garrels and Mackenzie (1967), who found
that the chemistry of saline waters of the Great Basin (western
USA) could be explained through evaporation of typical spring
waters of the area. Key to the geochemical evolution of these
waters was the effect of mineral precipitation on the chemistry
of residual fluids, thus leading to the idea of the chemical divide,
which effectively eliminates the ion that is lower in concentra-
tion at the time that supersaturation occurs (Hardie and Eugster,
1970). Garrels and Mackenzie (1967) relied on sepiolite to sim-
ulate the effect of Mg silicate precipitation. The purity of such
silicates, however, depends in large part on the amount of detrital
material in contact with the saline alkaline fluids. Abundant dioc-
tahedral smectite in ultrafine detritus results in the interstratifi-
cation of Mg-rich layers in the clay, thought to be kerolitic in
spe515-03 1st pgs page 50
composition (Jones, 1986; Banfield et al., 1991; Pickering and
Deocampo, 2013; Pickering, 2014). Therefore, spring-fed pond
sediments such as those of the Amargosa Desert (Nevada, USA)
or the Amboseli wetlands (Kenya) contain purer kerolitic smec-
tite, or in places sepiolite (Stoessell and Hay, 1978; Hay and
Stoessell, 1984; Hay et al., 1995; Deocampo, 2004a). In contrast,
lacustrine clays such as at Great Salt Lake (paleolake Bonneville;
Utah, USA), Lake Chad (Central Africa), or paleolake Olduvai
(Gac et al., 1977; Jones and Spencer, 1999; Deocampo et al.,
2009; Jones et al., 2009) are generally dominated by 2:1 illitic or
smectitic clays.
Well-known mudstones rich in trioctahedral (Mg rich) clay
minerals are also found in many of the Cenozoic basins of France,
Spain, and northern Africa (Martin de Vidales et al., 1991; Calvo
et al., 1999; Chahi et al., 1999; Rhouta et al., 2008). Other miner-
als commonly coexist with the Mg silicate phase; for example,
in an examination of the KM-3 core of Searles Lake (California,
USA), Hay et al. (1991) showed that incoming detrital Al-rich
clay and kaolinite were consumed in the reactions that produced
an authigenic silicate assemblage containing Fe-rich illite, Mg-
rich smectite, K-feldspar, and analcime.
All of these basins accumulating authigenic silicates have
several things in common: (1) high aqueous silica activity due to
weathering volcaniclastics and/or hydrothermal input; (2) alkaline
waters due to weathering of basic rocks and evaporative concen-
tration; and (3) significant time intervals of relatively low detrital
sediment input. In terrestrial basins, authigenic silicates, including
clay minerals, are therefore most likely to accumulate in lacus-
trine mudstones, because these tend to be environments in which
there is the potential for siliceous, alkaline waters with relatively
small proportions of detrital input. These conditions have also
been recognized in some pedogenic and paludal environments
(Stoessell and Hay, 1978; Khoury et al., 1982; Chahi, 1992; Deo-
campo, 2005; Furquim et al., 2010), although such environments
are not as extensively represented in the rock record.
Authigenic clay minerals are only one family of authigenic
silicate minerals that may form in evaporative, siliceous basins.
It is generally thought that clay minerals, along with commonly
associated opaline silica, zeolites, and feldspars, represent meta-
stable phases that are replaced over geological time scales by
more stable quartz, feldspars, and mica minerals (Hay, 1966;
Dibble and Tiller, 1981; Jones, 1986; Larsen and Crossey, 2000;
Larsen, 2008). This tendency is encouraged by thermal diagen-
esis, so older deposits tend to lose their primary authigenic clay
mineral signatures as diagenetic fluids interact with the sedi-
ments, particularly with significant burial. It is not clear how long
the authigenic clay mineral signature can be retained, but clearly
the thermal history is a critical parameter. For example, primary
lacustrine authigenic clay minerals (trioctahedral smectites indi-
cating saline, alkaline conditions) have been well characterized in
the Mesozoic deposits of the East Berlin Formation of the Hart-
ford Basin, and other basins of the Newark Supergroup (eastern
USA) (April, 1981), despite evidence for diagenetic metasoma-
tism involving Na-rich fluids (van de Kamp and Leake, 1996).

Authigenic clay minerals in lacustrine mudstones
In addition to phase changes caused by burial diagenesis, clay
minerals are often components of assemblages with variations due
to depositional conditions. For example, in Jurassic deposits of the
Morrison Formation (western USA), a large saline and alkaline
paleolake accumulated a rich assemblage with numerous authi-
genic and diagenetic silicates (Bell, 1986; Owen et al., 1989).
Turner and Fishman (1991) showed that this paleolake T’oo’dichi’
(Colorado Plateau, USA) produced a zoned authigenic mineral
assemblage that varied toward the basin center in the order smec-
tite → clinoptilolite → analcime ± K-feldspar → albite. Although
albite is commonly an indicator of advanced burial diagenesis, in
this case the assemblages reflect low-temperature processes influ-
enced by surface and pore water compositions.
In the siliceous lacustrine basins most likely to produce
authigenic clay minerals, transported weathering products com-
monly include kaolinite or halloysite in the most intense hydro-
lytic settings (Yuretich and Ervin, 2002; Deocampo, 2004a;
Jackson et al., 2010). In regions with less intense weathering,
smectites and illites are common, depending on the local parent
material and weathering regime (Velde and Meunier, 2008). With
little or no chemical weathering, the constituent detrital clay min-
eral assemblage is entirely dependent on country-rock lithology.
Weathering in upland soils not only releases these clays through
the hydrolysis of silicate minerals, but also leads to the acquisi-
tion of alkalinity and dissolved silica in surface waters (Drever,
1997). In evaporative or hydrologically restricted settings, water
is evaporatively concentrated as it moves basinward, with dis-
solved solid concentrations increasing potentially by many
orders of magnitude, depending on the basin hydrology (Eugster
and Hardie, 1978; Deocampo and Jones, 2014).
CHARACTERIZATION OF AUTHIGENIC
CLAY MINERALS
Characterizing the mineralogy and geochemistry of clay
minerals in mudstones has three main aspects: (1) identification
of the mineral family (e.g., smectite, illite, kaolinite), (2) char-
acterization of octahedral crystallography of the clay mineral,
and (3) chemical analysis and assignment of structural formulae,
if possible. Determination of the basic mineral family relies on
the traditional oriented X-ray diffraction (XRD) analysis, usu-
ally conducted from 2° to 32° 2θ (if using Cu radiation) with
the clay sample deposited on a glass slide or similar orienting
substrate (Moore and Reynolds, 1997). Such orientation of the
sample enhances diffraction X-rays due to interaction with the
basal layers of the sheet silicate. This step can be difficult in sedi-
ments with abundant glass shards or diatom fragments, which act
to disrupt sample orientation (Deocampo et al., 2010). Follow-
ing initial analysis in the air-dried condition, a number of subse-
quent treatments and analyses can be conducted to diagnostically
test the behavior of the clay minerals in order to identify them
(Moore and Reynolds, 1997).
If the clay minerals are detrital, then generally the first step
is sufficient in allowing initial interpretation of the provenance,
spe515-03 1st pgs page 51
51
transport history, and perhaps climatological inferences regard-
ing weathering regimes in the catchment areas. If the presence
of authigenic clay minerals is suspected, however, further anal-
ysis must be carried out to test for octahedral Mg enrichment,
the most common sort of clay mineral neoformation process in
lacustrine basins (Jones, 1986). Distinguishing between detrital
versus authigenic clay minerals can be problematic; field obser-
vations of depositional context can be combined with analytical
methods such as high-resolution transmission electron micros-
copy (HRTEM) to look for morphological indications of trans-
port, and other contextual data (Hover and Ashley, 2003; Larsen,
2008; Deocampo et al., 2009).
To test for octahedral Mg enrichment, it is necessary to
obtain XRD observations of the octahedral layer; these reflec-
tions are relatively weak, and are absent from oriented XRD
analyses. To obtain an XRD measurement attributable to the
octahedral sheet, clays must be randomly oriented (or better,
preferentially oriented with the basal layer planes perpendicular
to the XRD stage), to obtain hkl reflections (Moore and Reyn-
olds, 1997). Such peaks in the region 58°–62° 2θ (corresponding
to octahedral layer d-spacings of ~1.480–1.525 Å) can be attrib-
uted to the octahedral layer (Hay and Kyser, 2001). This peak,
crystallographically labeled the 060 peak, is strongly related to
the Mg content in authigenic clay minerals (Fig. 1). Furthermore,
it has also been shown that multiple peaks, representing multi-
ple authigenic phases of varying composition, may be present
in such materials, allowing quantitative assessment of variable
octahedral compositions (Deocampo et al., 2009).
Several different approaches may be used for geochemi-
cal analyses of purified clay mineral extracts. These include
Figure 1. Relationship between octahedral magnesium
content of <0.1 µm clays (atoms per half formula unit,
determined by electron microprobe) and d-spacing in-
dicated by 060 peak measurement (determined by X-
ray diffraction), from Deocampo (2004a). Black circles
are samples from Ngorongoro Crater (Deocampo,
2004a), plus signs are from Olduvai Gorge (Hay and
Kyser, 2001).

52 Deocampo
acid digestion followed by inductively coupled plasma analysis
(Jones and Spencer, 1999), fusion followed by quantitative X-ray
fluorescence analysis (Deocampo et al., 2002), electron micro-
probe analysis of dehydrated extracts (Deocampo et al., 2009),
and HRTEM analysis (Dong et al., 2009). These and other meth-
ods were outlined in Amonette (1994). It is crucial to recognize
that different spatial scales of analysis may yield different geo-
chemical results, and these may or may not be representative of
average phase compositions within the sample. Bulk analysis of
purified clays provides the average chemical composition. In the
ideal case the clays are monomineralic, but this is usually not the
case. For clay mineral mixtures, phases or end members need
to be identified and characterized by either HRTEM analyses,
which can approach the crystallite scale, as well as distinguishing
crystallographic data. Once phase compositions and structural
formulae are determined for identified phases, the octahedral
composition can be quantified in a number of different ways. As
discussed in the following, one approach is to employ the octa-
hedral cation index, which is the molar ratio of Mg to the sum of
Al + Fe (Deocampo, 2004a). This provides a convenient index
to compare the degree of trioctahedral domain development in
authigenic clays. Such an approach assumes that the geochemi-
cal compositions can be accurately apportioned between multiple
phases in the sample, if present.
CLAY MINERAL THERMODYNAMICS
AND KINETICS
Phyllosilicate minerals can be supersaturated at surprisingly
low levels of total dissolved solids. For example, Johnson and
Eisenreich (1979) noted that in Lake Superior (USA-Canada)
silica flux to the sediment cannot be accounted for by diatom
flux alone, and inferred some role for authigenic clay minerals
(presumably montmorillonite). Authigenic clay minerals in such
settings are unlikely to be easily detected, however, because they
are a minor component of the sediment compared to biogenic and
detrital components. In waters with higher dissolved solid con-
centrations, such as in hydrologically closed or restricted basins,
authigenic phases may be a much more significant fraction of
the sediment. As evaporative concentration proceeds, calcium
carbonate is typically the first mineral to reach supersaturation
(Hardie and Eugster, 1970; Deocampo and Jones, 2014). Even if
Mg carbonates reach supersaturation, they are not likely to pre-
cipitate, although some well-known cases of primary dolomite
are noted (Deocampo, 2009), because of the kinetic barriers to
dehydration of the hydration sphere surrounding Mg2+ required
for Mg-bearing carbonates to precipitate. Once silicates precipi-
tate, therefore, they are often precipitating in an Mg-enriched
aqueous environment, leading to Mg enrichment of the silicate
phase, or even pure Mg silicate in the absence of detrital sub-
strates (Jones, 1986).
The thermodynamics of authigenic clay minerals have long
been difficult to model, mostly because of the poorly known fun-
damental thermodynamic properties of the materials. Chemical
spe515-03 1st pgs page 52
and crystallographic variability in such clay minerals also may
render thermodynamic interpretations problematic because the
thermodynamic behavior is inconsistent. It is useful to consider
the thermodynamics of better understood phases such as sepio-
lite [Mg4Si6O15(OH)2•6H2O] or kerolite [also known as disor-
dered talc; Mg3Si4O10(OH)2•H2O]. Even though these materials
are not necessarily the specific phases precipitating in particular
lacustrine or other environments, because they are hydrous Mg
silicates they may broadly represent the general behavior of such
authigenic clay minerals.
The fundamental control on precipitation of authigenic
clay minerals is supersaturation with respect to the mineral.
As an example, the saturation state of waters with respect to
sepiolite (sep) can be described (following Stoessell, 1988) for
Mg2Si3O7.5(OH)•3H2O as
Log IAPsep =
2 log (αMg2+) (αH+)–2 +3 log [aSiO ] + 5.5 log (αH O), (1)
2(aq) 2
where IAP is ion activity product. Examination of the
equation shows the importance not only of magnesium and
silica content, but of the pH of the solution, which is controlled
by many complex factors such as alkalinity derived from rock
weathering and biological activity (Drever, 1997). Figure 2
shows chemical analyses of modern environments in the stabil-
ity diagram of the system MgO-SiO2-H2O (field boundaries fol-
low Christ et al., 1973; Jones, 1986; Stoessell, 1988). The sta-
bility diagram shows that the principal controls on precipitation
of Mg silicates are magnesium and silica activities, along with
pH. It is less obvious, however, that pCO is also a crucial con-
2
trol, because of the strong effect that pCO has on pH, particu-
2
larly in waters that are not at equilibrium with atmospheric CO2
(Deocampo and Ashley, 1999; Deocampo, 2005). In cases such
as in sublacustrine pore waters or in marshes, microbial respira-
tion can increase pCO by orders of magnitude, resulting in pH
2
changes of 2 or more pH units. This has a significant impact
on the solubility of not only Mg silicates, but on all acid-base
mineral systems. Substantial input of CO2-charged hydrother-
mal waters could also potentially have a large effect on solution
pH, depending on the rapidity of degassing.
In basin-wide studies of evaporative basins, assuming that
silica levels are >~15 mg/L SiO2, it seems that pH variation has
the strongest impact on whether Mg silicates precipitate. For
example, most of the variability in the Eyasi and Ngorongoro
Basins (Tanzania) is in the vertical axis attributable to pH (Fig. 2;
Deocampo, 2005). The same was found in studies of the alkaline
Pantanal wetlands of Brazil, where Mg-rich smectite is precipi-
tating today (Barbiero et al., 2002; 2007; Furquim et al., 2008).
Even in highly evaporatively concentrated brines in which evapo-
rite mineral precipitation has been substantial, such as the Great
Salt Lake or Lake Magadi, waters plot near enough to the stability
field boundary that the pH effect of biotic CO2 is great enough to
cause Mg silicate stability to drop. Tosca et al. (2011) presented
experimental evidence reinforcing the importance of pH control
 spe515-03 1st pgs page 53

Authigenic clay minerals in lacustrine mudstones 53

on Mg silicate precipitation, being of even greater importance 2002, 2010; Deocampo and Tactikos, 2010). Complementary but
than Mg2+ and SiO2 concentrations. Bristow et al. (2012) showed independent data would be required to discern the cause.
the importance of carbonate systematics for authigenic silicates The precise mechanisms of magnesium and silica precipi-
(and vice versa) in the Green River Formation, with implications tation are not well understood. It is clear, however, that kinetic
for Mg partitioning between carbonates and silicates. conditions are important determinants of what phases form.
The effect of pCO on Mg silicate supersaturation can be mod- Jones (1986) proposed topotactic (template like) precipitation of
2
eled by calculating the pH resulting from aqueous pCO greater
2
than atmospheric concentration. As shown in Figure 3, lake-
margin mudflat waters from Ngorongoro Crater are supersatu-
rated with respect to Mg silicates. Model calculations predict that
increased CO2 levels would result in dissolution of Mg silicates
(Deocampo, 2005). This has tremendous implications for under-
standing the diagenesis of Mg silicates. In mudstones rich in Mg
silicates, regions or stratigraphic intervals where Mg silicate con-
tent drops could have occurred due to a lack of primary precipi-
tation, or biogenic CO2-induced dissolution (Deocampo et al.,

Figure 2. Mg silicate stability of selected lake waters, and basin-scale

variability in Mg silicate stability in the Lake Eyasi, Ngorongoro Cra-
ter, Lake Naivasha, Great Salt Lake, Lake Albert, Lake Michigan,
and Pantanal basin. Eyasi and Ngorongoro data are from Deocam-
po (2005); Pantanal data are from Barbiero et al. (2002); Great Salt
Lake data are from Spencer et al. (1985); Lake Abert data are from
Phillips and Van Denburgh (1971); Lake Michigan data are from the
U.S. Geological Survey National Water Information System, https://
catalog.data.gov/dataset/national-water-information-system-nwis;
Lake Naivasha data are from Kilham (1971); Lake Magadi data are
from Jones et al. (1977). The Eyasi, Ngorongoro, and Pantanal data
show the importance of pH variation, which is a major source of vari-
ability in Mg silicate stability, seen in the y-axis. Speciation was cal-
culated using the PHREEQC program (Parkhurst and Appelo, 1999).
Figure 3. Mg silicate stability in Ngorongoro Crater lake-margin
mudflat waters (from Deocampo, 2005). Actual values from the
field are the leftmost values in both plots. Model calculations using
the PHREEQC program (Parkhurst and Appelo, 1999) show the ef-
fects of increased pCO produced by microbial respiration (Langmuir,
2
1997; Deocampo and Ashley, 1999). Number labels in A show model
log pCO values; labels in B show model pH values. IAP—ion activity
2
product; KT—equilibrium constant for the temperature of the water.

54 Deocampo
kerolite as interstratifications in smectite as Mg sorbs to inter-
layer sites following desorption of Ca from largely dioctahedral
(Al or Fe rich) clay minerals (Eberl et al., 1982). Other slightly
modified models emerged from studies of the alkaline volcanic
lakes of the Pacific Northwest, in which not kerolite, but rather
Mg-rich smectite precipitated (Banfield et al., 1991; Colak
et al., 2000). Examining Pleistocene lacustrine deposits of the
Olduvai Gorge, Hover and Ashley (2003) proposed a dissolution-
precipitation reaction that replaced end-member dioctahedral
smectite (montmorillonite) with end-member trioctahedral smec-
tite (stevensite or saponite). In Deocampo et al. (2009) both solid
state and dissolution-precipitation reactions were demonstrated
for the Olduvai deposits (Fig. 4), and the first unequivocal evi-
dence of truly intermediate dioctahedral or trioctahedral occu-
pancy in a 2:1 phyllosilicate at the crystallite scale, rather than
simply mixtures of the end members, was provided.
Based on studies of clay mineral alteration in lacustrine
environments, it appears that two main groups of reactions can
occur: (1) the smectite to illite transition, which in geologically
young deposits has occurred in a low-temperature setting, unlike
thermally induced illitization of smectite associated with burial
diagenesis (Elliott and Aronson, 1987); and (2) changes in the
proportion of dominant cations in the octahedral sheet of the clay
minerals. The two are related, as octahedral changes can affect
layer charge and thus illitization. Low-temperature illitization
is known to occur in a number of different ways in lacustrine
settings. It is well known that repeated wetting and drying can
enhance potassium fixation, through either K increase due to
evaporation, or progressive reduction of octahedral Fe(III) to
Fe(II), hence increasing the overall layer change and the ten-
Figure 4. High-resolution transmission electron microscopy image of
lattice fringe from <0.1 µm clay sample from Olduvai Gorge (from
Deocampo et al., 2009). The arrow indicates a region with a lateral
transition from illite (I) to smectite (S) in the same layer, suggesting
a solid-state reaction mechanism for this example of low-temperature
illitization of smectite, decoupled from octahedral transformations.
spe515-03 1st pgs page 54
dency to fix K (Eberl et al., 1986, 1993; Huggett and Cuadros,
2005). Abundance of authigenic illite in more perennially wet
conditions, for example lake bottom muds, also suggests that
illitization can occur simply due to interaction with K-rich brines
(Singer and Stoffers, 1980; Hay and Kyser, 2001; Hover and
Ashley, 2003; Deocampo, 2004a). Detailed studies of clays at
Olduvai Gorge, with XRD, HRTEM, Fourier transform infra-
red spectroscopy (FTIR), electron microprobe, and NEWMOD
(Yuan and Bish, 2010) numerical models have shown that the
process of layer charge increase (eventually leading to illitiza-
tion) may be decoupled from the K fixation (Fig. 4; Deocampo et
al., 2009). Most of the layer charge increases are due to octahe-
dral layer changes attributable to interaction with saline and alka-
line fluids. This further emphasizes the point that, for purposes of
reconstructing paleosalinity and paleoalkalinity of lake waters, it
is crucial to understand octahedral compositions beyond the sim-
ple illite versus smectite identification. Plotting the octahedral
cation composition shows the variability to be expected among
detrital and authigenic clays (Fig. 5).
Acid saline lakes are exceptional cases to which these
models of clay mineral authigenesis do not generally apply.
Although they are not widespread on the Earth’s surface, they
dominate certain areas of southern and western Australia, and
they are of particular interest because of potential analogues for
Martian paleoenvironments (Bowen and Benison, 2009). These
lakes often form in settings where the marine hydrochemical
signal dominates (Bodine and Jones, 1986), and surface waters
are isolated from the buffering effects of basic bedrock. Evapo-
rative concentration and mineral precipitation in such an envi-
ronment effectively eliminates alkalinity, thus producing sulfo-
chloride brines with pH values as low as 2 or even lower (Jones
et al., 1994; Deocampo and Jones, 2014). Clay mineral authi-
genesis in these lakes is dominated by Al-rich phases that are
stable in acidic conditions, such as kaolinite or halloysite; Mg-
or Fe-bearing clay minerals found in deposits of these lakes are
generally thought to be detrital input phases, perhaps with the
expected dissolution inhibited by salinity-related kinetic factors
(Story et al., 2010).
NGORONGORO CRATER: A MODERN EXAMPLE
Several modern lake systems are instructive about the pro-
cesses leading to deposition of authigenic clay minerals in lacus-
trine mudstones. The Ngorongoro Crater (northern Tanzania),
is an excellent example because of its small basin size, more or
less uniform catchment geology, and somewhat uniform climate.
The internally drained caldera collapsed ~2 m.y. ago, creating
a small hydrologically closed basin within the Ngorongoro Vol-
canic Highland (Hay, 1976; Deocampo, 2004a). The catchment
for Ngorongoro Crater is dominated by trachytic volcanic and
volcaniclastic rocks, with minor basaltic components (Mollel
and Swisher, 2012). The nearby carbonatitic volcano Ol Doinyo
Lengai episodically delivers highly alkaline and weatherable
airfall volcaniclastics to the entire region, although the direct
 spe515-03 1st pgs page 55

Authigenic clay minerals in lacustrine mudstones 55

contribution of these volcaniclastics is a minor component of the
overall sediment load (Hay, 1976; Dawson et al., 1994).
Soils of the region are variable, but sloped surfaces in the
catchment are commonly what Anderson and Herlocker (1973)
referred to as ferruginous tropical soils; acidic conditions (soil
pH ~ 5.5), depleted base cations, low cation exchange capacity,
and variable clay content. It therefore is well classified as rang-
ing between inceptisols and ultisols (Soil Survey Staff, 1999).
Detrital clay contributing to the drainage is commonly composed
of either kaolinite or dioctahedral smectite (Al- or Fe-rich beidel-
lite or nontronite, respectively) (Deocampo, 2004a; Deocampo
et al., 2009).
The floor of Ngorongoro Crater hosts a diverse array of
African savannah environments, including acacia forests lining
inflowing streams, groundwater-supported forests, grassland,
marshes, and the terminal saline Lake Makat. In a study of sur-
face and spring waters sampled from 1995 to 1999, total dis-
solved solids in Ngorongoro waters ranged from 130 to nearly
10,000 mg/L, with the freshest waters found in inflowing streams
and the most saline waters found in Lake Makat (Deocampo,
2004b). Examination of the proportion of cations shows the pro-
gressive loss of calcium and magnesium (Fig. 6). In the most
dilute waters, calcium and magnesium dominate the cations, but
as the waters become progressively evaporatively concentrated,
sodium and potassium come to dominate. This reflects the pro-
gressive loss of the alkaline earths to mineral precipitation (Deo-
campo and Jones, 2014). Although the fate of calcium is easily
established as calcite, which is abundant on the land surface
throughout the crater floor, the fate of magnesium is not as clear,
as no Mg-bearing carbonates have been identified.
Examination of clay minerals shows that, although the
incoming detrital material is kaolinitic or dioctahedral smec-
tite, clay minerals found on the basin floor include varieties rich
in magnesium. Such comparisons are best made on submicron

Figure 5. Plot of major octahedral cation compositions (OCI—octahedral cation index), reported as atoms per half
formula unit; see legend for abbreviations. NG, NA, OL, and AM data are from Deocampo (2004a); GR data are from
Dyni (1976); EB (East Berlin Formation) data are from April (1981). Green and brown claystone analyses are elec-
tron microprobe analyses of <0.1 µm mixed illite and smectite clays from the Miocene Barstow Formation, showing
typical octahedral variability of chemical compositions in lacustrine authigenic clay-rich mudstones (Deocampo and
Pedone, 2004).

56 Deocampo
fractions of clays separated from bulk material to obtain the finest
fraction. This eliminates most of the detrital or biogenic mate-
rial present, and isolates the fraction with the most surface area
and near-colloidal behavior, increasing the likelihood that they
more closely reflect the thermodynamic conditions at their time
of formation (McLean et al., 1972; Webster and Jones, 1994).
Although the most notorious contaminants in such sample prepa-
rations are fine-grained shards of volcanic glass or diatom frag-
ments (Deocampo et al., 2010), care should always be taken to test
for the presence of other common detrital materials. Ngorongoro
soil clays <0.2 µm prepared in this way and analyzed by elec-
tron microprobe were found to have ~0.7 wt% MgO, whereas
those in some wetlands and lake-margin mudflats of the crater
floor were as high as 15 wt% MgO (Deocampo, 2004a, 2005).
This showed that significant Mg enrichment occurred in the sili-
cate phases between catchment soils and the basin floor. These
results were broadly consistent with other previous comparisons
of detrital input and depositional silicate compositions in sev-
eral other modern basins, such as the saline alkaline Lake Abert
(Oregon) (Jones and Weir, 1983), the slightly saline but highly
alkaline Lake Turkana (Kenya) (Yuretich and Ervin, 2002), the
borate-rich saline Searles Lake (Hay et al., 1991), and others.
Studies in these evaporative systems around the world have con-
firmed the depositional models proposed by Millot (1954, 1964),
inspired by his observations of Mg enrichment in the clay frac-
tion toward the depocenter of Lake Chad. Although aspects of the
Millot model of Mg enrichment have been documented in basins
around the world, lateral zonations are not universally found, and
Figure 6. Cation concentration data from Ngorongoro Crater surface
waters, determined by inductively coupled plasma–atomic emission
spectroscopy (ICP-AES) on filtered and acidified samples (from Deo-
campo, 2004b). Dilute inflow has mixed cation composition, but with
progressive evaporative concentration, Ca and Mg are lost to mineral
precipitation. Ca is primarily taken up by carbonate phases, whereas
Mg is primarily taken up by silicates (Deocampo and Jones, 2014).
spe515-03 1st pgs page 56
mineral assemblage compositions can be profoundly affected by
complexities of kinetics and biota.
The crystallographic composition of clay minerals can be
estimated by translating the oxide chemical composition of these
clays into structural formulae assuming crystallographic struc-
tures (e.g., 2:1 tetrahedral to octahedral) based on XRD data
(Moore and Reynolds, 1997). This assumes relative phase purity,
although if phase abundance can be constrained by an indepen-
dent analytical method (e.g., FTIR or XRD), it is possible to pro-
portionally assign chemical compositions among more than one
phase (Deocampo et al., 2009). Plotting the octahedral composi-
tion shows significant Mg enrichment in the Ngorongoro clay
minerals (Fig. 7), even surpassing the Mg content in Great Salt
Lake clay minerals (Jones and Spencer, 1999).
ANCIENT MUDSTONE EXAMPLES
The complex depositional and diagenetic histories of sedi-
ments must be considered to assess the origins of authigenic clay
minerals and other silicates. The effects of burial diagenesis and
hydrothermal alteration can significantly change the mineral-
ogical and geochemical assemblage. For example, Larsen and
Crossey (2000) suggested that, in the Oligocene Creede Forma-
tion, lacustrine deposits derived from volcaniclastic weathering
retained an assemblage of primary depositional authigenic sili-
cates only in the youngest interval. Authigenic silicates, including
clay minerals, in most of the formation show the effects of hydro-
thermal events known to have occurred in the region (Barton
Figure 7. Comparison of octahedral layer Al and Mg
content in several modern clays. In general, detrital
sources are Al rich, whereas clays deposited under sa-
line, alkaline conditions are Mg enriched. Ngorongoro
data are from Deocampo (2005); Great Salt Lake data
are from Spencer (1982); Lake Chad data are from
Tardy et al. (1974); Amboseli data are from Hay et al.
(1995); Pantanal data are from Furquim et al. (2008).

Authigenic clay minerals in lacustrine mudstones
et al., 2000). In addition to field observations of how mineral
assemblages did not correlate with depositional environments, an
important indicator of advanced hydrothermal alteration was the
prominence of potassium feldspar, along with chlorite in the clay
mineral assemblage (Larsen and Crossey, 2000). Understanding
field relationships is therefore critical, as mineralogy alone is not
sufficient to interpret the genesis of mineral assemblages.
Two Quaternary basins in East Africa, the Olorgesailie and
Olduvai Basins, can serve as end members demonstrating some
of the patterns of authigenic clay mineral accumulation in lacus-
trine mudstones. Sediments of the Olorgesailie Formation range
in age from ca. 1.2 Ma to ca. 490 ka (Behrensmeyer et al., 2002;
Potts et al., 2004; Owen et al., 2008). The Olorgesailie Formation
is composed of diatomaceous silts and clays, some diatomite,
volcaniclastic sands and gravels, and tuff (Isaac, 1978; Shack-
leton, 1978; Owen and Renaut, 1981; Potts et al., 1999; Beh-
rensmeyer et al., 2002). The abundance of diatoms has allowed
a paleoenvironmental reconstruction of the basin based on the
environmental tolerances of found species (Owen et al., 2008,
2014). The diatoms show that the basin held lake or wetland envi-
ronments with largely freshwater conditions over much of its his-
tory, although some saline episodes are also noted. The presence
of biogenic amorphous silica alone in these deposits is a strong
indicator that the highly saline and alkaline conditions present in
much of the region were absent at Olorgesailie, at least for much
of its history (Deocampo and Ashley, 1999).
In contrast, mudstones from the early lacustrine phase of the
Olduvai Gorge, dating from ca. 2.0 Ma to ca. 1.8 Ma, record a
highly saline and alkaline lake history (Hay, 1976). Casts of trona
and gaylussite, a paucity of calcareous fossils and biogenic silica,
and indicators of strong geochemical gradients from freshwater
lake margin springs to evaporative mudflats, all point to highly
saline and alkaline conditions (Hay and Kyser, 2001; Deocampo
et al., 2002; Deocampo and Tactikos, 2010; Ashley et al., 2010).
In both basins, surface waters carried pedogenic clay miner-
als that originated in upland soils developed on volcanics and
volcaniclastics of the East African Rift. In the Olorgesailie Basin,
these were predominantly trachytic to basaltic volcanic sources,
including rift-margin basaltic flows and Mount Olorgesailie
(Owen et al., 2014). At Olduvai, most of the drainage originated
in trachytic to trachyandesitic volcanics of the Ngorongoro Vol-
canic Highland (Hay, 1976; Mollel and Swisher, 2012), with an
additional western source draining the quartzofeldspathic meta-
morphic rocks of the Serengeti highlands (Hay, 1976). In both
cases, detrital sources delivered Al- or Fe-rich pedogenic clays to
the basin. At Olduvai, this is confirmed by the presence of diocta-
hedral Al-rich and Fe-rich smectite (beidellite to nontronite) in the
volcaniclastic alluvial fan upslope from the paleolake (Hay and
Kyser, 2001; Hover and Ashley, 2003; Deocampo et al., 2009).
At Olorgesailie, paleostream valleys contain Al-rich dioctahe-
dral smectite (Deocampo et al., 2010). In both localities, mod-
ern soils contain dioctahedral smectite and kaolinite (Deocampo,
2004a; Deocampo et al., 2010). It is unclear whether kaolinite
was produced in Quaternary time and did not survive exposure to
spe515-03 1st pgs page 57
57
waters in the basin, or if weathering at that time was not intense
enough to produce pedogenic kaolinite. Paleosol studies in the
two basins have only yielded dioctahedral smectite (Ashley and
Driese, 2000; Deocampo et al., 2010); both of these, however,
were at low elevation in their respective basins, and so likely do
not reflect unaltered source contributions of detrital sediment.
In the two basins, once detrital clays were delivered to the
paleolake, they encountered surface waters of differing geochem-
istry. Both basins had high silica levels; this is clearly indicated
by the abundance of diatoms in the Olorgesailie sediment, and
by the abundance of authigenic silicates at Olduvai. In contrast
to Olorgesailie, however, the Olduvai paleolake waters were
never fresh enough to preserve biogenic amorphous silica in the
sediment, except for localized marshes surrounding freshwater
sources such as springs and streams (Deocampo and Ashley,
1999). Although the chemistry of both paleolakes varied consid-
erably through time, in general the Olduvai paleolake had much
greater salinity and alkalinity, with pH > 9.5 or 10 for much of its
history (Hay and Kyser, 2001). Detrital clays reached the Olduvai
paleolake and were immersed in a highly alkaline environment
rich in dissolved silica, likely containing some dissolved Mg.
With such high pH and silica, very little Mg is required to reach
supersaturation with respect to some Mg silicates (Stoessell,
1988). Moreover, if detrital incoming clay minerals held inter-
layer Ca, as is commonly the case in terrestrial environments, it
could rapidly exchange for both Na and Mg, potentially leading
to Mg silicate interstratifications, as proposed by Jones (1986). At
Olorgesailie, although waters were alkaline, they were not appar-
ently highly saline except for certain intervals, based on diatom
data (Owen et al., 2008). The abundance of authigenic Mg-rich
clays, and the degree of Mg-rich interstratification within those
clays, should therefore be much lower.
Comparing the octahedral cation chemistry of ultrafine
clays (<0.2 µm or <0.1 µm) of the two basins shows that the
Olorgesailie clays (members 1 and 7) plot mostly at the same
Al- and Fe-rich end of the ternary diagram as those from Oldu-
vai (beds I and II) deposited in fresher water (Deocampo et al.,
2009, 2010). The Olorgesailie clays show substantial Mg enrich-
ment (to 50 mol% Mg), but nowhere near the extent of the Oldu-
vai clays (Fig. 8).
The geochemistry of ultrafine clays is highly variable within
individual basins and within individual beds. Although several
stratigraphic units are represented in Figure 8, similar ranges
of geochemical variability can be found within discrete, fine-
grained and lithologically uniform stratigraphic horizons (Hay
and Kyser, 2001; Deocampo et al., 2002). For example, Figure
9 shows the molar ratio of Mg to Al in <0.2 µm clays across
~1.5 km of the eastern lake margin at Olduvai, all sampling the
~10-cm-thick basal claystone of lowermost bed II (Ashley and
Hay, 2002; Blumenschine et al., 2003). In this case, the lower
Mg content found in the eastern area was interpreted to have been
caused diagenetically by leaching beneath freshwater marshes
that developed in the east (Deocampo et al., 2002; Deocampo and
Tactikos, 2010). When lake water covered the entire lake margin,

58 Deocampo
Mg-rich smectites were deposited with more or less uniform
geochemistry across the lake margin; only with subsequent dif-
ferential diagenesis due to highly localized freshwater (and pCO -
2
induced pH suppression) was significant variability introduced.
Another example of within-unit variability in clay geochem-
istry is found in <0.1 µm clays of member 1 of the Olorgesailie
Formation (Deocampo et al., 2010). In this example, over ~4 km
of the basin, octahedral clay mineral composition is more or less
uniform within the upper member 1 paleosol, with the exception
of the farthest western samples. Those samples show some Mg
enrichment, though not to the extent of the Olduvai clays. Rather
than reflecting differential diagenesis, in Deocampo et al. (2010)
this signal was interpreted to reflect the influence of the inflow
of Mg-bearing (though perhaps dilute) waters into the lake and
wetland complex after flowing through basaltic fractured rocks
in that portion of the basin. At the time of deposition, basaltic
lavas in that area would have formed islands or peninsulas, with
the potential to introduce Mg-enriched groundwaters (Potts et al.,
1999; Behrensmeyer et al., 2002).
In addition to lateral variability within sedimentary facies,
significant variation is seen in stratigraphic analyses of authi-
genic clay compositions, even when constraining analyses to
identical lithologies. In a study of ~25 m of section in the Pleis-
tocene to Holocene Double Lakes Formation (Texas, USA),
Webster and Jones (1994) showed the stark differences between
the Mg-rich lacustrine clay minerals in the sediment versus the
illitic and kaolinitic Ogallala Formation that contributed detrital
Figure 8. Olduvai data are open circles, <0.2 µm clays (from Deo-
campo et al., 2002) and <0.1 µm clays (from Deocampo, 2004a);
dashes, <2.0 µm clays (from Mees et al., 2005); diamonds, high-
resolution transmission electron microscopy–analytical electron
microscopy analyses from Hover and Ashley (2003). Olorgesailie
data are all from Deocampo et al. (2010); the caret symbol indicates
upper member 1, and x indicates member 7 (see Behrensmeyer et
al., 2002). Whole-rock mole fractions of Al and Fe are plotted on
the right axis. Trachyte values are based on Carmichael (1965),
whereas GSP-2, BHVO-2, and AGV-2 all refer to U.S. Geological
Survey standard reference materials.
spe515-03 1st pgs page 58
material. Webster and Jones (1994) argued that highest lake lev-
els were represented by sepiolite deposits, low lake levels were
represented by palygorskite, and intermediate lake levels (when
detrital input was at its greatest), were represented by Mg-rich
smectite. Stratigraphic variations in the authigenic clay com-
positions are therefore potentially important sources of data on
changes in lake-water chemistry.
This idea has also been tested at Olduvai, in the center of the
paleolake at locality 49 (Hay, 1976). Over an ~2.6 m stratigraphic
interval dominated by lacustrine mudstone, the molar ratio
Mg/(Al + Fe), termed the octahedral cation index (OCI), of
<0.1 µm clays varied considerably, ranging from 1.0 to 4.6 (Fig.
10; Deocampo 2004a). Although uncertainties in the geochronol-
ogy must be considered, the significant freshening in the lake that
is implied by the shift in Mg/(Al + Fe) ratios from 4.6 to ~1 that
occurred ~1.79 m.y. ago roughly corresponds to a major increase
in African moisture indicated by offshore eolian dust records
(deMenocal and Bloemendal, 1995). This event was represented
by stratigraphic evidence of lake expansion and transgression on
the lake margin (Hay, 1976; Ashley and Driese, 2000; Hay and
Kyser, 2001), and it likely correlates to the regional expansion of
lakes at this time documented elsewhere such as in central Kenya,
Lake Turkana, and the Afar Basin, northern Ethiopia (Trauth et
al., 2005). A subtle lake contraction is also implied ~1.78 m.y.
ago at Olduvai, where Mg/(Al + Fe) increased to ~2. Although
this is well represented stratigraphically on the lake margin as
a lacustrine regression (Ashley and Driese, 2000; Deocampo et
al., 2002), it does not appear to correlate to a well-documented
global or regional signal. The event therefore could have been
either too subtle a climatic event to be recognized regionally, or
Figure 9. Lateral variability in <0.2 µm clay octahedral geochem-
istry within lowermost bed II, Olduvai Gorge, in atoms per half
formula unit, from Deocampo et al. (2002). Mg/Al values are low
~1 km east of locality (loc.) 45b due to the development of fresh-
water paleowetlands that preferentially leached clays of Mg in that
locality (Deocampo et al., 2002; Deocampo and Tactikos, 2010).
“loc.” terminology and FLK-NN location terminology are from
Hay, 1976.

Authigenic clay minerals in lacustrine mudstones
it was unrelated to climate and was more of a local, perhaps tec-
tonic or volcanic-related event (Deocampo, 2004a).
LAKE TYPE AND THE INFLUENCE OF TECTONICS
AND CLIMATE
Carroll and Bohacs (1999) and Bohacs et al. (2000) presented
a means of classifying lake basins based on the competing effects
of sediment and water supply versus potential accommodation.
This has provided an excellent framework for understanding the
evolution of lake basins through time, and provides a framework
for various facies-based stratigraphic models. The classification
has already been widely applied to our understanding of evap-
orite-producing basins (Pietras and Carroll, 2006; Smith et al.,
2008), and it provides a good context for understanding authi-
genic clay assemblages because many of the same factors are
involved. With the exception of the additional requirement of
high aqueous silica concentrations, the tectonic-climatic factors
leading to authigenic clay minerals are identical to those leading
to evaporites. Therefore evaporative basins that have high silica
tend to produce both authigenic silicates (including clays) as well
as saline evaporites, whereas those that do not have high silica
only produce the saline evaporites (Deocampo and Jones, 2014).
Abundance of authigenic silicates in the assemblage therefore
suggests a strong siliceous input, such as weathering of volcani-
clastics or substantial hydrothermal input.
If the condition of high siliceous input is met, then the poten-
tial exists in a basin for substantial authigenic clay mineral accu-
mulation, subject to the tectonic and climatic framework (Carroll
and Bohacs, 1999, 2001). In overfilled lakes, in which most water
spe515-03 1st pgs page 59
59
exits the basin via groundwater recharge or a spillway, even if
authigenic clay minerals are supersaturated due to the geochem-
istry of the inflowing water, they will not accumulate because
they are diluted by detrital or biogenic material.
Underfilled lakes lose nearly all of their waters to evapo-
ration, thereby increasing solute concentrations to the limits of
mineral solubility (Deocampo and Jones, 2014). Assuming that
the dilute inflow waters contain at least some alkalinity (unlike,
for example, the acid Australian saline lakes; Dickson and Gib-
lin, 2008), the evaporatively enriched brines can reach very high
alkalinities and high pH (Deocampo and Jones, 2014). Depend-
ing on diatom productivity, pH, and kinetic factors affecting
dissolved silica concentrations, silica levels in such settings can
reach >100 mg/L, far above the saturation of amorphous silica
(Rimstidt, 1997). In such settings, which are likely to accumulate
free silica and sodium silicates (Hay, 1968; Dietzel and Letof-
sky-Papst, 2002), authigenic clays are likely to form as well, par-
ticularly in the presence of detrital clays. At such high pH and
silica levels, not much Mg is required to favor the precipitation
of authigenic Mg-rich smectite, or illite if K-rich brines are pres-
ent (Deocampo et al., 2009). The hyperalkaline Lake Magadi
is a classic example of such a situation, dominated by sodium
carbonate brine with hydrothermal and volcaniclastic silica input
(Jones et al., 1977; Deocampo and Jones, 2014). Nevertheless,
even the sulfo-chloride Great Salt Lake can produce Mg-rich
authigenic clay, because of its slight alkalinity, Mg content, and
hydrothermal input into the lake (Spencer et al., 1985; Jones and
Spencer, 1999).
Between these two extremes are the balance-filled lakes, in
which substantial evaporative concentration may occur, but still
Figure 10. Correlation between high-
resolution stratigraphic analysis of au-
thigenic clay composition at locality 49
(Hay, 1976), in the center of the paleo-
lake at Olduvai Gorge, with the shore-
line stratigraphic record and an offshore
record of African dust flux. ODP—
Ocean Drilling Program.
 spe515-03 1st pgs page 60

60 Deocampo

have spillways regulating hydrology, at least episodically (Car-
roll and Bohacs, 1999). At times, however, lake levels may drop
below the level of the spillway, potentially allowing evaporative
concentration, the development of evaporitic facies, and precipi-
tation of authigenic clay minerals. An example is Lake Albert in
the East African Rift, which has somewhat elevated salinity due
to inflowing waters, but is dominated by detrital and biogenic
sediment (Beadle, 1974; Sserubiri and Scholz, 2012). In a study
of the Lake Albert clay minerals, Stoffers and Singer (1979)
found subtle shifts between kaolinite, smectite, and illite clay
mineral assemblages. Stoffers and Singer (1979) recognized that
dioctahedral smectites were associated with fresher lake phases,
indicated by diatom assemblages, whereas the illitic assemblages
were associated with phillipsite and chabazite, a clear indication
of elevated salinity and alkalinity.
Using the molar ratios of the octahedral cation composi-
tion Mg/(Al + Fe), the OCI (Deocampo, 2004a), approximate
ranges of values can be assigned to the three fields of the Carroll
and Bohacs (1999) model (Fig. 11A). Overfilled lake basins are
predicted to be dominated by only those clay minerals washing
into the basin as detrital sediment. Therefore the ultrafine clay
fraction will be composed of those clays produced by weather-
ing in the uplands. These are most likely to be Al- or Fe-rich
clays such as kaolin-type minerals or dioctahedral smectites or
illites. Although the bulk clay mineralogy (<2 µm) may more
closely reflect the clay mineralogy of detrital sources (which
may not be dioctahedral in nature), the ultrafine fractions
(<0.1 µm) are more likely to reflect the weathering (or diage-
netic) regime (Velde and Meunier, 2008). Therefore the OCI
values will be approximately <0.2, the approximate maximum
of typical dioctahedral 2:1 clays. In more intense weathering
regimes, it will approach zero, as kaolinite and related clay min-
erals have no alkali cation content.
Authigenic clays precipitated in balance-filled lakes may
show somewhat higher OCI values, perhaps as high as 0.5. Only
the underfilled lakes have the extreme conditions maintained
for significant time intervals to produce the high OCI values,
>>0.5, seen in deposits such as the Olduvai Basin or Green River
Formation. In part this pattern of authigenic clay OCI values
reflects the fact that the purest Mg silicate phases (e.g., pure
trioctahedral smectite or illite, sepiolite) only form under the
most extreme conditions; when these phases begin to dominate
the assemblage, the ultrafine clay fraction OCI values increase
dramatically (Fig. 11B).
CONCLUSIONS
Authigenic clay minerals are substantial components of ter-
restrial mudstones in settings where detrital sediment is limited,
and surface waters are alkaline, rich in silica, and have at least
some dissolved Mg. In the absence of these conditions, detrital
clay minerals dominate, but when these conditions are met, new
clay minerals may form, usually reflecting increased Mg and Si
content. Availability of Al- or Fe-rich detrital clays likely leads to

Figure 11. (A) Lake classification of Carroll and Bohacs (1999), showing approximate ranges of authigenic clay
octahedral cation indices (OCI) predicted based on expectations of basin salinity. Such a model assumes an abundant
source of aqueous silica in the basin to enable authigenic clay precipitation. Such a model would not apply to acid
saline lakes, such as those of southern and western Australia (Benison et al., 2007; Story et al., 2010; Deocampo and
Jones, 2014). Evap—evaporation. (B) Ternary plot of octahedral cation compositions, with OCI values labeled, and
several of the potential major end-member clay mineral phases. M—montmorillonite (Clay Mineral Society standard
SWy-1); K—kaolinite; N—nontronite (Nau-1); P—palygorskite (PFI-1); Se—sepiolite (SepSp-1); St—stevensite
(from Martin de Vidales et al., 1991); Sa—saponite.

Authigenic clay minerals in lacustrine mudstones
Mg-rich smectite formation, whereas those environments lack-
ing such detritus may form purer Mg silicates such as sepiolite
or kerolite. Available evidence from a number of basins around
the world suggests that illitization and increased octahedral
occupancy are decoupled, and therefore indicative of different
processes. Therefore the analysis of basal layer reflections by
XRD should also be supplemented by analysis of hkl reflections
to characterize the 060 peaks present, as well as geochemical
analyses to determine structural formulae and octahedral cation
ratios. Variations in these parameters can be used within units to
interpret paleoenvironmental variations across paleolandscapes,
as well as in stratigraphic contexts to reconstruct environmental
changes over time. In general authigenic clay minerals are more
common in underfilled lake basins, and they may be closely asso-
ciated with evaporitic basins with strong silica input from weath-
ering volcaniclastics or hydrothermal input.
ACKNOWLEDGMENTS
I thank the Olduvai Landscape Paleoanthropology Project
(OLAPP), the Smithsonian Institution Human Origins Pro-
gram, the National Museums of Kenya, the Olduvai Paleoan-
thropological and Paleoecological Project (TOPP), the National
Natural History Museum of Tanzania, and the Natural History
Museum of London for field and laboratory support and col-
laborations. Some of the results reported here were supported
by the U.S. National Science Foundation (grants 0202612,
1029020, 1349599). Acknowledgment is made to the Donors
of the American Chemical Society Petroleum Research Fund
for partial support of this research. I acknowledge Dick Hay
(1929–2006) for his patient science, his great understanding
of silicate diagenesis, and his inspirational contributions and
conversations. I thank Gail Ashley, Blair Jones, Bernie Owen,
Rebecca Pickering, Nate Rabideaux, and Robin Renaut for
helpful discussions that contributed to this paper.
DEDICATION
This paper is humbly dedicated to Blair Jones (1934-2014),
who passed away during its preparation. Blair was a driving
force behind the understanding of the complex interactions
between water, minerals, and organisms near the Earth’s sur-
face. He had an impact on entire disciplines, including aqueous
geochemistry, clay mineralogy, soil science, and limnogeology.
Over 50 years, he inspired generations of geoscientists, and he
will be missed.
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