Earth-Science Reviews 104 (2011) 213–239

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Earth-Science Reviews
j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / e a r s c i r ev

Searching for travertines, calcretes and speleothems in deep time: Processes,

appearances, predictions and the impact of plants
A.T. Brasier ⁎
Scottish Universities Environmental Research Centre, Rankine Avenue, East Kilbride, Scotland, UK, G75 0QF

a r t i c l e i n f o a b s t r a c t

Article history: Common models for modern calcite precipitation in and around caves, soils, springs and streams involve CO2
Received 21 April 2010 supplied by thick, high pCO2 biogenic soils which were probably thin or non-existent before vascular plants.
Accepted 27 October 2010 Indeed plant-influenced chemical weathering might have caused accelerated terrestrial carbonate production
Available online 4 November 2010
from the Devonian onwards. However terrestrial carbonates have also been documented from the Archaean,
Proterozoic, Cambrian, Ordovician and Silurian. Mechanisms which could have caused non-marine carbonates
Keywords:
to precipitate without organic-rich soils are described, and some geological events likely to have influenced
calcrete
travertine
non-marine carbonate precipitation up to the origin of vascular plants are highlighted. As organisms have
speleothem evolved, so have the petrographic characteristics of non-marine carbonates; some examples of this are also
terrestrial vegetation given here.
Palaeozoic © 2010 Elsevier B.V. All rights reserved.
Precambrian

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 214
2. Definitions of travertine, speleothem and calcrete . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 214
3. Vascular plants and weathering . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 215
3.1. Significance of plant roots . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 216
3.2. Chemical weathering in the rhizosphere and the role of fungi . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 216
3.3. Did the origin of plant roots cause increased terrestrial carbonate abundance? . . . . . . . . . . . . . . . . . . . . . . . . . . . 216
4. Precipitation of calcretes, SSL carbonates and speleothems before plants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 219
4.1. Calcite dissolution and precipitation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 219
4.2. Calcite precipitation models including carbonic acid-rich, high pCO2 soils . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 222
4.3. Calcite precipitation mechanisms without high pCO2 soils . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 222
4.3.1. Degassing mechanisms: temperature rise. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 222
4.3.2. Degassing mechanisms: deep-sourced CO2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 223
4.3.3. Degassing mechanisms: turbulence . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 223
4.3.4. Evaporation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 223
4.3.5. Common-ion effect . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 223
4.3.6. Freeze-out . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 224
4.3.7. Precipitation from boiling springs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 224
4.4. Biological influences on non-marine carbonates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 229
4.4.1. Cyanobacteria . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 229
4.4.2. Fungi and lichens . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 229
4.4.3. Vascular plants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 230
4.5. Temporal changes in non-marine carbonate precipitation up to the Devonian . . . . . . . . . . . . . . . . . . . . . . . . . . . . 230
5. Recognising Silurian and older non-marine carbonates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 231
5.1. Petrographic changes of non-marine carbonates through time? . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 231
5.2. Further examples of Proterozoic terrestrial carbonates from North America . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 232
5.3. Do non-marine carbonates contain a record of pre-Silurian land surface habitation? . . . . . . . . . . . . . . . . . . . . . . . . . 233
5.4. Are Silurian and older non-marine carbonates usually recognised and reported? . . . . . . . . . . . . . . . . . . . . . . . . . . 233

⁎ Tel.: +44 1355 270 147; fax: +44 1355 229 898.
E-mail addresses: alex_brasier@yahoo.co.uk, a.brasier@suerc.gla.ac.uk.

0012-8252/$ – see front matter © 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.earscirev.2010.10.007
214 A.T. Brasier / Earth-Science Reviews 104 (2011) 213–239

5.4.1. Cave carbonates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 233

5.4.2. Spring, stream and lacustrine deposits . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 233
5.4.3. Calcretes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 233
6. Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 234
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 234
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 234

1. Introduction
Terrestrial carbonates are frequently used in palaeoclimatic and
palaeoenvironmental reconstructions (e.g. Retallack, 1997; Andrews
and Brasier, 2005; Andrews, 2006; Fairchild et al., 2006). Most of what
is currently known about such carbonates, however, has come from
the Devonian to Holocene record of soil (e.g. Esteban and Klappa,
1983; Wright and Tucker, 1991; Wright, 2007), spring, stream, lake
(e.g. Pedley, 1990; Ford and Pedley, 1996; Jones and Renaut, 2010)
and cave carbonates (e.g. Fairchild et al., 2006; Frisia and Borsato,
2010), so that pathways leading to terrestrial carbonate lithogenesis
have largely been viewed in terms relating to the influence of vascular
land plants with roots. Much less is known about the character and
distribution of terrestrial carbonates before this time. The purpose of
this review is to explore some questions relating to non-marine
carbonate processes both before and after the arrival of terrestrial
vascular plants in the Silurian (e.g. Edwards, 1996).
Terrestrial carbonates are commonly thought to have become
established as a result of the influence of vascular plant root systems
upon silicate mineral weathering. For example, it has been suggested
that weathering by vascular plants (from the Silurian onwards) and
particularly their roots (since the Devonian) could have released
significant amounts of calcium ions from silicate rocks, leading towards
a burgeoning of non-marine carbonate precipitation from the Siluro–
Devonian onwards (e.g. Knoll and James, 1987; Berner et al., 2003;
Alonso-Zarza and Tanner, 2010). A major prediction of this hypothesis is
that pedogenic calcite should be rare and lack root-related features in
any examples older than Devonian.
Hitherto, predictions about the nature of the Silurian and older record
of terrestrial carbonates have barely been explored. There are a few
exceptions to this. Jutras et al. (2009), for example, reported both
‘pedogenic calcite’ and stable K-rich minerals from Middle Ordovician
palaeosols in Nova Scotia. They believe this to be due to more alkaline
groundwaters prior to the presumed emergence of acid soils during the
Silurian. Investigating the possible role of vascular plants in enhancing
silicate weathering and raising levels of terrestrial carbonate precipitation
is clearly important for reconstructing global carbon budgets through
deep time.
When considering the evolution of such ancient terrestrial
carbonates, a succession of questions emerge. For example, to what
extent do vascular plant roots affect calcium ion availability and
terrestrial water alkalinity? In which environments could non-marine
carbonates exist without the (direct or indirect) influence of vascular
plants? How could cave calcite precipitation proceed without the high
pCO2 soils which seem integral to Quaternary speleothem genesis?
How have the physical appearances of non-marine carbonates
changed through time? And could non-marine carbonates contain
an important record of pre-Silurian land surface habitation?
2. Definitions of travertine, speleothem and calcrete
The terms ‘tufa’ and ‘travertine’ have been used since Roman times
and have therefore acquired many different meanings. Tufa originally
meant a porous building stone, including volcaniclastic rocks now
called ‘tuff’. ‘Travertine’ was an alternative Latin name for a calcareous
building stone found around the river Tibur. Definitions of ‘tufa’ and
‘travertine’ have drifted from descriptive terms which can be simply
applied to ancient deposits. Recent articles on travertine and tufa have
tended to focus upon genetic definitions, based for example upon the
source of carbon dioxide, or water temperature, at the time of
deposition (e.g. Pedley, 1990; Pentecost and Viles, 1994; see also Jones
and Renaut, 2010) or upon the chemical mechanism involved in
precipitation (e.g. Pentecost, 2005). Thus ‘travertine’ has been
reserved by some (mostly European) researchers as a term for
warmer water hydrothermal precipitates whereas ‘tufa’ has been
reserved for cooler water deposits (e.g. Pedley, 1990; note many
North American authors use ‘travertine’ in both cases). For temper-
ature-based definitions, water temperatures have been measured
directly in active deposits, or estimated indirectly from included
organisms and fossils (e.g. Pedley, 1990; Koban and Schweigert,
1993). Definitions of cool water tufa frequently mention a likelihood
of, or even require, macrophyte content. Clearly, such definitions
cannot be applied with ease to terrestrial carbonates deposited before
the radiation of macroscopic land plants in the Silurian.
Another definition of ‘travertine’ has recently suggested restricting
use of the term to carbonates formed by degassing (see, Pentecost,
2005), thereby excluding many spring, stream and lacustrine
carbonates formed by the common-ion effect (Section 4.3.5) even
though such deposits can be petrographically indistinguishable from
those formed principally by CO2 degassing. Restricting ‘travertine’ to
deposits formed by degassing would clearly make usage of this term
almost impossible to apply to rocks from the distant past, where such
phenomena cannot be directly observed or confidently inferred.
Thus while definitions based upon specific physical processes can be
applied to young and active deposits (e.g. Pedley, 1990; Andrews and
Brasier, 2005; Andrews, 2006) they cannot be confidently used where
only the broad habitat of deposition is known (e.g. a spring or a lake) or
where the physical conditions themselves are moot. To add confusion,
some Proterozoic marine deposits now better called seafloor crusts
(Grotzinger and Knoll, 1995) have previously been referred to as ‘tufas’
(e.g. Grotzinger, 1986; Sami and James, 1994; see Riding, 2008), while
similarly ancient (?hydrothermal) spring deposits have (perhaps
correctly) been called travertine (Melezhik et al., 2004; Rainbird et al.,
2006). The problem with application of these terms is further illustrated
by Fig. 1, which shows there is often a degree of ambiguity in the naming
of a specimen: a theoretical continuum exists between tufa/travertine,
calcrete and speleothem based on varying degrees of biological
involvement and habitats of deposition. Such deposits might be relatively
easy to name where observed forming today, but precise, restrictive
definitions can be a hindrance to understanding once depositional
conditions are lost in time.
Studies of terrestrial carbonates in deep time therefore require
definitions that are applicable to deposits across a wide time span, so
that temporal trends can be plotted from Proterozoic to Recent.
Alternative phrasing to tufa and travertine, such as ‘spring carbonate’,
‘stream carbonate’ and ‘lacustrine carbonate’, can be applied where
depositional environment can be deduced from the stratigraphy. This
less restrictive terminology is relevant to discussions of deposition in
different terrestrial settings in this review (e.g. Section 4). Spring,
stream and lacustrine (‘SSL’) carbonate is thus used here for all
authigenic carbonates precipitated in and around springs, streams or
lakes, regardless of the temperature of deposition or cause of
 A.T. Brasier / Earth-Science Reviews 104 (2011) 213–239 215

Fig. 1. Circular diagram showing the theoretical continuum that exists between the concepts of tufa/travertine, calcrete and speleothem. Calcrete alpha-fabrics are usually regarded
as abiological and beta fabrics as biological (for examples see Section 5.1 and Table 2). Tufa and travertine are used respectively for ambient temperature and hydrothermal deposits
in spring, stream and lacustrine environments. They are not used in this review because of the difficulty in deducing water temperature in ancient examples. Speleothem is used for
carbonates deposited in caves. Examples and positions of various rock types within this classification are shown outside the circle.

precipitation which might be implied by using ‘tufa’ or ‘travertine’. these that our current theories about SSL carbonates, speleothems and
The term ‘speleothem’ is similarly used here for carbonate precipi- calcretes have mainly been developed. Later sections examine the
tated in a cave because it is relevant to discussions of carbonate theoretical context for, and some documented examples of, Archaean
deposition in different terrestrial settings, although descriptive to Silurian carbonates of terrestrial origin.
language such as ‘laminar sparry calcite cement’ might be more
useful in reference to individual specimens.
The term calcrete (synonymous with caliche when the latter is 3. Vascular plants and weathering
composed of calcium carbonate) meaning ‘a near surface, terrestrial
accumulation of predominantly calcium carbonate, which occurs in The evolution of vascular plants with rhizomes in the Silurian, and
a variety of forms from powdery to nodular to highly indurated’ (Wright with deeper root systems in the Devonian (see for example Algeo and
and Tucker, 1991) is applied to both pedogenic (soil) carbonates and to Scheckler, 1998; Kenrick and Davis, 2004), might have exerted a
non-pedogenic ‘groundwater’ carbonates (Section 4.1; see also Arakel, major influence upon silicate weathering and thus terrestrial
1986; Wright and Tucker, 1991; Nash and Smith, 2003); the latter being groundwater composition from the Silurian Period onward. This
precipitated by subterranean groundwaters. Even in modern examples could have happened because chemical weathering of calcium
pedogenic and groundwater calcretes are hard to distinguish, with silicates (arguably enhanced by plant roots) produces free calcium
many deposits showing features of both types (e.g., Mack et al., 2000). and bicarbonate ions (e.g. Berner, 1992), for example (Eq. (1)):
The term ‘calcrete’ (which does not require reference to pedogenic or
2þ −
groundwater types) is thus relatively easy to apply in deep time because 2CO2 þ 3H2 O þ CaAl2 Si2 O8 →Ca þ 2HCO3 þ Al2 Si2 O5 ðOHÞ4 ð1Þ
the word in itself is not too restrictive, implying no specific set of
depositional circumstances, cause of precipitation or degree of biological Similarly, weathering of magnesium silicates by the same
involvement. The term ‘cement’ is usually applied to mineral pre- phenomena produces further bicarbonate ions, plus free magnesium
cipitates that fill voids or hold sediment together, but in this field of ions (Eq. (2)):
research ‘cement’ can also be used to describe a precipitate which
neither fills voids nor binds (for example ‘tufa cements’ often coat 4CO2 þ 4H2 O þ Mg2 SiO4 →2Mg
2þ −
þ 4HCO3 þ H4 SiO4 ð2Þ
biological substrates), and this broad usage is followed here.
Soils can be regarded as rocks altered by hydrolitic weathering
The net result of this silicate weathering by land plant ecosystems
(Retallack, 2007). This usage allows for discussion of carbonates
can be the precipitation of carbonate minerals (Eqs. (3) and (4)):
formed in and around ‘soils’ before the Devonian evolution of vascular
plants with root systems. For a wider discussion of the evolution of 2þ −
Ca þ 2HCO3 ↔CO2 þ H2 O þ CaCO3 ð3Þ
soils themselves, see reviews in Retallack (1990, 2007, 2008).
The following section begins with questions relating to terrestrial 2þ 2þ −
carbonates of the post-Silurian to modern periods, because it is from Ca þ Mg þ 4HCO3 ↔2CO2 þ 2H2 O þ CaMgðCO3 Þ2 ð4Þ
216 A.T. Brasier / Earth-Science Reviews 104 (2011) 213–239
If vascular plants caused a significant post-Silurian increase in
silicate weathering, the geological record should show at least three
features compared to preceding times: (1) measurably increased
carbonate precipitation (e.g. Eq. (3) and (4)) and (2) increased clay
levels (e.g. Eqs. (1) and (3)) decreased atmospheric CO2 levels (net
result of Eqs. (1)–(4); see for example Ebelmen, 1845; Urey, 1952;
Jutras et al., 2009; Berner, 1992; Berner, 1998). The question
answered in this section is thus whether it is likely that the arrival
of vascular plants (and their ecosystems; e.g. Retallack, 1997)
increased chemical weathering of silicates (e.g. Basu, 1981a,b; Knoll
and James, 1987), leading to an increase in Ca2+ and HCO−
3 availability
and non-marine carbonate production (e.g. Alonso-Zarza and Tanner,
2010)?
3.1. Significance of plant roots
Microbial and lichen crusts were arguably the only form of
vegetative covering on land before the Ordovician (for example
Campbell, 1979; Golubic and Campbell, 1979; Shear, 1991; Knauth
and Kennedy, 2009; see Section 5.3). A basic feature of land plants, at
least from the Middle Devonian onwards, is their formation of root
systems specialised for anchorage and for uptake of water plus
biolimiting nutrients. Many of the essential cations (including Ca2+,
Mg2+ and Fe2+) come from rock weathering plus decomposition and
recycling of organic matter (see for example Knoll and James, 1987;
Berner et al., 2003). The ability of plants to grow on rocky, ‘infertile’
slopes itself suggests that plant roots can cause release of nutrients
from rocks (Boyle and Voigt, 1973). It is thus unsurprising that the
Silurian arrival of vascular plants, followed by the Devonian arrival of
plant roots, has been linked with hypothesised enhanced chemical
weathering (e.g., Berner, 1992, 1998; Algeo et al., 2001) leading to
enhanced soil carbonate formation (e.g. Alonso-Zarza and Tanner,
2010).
One reason for believing chemical weathering of silicate rocks
might have increased since vascular plant diversification in the
Devonian is the relatively high surface area and depth of penetration
such roots provide (for example Algeo et al., 1995). This is illustrated
by a global study of modern root systems by Canadell et al. (1996).
They reported living vascular plant roots extending to depths of up to
68 m (in the water-limited central Kalahari desert), while average
maximum tree root depth was 7.0 ± 1.2 m, and global average root
depth was 4.6 ± 0.5 m. Current understanding is that Silurian to early
Devonian vascular plant roots were shallow, to depths of only a few
centimetres, but that depths of around 1 m were achieved by the
Middle to Upper Devonian (see Algeo and Scheckler, 1998; Algeo et
al., 2001; Kenrick and Davis, 2004). The geological record of soils
broadly supports this view: early Palaeozoic soils show weathering
concentrated at the surface, whereas mid-Palaeozoic and later soils,
often with large root traces, show deeper and greater chemical
weathering with clay contents that extend well below the surface
layers (Retallack, 1997).
3.2. Chemical weathering in the rhizosphere and the role of fungi
The ‘rhizosphere’ (Hiltner, 1904; Darrah, 1993; Gregory, 2006;
Hinsinger et al., 2006 and references therein) around plant roots
exhibits conditions which favour locally enhanced chemical weath-
ering. Firstly, the pH of the rhizosphere may differ from that in
surrounding soil by as much as 1–2 units, largely because plant roots
maintain their charge balance by releasing protons (H+) whenever
they take up more cations than anions, and vice-versa (see Hinsinger
et al., 2006). Root respiration also produces significant levels of CO2
(and hence of carbonic acid) which contributes to lowering of
rhizosphere pH (Hinsinger et al., 2006) down to values as low as 3
(Arthur and Fahey, 1993). This acidity certainly assists in carbonate
bedrock dissolution and may also help to increase silicate weathering
rates (Meheruna and Akagi, 2006), although the effect of pH alone on
silicate dissolution may be small (see Drever, 1994).
Many studies have shown that plant roots, or their associated
microbes, can cause release of nutrients from mineral grains (e.g. Boyle
and Voigt, 1973; Basu, 1981a,b; Meheruna and Akagi, 2006), although
the direct role of the plant root vs that of symbiotic micro-organisms is
not often distinguished (see Kelly et al., 1998). This distinction (which
can be difficult to make in practice) is important because it has been
shown that mycorrhizal fungi alone can cause an increase in mineral
weathering rates (e.g. Fisher, 1972; Griffiths et al., 1994; Jongmans
et al., 1997) such that high rates of silicate weathering may pre-date
the arrival of vascular plant roots (see for example Humphreys et al.,
in press). Modern mycorrhizal fungi allow access to mineral sources
that are otherwise physically inaccessible to plant roots (van Breemen
et al., 2000). For example, tubular pores some 3–10 μm wide in
feldspar and hornblende grains (which could be preserved as trace
fossils) have been attributed to dissolution by organic acids produced
by mycorrhizal fungi (Jongmans et al., 1997; van Breemen et al., 2000).
Mycorrhizal fungi are also known to help the release of essential
biolimiting phosphorus ions (e.g. Wallander et al., 1997; Ness and
Vlek, 2000; Wallander, 2000) and (importantly here) calcium
ions (e.g. Blum et al., 2002) from relatively insoluble apatite crystals
(Ca5(PO4)3(F,Cl,OH)) as well as potassium ions from micas (e.g. Boyle
and Voigt, 1973; Leyval and Berthelin, 1991; Bonneville et al., 2009).
Apatite is a common accessory mineral in many silicate rocks. Blum et
al. (2002) estimated that ~35% of calcium in a US forest stream came
from weathering of apatite by mycorrhizae, with a further ~35% from
weathering of silicate minerals and ~30% from atmospheric sources.
Fungal dissolution of apatite (which occurs N103 times faster than
dissolution of hornblende, plagioclase and K-feldspar; see Blum et al.,
2002) may be encouraged by uptake of calcium and phosphorus ions
by the fungal hyphae themselves, thereby reducing the concentra-
tions of Ca and P around the dissolving apatite grains (Khasawneh and
Doll, 1978; Ness and Vlek, 2000). Even so, Le Chatelier's Principle
should only be applied with caution for predictions about increased
weathering rates of soil solutions upon silicate rocks (e.g. Drever,
1994). This is because soil solutions can often exist in states far from
equilibrium, meaning that weathering rates are unlikely to increase
dramatically as a result of localised uptake of cations by microbes or
plants. A precise mechanism for the microbial release of nutrients
from apatite grains has yet to be elucidated. It is believed to involve
the production of oxalic acid by the fungi at their hyphal tips (e.g.
Griffiths et al., 1994; Ness and Vlek, 2000; Wallander, 2000).
3.3. Did the origin of plant roots cause increased terrestrial carbonate
abundance?
The influence of plant roots and (and associated ecosystems; e.g.
Retallack, 1997) on local rock weathering, by exposing rock surfaces
and causing cation and anion release, therefore seems clear. But have
vascular plants brought about a net acceleration of chemical
weathering through geological time (e.g., Basu, 1981a,b; Knoll and
James, 1987; Berner, 1992; Algeo et al., 1995, 2001), leading to greater
global availability of Ca2+ and HCO− 3 ions (above and beyond that
produced by lichens and fungi), and thus more post-Silurian non-
marine carbonates?
This can be questioned on short timescales since soil also inhibits
chemical weathering of bedrock by providing a protective clay
mineral barrier (Berner, 1992). But the relative rarity of fossil soils
identified in the geological record probably reflects the ease with
which such clay barriers are eroded, so this barrier effect is less
significant on longer timescales.
In addition to silicate weathering, carbonate bedrock dissolution
would probably also have accelerated in the relatively deep (and acidic?)
post-Middle Devonian rhizosphere. This could have caused some locally
increased groundwater alkalinities and calcium ion activities, resulting in
 A.T. Brasier / Earth-Science Reviews 104 (2011) 213–239 217

re-distribution of carbonate minerals from relatively soluble bedrock to
soil and stream precipitates. This is despite global (including marine
environment), long term balance between carbonate mineral dissolution
and precipitation (see also Berner et al., 2003).
However marine carbonate bedrock abundance and distribution
have not been constant through time: geological events which have
affected these factors, in addition to the major development of
vascular plants with deep roots, must have exerted some influence on
the temporal abundance and distribution of non-marine carbonates
(Fig. 2). Abundant calcium sulphates in some pre-Silurian rocks (for
example Melezhik et al., 2005b) provide a further reason for thinking
that, at least locally, pre-Devonian terrestrial carbonate precipitation

Fig. 2. A timeline from the origin of the Earth to the end of the Devonian, with events of importance to non-marine carbonate processes noted. Note the breaks in scale between the
Hadean (from which no sedimentary rocks are known) and the Archean, and at the Precambrian–Cambrian boundary. Horizontal arrows and vertical lines of the same colour as the
associated text show dates or durations of events, respectively. Isua Gp sediments (e.g. Moorbath et al., 1973) are interpreted as marine, but unconformable surfaces and possible
'soils' (e.g. Johnson et al., 2009) are also reported from ancient times.
218 A.T. Brasier / Earth-Science Reviews 104 (2011) 213–239

Table 1
Non-marine carbonate examples of pre-Devonian age, with some cases (asterisked) where non-marine carbonates might be found on further examination. Gamagara Formation
laterites reported by Gutzmer and Beukes (1998) are not carbonate themselves, but terrestrial sideritic concretions are known from this same formation (Gutzmer, personal
communication, 2010). Petrographic features: Cg = coated grains (sizes and internal structures undifferentiated); Cr = circumgranular cracking; Cu = clay cutans; Cy = crystallaria;
D = desiccation cracks; E = evaporite pseudomorphs; Fg = floating grains; L = laminar crusts; M = massive carbonate bed; N = nodules; O = oncoliths; Oo = ooliths; P = pisoliths;
Pd = peloids; S = stromatolites; Sp = spar cement; Tp = tepee structures.

Reported age Unit Location Description References Selected

petrographic
structures

2.78 to 2.63 Ga Tumbiana Formation Pilbara, lacustrine stromatolites Bolhar and van Kranendonk S
Australia (2007); Awramik and Buchheim
(2009)
~ 2.7 Ga Klippan and Botheville South Africa lacustrine, fluvial and alluvial fan Buck (1980); date from D,Oo,S,Sp
Formations, Ventersdorp with stromatolites Armstrong et al. (1991)
Supergroup
2.6 Ga ‘pre-Chuniespoort Group’ South Africa silcrete and dolocrete crusts Martini (1994)
2.6 Ga basement complex South Africa soil carbonate Watanabe et al. (2000)
2.35 +/− 0.1 Ga Espanola Formation, Bruce Ontario, lacustrine limestone Veizer et al. (1992); Bernstein
“Limestone” Member Canada and Young (1990)
Palaeoproterozoic NW Canada soil and groundwater calcrete Aspler and Donaldson (1986) M,N
2.33 to 2.25 Ga Kuetsjarvi Sedimentary Fennoscandian lacustrine coastal plain, with calcretes Melezhik and Fallick (2001); Cg,E,L,N,P,S,Tp
Formation Russia and hydrothermal travertines Melezhik et al. (2004)
2.2 to 2.0 Ga Gamagara Formation South Africa *paleokarst-hosted laterites Gutzmer and Beukes (1998) L,P
1.85 Ga Missi Group–Amisk Group NW Canada possible pedogenic carbonate in the Holland et al. (1989)
contact ‘Flin Flon paleosol’
1.84–1.79 Ga Baker Lake Group Nunavut, carbonate cements in conglomerates, Mustard and Donaldson
Canada magnesite “chemogenic lake beds” (1990)
1.785 +/− 0.003 Ga Kunwak Formation, Baker Lake Nunavut, hydrothermal travertine Rainbird et al. (2006) E,L,N,Sp
Group Canada
1.3 to 1.865 Ga Murky Formation NW Canada alluvial fan carbonates Hoffman (1976) S
~ 1.27 Ga Dismal Lakes Group Arctic Canada speleothem cements—“marine, ? Glover and Kah (2006) P
phreatic, vadose”
Mesoproterozoic Kanuyak Formation NW Canada lacustrine and fluvial with calcretes Pelechaty et al. (1991); M, Oo,P,Pd,Sp,
Pelechaty and James (1991) Tp
1.199 +/− 0.07 Ga Poll a'Mhuilt Member, Stoer NW Scotland lacustrine limestone Upfold (1984); Turnbull et al.
Group (1996); Stewart (2002)
Proterozoic Staca paleosol (sub-Torridon NW Scotland palaeosol carbonate Retallack et al. (1994); Oo
Group) Williams and Schmidt (1997)
N 1.1 Ga Mescal Limestone Arizona, USA speleothem Skotnicki and Knauth (2007) L,Sp
1.2 Ga Mescal Limestone Arizona, USA calcrete Beeunas and Knauth (1985) L
~ 1.1 Ga Portage Lake Volcanics Michigan, USA calcrete Kalliokoski and Welch (1985) Cg,Cy,Fg,L,N,Sp
1.1 Ga Oronto Group Michigan, USA calcrete in fluvial and alluvial fan Kalliokoski (1986) Cg,Fg,N
sediments
1.087 Ga Oronto Group, Copper Harbor Michigan, USA alluvial fan and stream carbonate Elmore (1983); Davis and O,S
Conglomerate Paces (1990)
700–600 Ma Sarnyere Formation Mali calcrete Bertrand-Sarfati and Cg,Cr,D,N,L,Sp
Moussine-Pouchkine (1983)
Neoproterozoic Contact between Ravensthroat NW Canada *palaeokarst James et al. (2001)
Formation and Hayhook Formation
Neoproterozoic Contact between Sierras Bayas Tandilia *palaeokarst Gomez-Peral et al. (2007)
Group and Cerro Negro System,
Formation Argentina
Neoproterozoic Tsagaan Oloom Formation western *palaeokarst Shields et al. (2002)
Mongolia
Neoproterozoic Jbeliat Group cap carbonate Taudéni basin, *palaeokarst, cavities lined Shields et al. (2007)
NW Africa with barite
Neoproterozoic Krol Group and Infra-Krol Lesser palaeokarst and calcrete Jiang et al. (2003) Fg,N,P
(maximum age 590 Ma) Formation Himalaya,
India
Neoproterozoic to early Contact between Matjies River South Africa *palaeokarst Praekelt et al. (2008)
Cambrian (~ 547 Ma) Formation and Groenfontein
Formation
Neoproterozoic to early Unicoi Formation Appalachian alluvial fan conglomerates (*no Simpson and Eriksson (1989)
Cambrian orogen, USA terrestrial carbonates reported)
Early Cambrian Hawker Group Flinders palaeokarst at unconformity, with James and Gravestock (1990)
Ranges, possible cave pearls and calcretes
Australia
Cambrian Flinders paleosol calcrete Retallack (2008) E,N,Sp
Ranges,
Australia
Cambrian Davis Bore Conglomerate; Officer Basin, calcite cemented conglomerates, White and Youngs (1980); L,S,Tp
Observatory Hill Beds S. Australia playa lake stromatolitic carbonates Southgate et al. (1989)
Lower Cambrian Chapel Island Formation Newfoundland, calcrete Landing and MacGabhann Cy
Canada (2010); Landing et al. (1989)
Lower Cambrian White Point Conglomerate Kangaroo alluvial fan conglomerates (*no Daily et al. (1980)
and Boxing Bay Formation Island, South terrestrial carbonates reported)
Australia
 A.T. Brasier / Earth-Science Reviews 104 (2011) 213–239 219

Table 1 (continued)
Reported age Unit Location Description References Selected
petrographic
structures

Uppermost Lower Cambrian Eastern Anti- calcrete Buggisch and Siegert (1988) Fg
Atlas, Morocco
Middle Cambrian Mount Roosevelt British peritidal to supratidal calcrete, calcite Post and Long (2008) N
Colombia, cemented conglomerates
Canada
Cambrian Guaritas Sequence Brazil alluvial fan calcrete De Ros et al. (1994) L,N, Sp
Uppermost Cambrian La Flecha Formation Argentine calcrete Keller et al. (1989); Buggisch et Cu?,D,E,L,P,S,
Precordillera al. (2003) Tp
Cambro-Ordovician North China *palaeokarst and palaeosols (no Meng et al. (1997)
terrestrial carbonates described)
Cambro-Ordovician Haima Group Oman alluvial fan conglomerates (calcretes Heward (1989)
said to be absent; calcite cement
present)
Lower Ordovician Puddinga Beds Sardinia, Italy *Fluvio-lacustrine and alluvial fan Martini et al. (1991)
conglomerates (no terrestrial
carbonates reported)
Lower Ordovician Beekmantown Group Ontario, vadose cements in palaeokarst (N.B., Dix et al. (1998)
Canada some cements may post-date
Ordovician)
Lower to Middle Maggol Limestone Taebaeksan *palaeokarst (no terrestrial carbonates Ryu et al. (2005)
Ordovician Basin, South reported)
Korea
Middle Ordovician Newmarket Limestone West Virginia, vadose cements in marine carbonates Read and Grover (1977); Grover
USA and Read (1978)
Middle Ordovician Chickamauga Formation Alabama, USA palaeokarst with meteoric cements Tobin and Walker (1994) Sp
Middle Ordovician Dunn Point Formation Nova Scotia calcrete (palaeosol carbonate) Jutras et al. (2009)
Ordovician (Ashgill) Juniata Formation Pennsylvania, calcrete (palaeosol carbonate) Retallack (1985); Retallack Cu,N
USA (2001)
Ordovician Huanghuachong Formation South China *palaeokarst (no terrestrial carbonates Jia-yu and Johnson (1996)
(Caradoc to Ashgill; reported)
capped by early Silurian)
Silurian Dronningveien Siltstone Norway fluvial red beds with concretions Turner (1974); Davies et al. N,P
Member, Ringerike Group (2005)
Silurian Niagara Group Michigan, USA calcretised stromatolites Sears and Lucia (1979) L,P
Silurian (Wenlock) Mill Cove Formation Ireland playa lake muds with incipient calcretes Wright et al. (1992) D,N
Silurian (Ludlow–Pridoli) Bloomsburg Formation Pennsylvania, pedogenic calcrete Mora et al. (1991) Fg,N
USA
Siluro–Devonian Lower Old Red Sandstone Wales and calcretes Allen (1974); Marriott and Cy,N,L
England Wright (1993)

was not limited by low calcium ion activities from a lack of plant root- 2004; Melezhik et al., 2005b). Nevertheless, carbonic acid is
associated weathering. responsible today (and presumably for much of Earth history) for
much carbonate dissolution, and results from mixing of carbon
4. Precipitation of calcretes, SSL carbonates and speleothems dioxide and water (Eq. (5)).
before plants
CO2 þ H2 O→H2 CO3 ð5Þ
The role of high pCO2 soils in precipitation of modern soil, cave and
spring calcites is well studied. Given there are examples of pre- This carbonic acid dissociates twice, first producing bicarbonate
vascular plant terrestrial carbonates preserved in the rock record (HCO− + 2−
3 ) and H ions (Eq. (6)), and then carbonate (CO3 ) and further
(Table 1), one might question how cave (Fig. 3A) and soil (Fig. 4) +
H (Eq. (7)).
calcites formed, and how Silurian and older carbonate depositional
patterns might have differed from those of later times? Here it is þ −
H2 CO3 ↔H þ HCO3 ð6Þ
helpful to examine possible precipitation mechanisms for spe-
leothems, SSL carbonates and calcretes both including and excluding − þ 2−
HCO3 ↔H þ CO3 ð7Þ
high pCO2 soils.
Groundwaters with pH higher than ~9 will have used up all
4.1. Calcite dissolution and precipitation available H+ ions and so predominantly contain carbonate (CO2− 3 )
species, whereas those with pH below ~ 5.5 have a majority of H2CO3
The common model for precipitation of abiotic calcite speleothem molecules over carbonate and bicarbonate ions. Waters with pH of 4
in caves requires an organic-rich high pCO2 soil zone above carbonate or less will have had all of their carbonate converted to carbon dioxide
bedrock (Fig. 3A). To understand why, it is necessary to consider what (Eq. (8); see also Andrews et al., 2004).
governs calcite dissolution and precipitation from carbonic acid-rich
groundwater solutions (see also Andrews et al., 2004). This discussion − þ
HCO3 þ H ↔H2 O þ CO2 ð8Þ
assumes the principle acid in question is carbonic, which may not
always have been the case. For example, local H2SO4 production is Carbonic acid coupled with calcium ions from silicate (see
likely to have increased following oxygenation of the atmosphere and Section 3.1) or carbonate bedrock weathering can thus produce
oxidation of sulphides in the Palaeoproterozoic (e.g. Bekker et al., calcite.
220 A.T. Brasier / Earth-Science Reviews 104 (2011) 213–239

Whether a low ionic strength solution will abiotically precipitate a The solubility product Ksp is an equilibrium constant (e.g. for
mineral is measured by the saturation index (SI — see Eq. (9)). SI calcite, Eq.(10)).
values N1 indicate supersaturation with respect to that mineral and it
may precipitate. Conversely, values of b1 indicate undersaturation 2þ 2−
Ksp ¼ aCa :aCO3 =aCaCO3 ð10Þ
and dissolution is expected.

SI ¼ IAP=Ksp ð9Þ where (for example) aCa2+ and aCO2− 3 are the activities of the
reactants (activity is proportional to concentration), and aCaCO3 is the
where IAP is the ion activity product and Ksp the solubility product of activity of the solid calcium carbonate product (solids are assigned a
the mineral in question (explained further below). value of 1; for further information see Andrews et al., 2004). Because

Fig. 3. Speleothem formation with and without organic-rich soils. Diagrams are not to scale. (A) An organic-rich soil above the cave provides high pCO2 acidic soil solutions which
dissolve carbonate bedrock and precipitate speleothem type carbonate when emerging in a lower pCO2 atmosphere. For degassing and subsequent precipitation to occur the cave
must be open to the (lower pCO2) atmosphere. This model accounts for most speleothem precipitation in warm, humid climates today. (B) A high pCO2 atmosphere (for example in
the Palaeoproterozoic) might allow bedrock dissolution, but degassing and precipitation will not occur unless solutions equilibrate with a lower pCO2 atmosphere. (C) Calcite
precipitation under ice cover by warming of waters and freeze-out. How warming causes precipitation is shown in the plot of Ca concentration vs pCO2 (adapted from Dreybrodt,
1982). In this plot, the curved lines show Ca concentration in equilibrium with pCO2 for given temperatures. For example, waters at 0 °C with a Ca concentration of X1 and pCO2 of Y
are in equilibrium at point A. When these 0 °C calcite-saturated waters enter bedrock and warm to 4 °C, the Ca concentration of the solution remains the same (X1) but pCO2 must
increase to maintain equilibrium at the elevated temperature, moving the composition of the solution along a horizontal line to point B. Degassing of CO2 begins on entering the cave,
returning the composition of the solution to point A, but now at elevated temperature, such that calcite must precipitate to decrease the calcium concentration to X2 and return the
system to equilibrium at point C. For full details see Dreybrodt (1982). When waters freeze Ca ions preferentially remain in the liquid which can also lead to local calcite
supersaturation. (D) Carbonic acid can be produced by mixing of groundwaters with deep-sourced CO2. Such groundwaters degas on emergence in a lower pCO2 atmosphere,
thereby leading to calcite precipitation. (E) Calcite supersaturation caused by the common-ion effect. Solutions saturated with respect to calcite may become supersaturated if extra
calcium is supplied from sources such as dissolution of calcium sulphates or incongruent dissolution of dolomite.
 A.T. Brasier / Earth-Science Reviews 104 (2011) 213–239 221

Fig. 3 (continued).

activities are used rather than concentrations, solubility products can rise above 1 favouring calcite precipitation. According to Le
should be constant for all environments at a given temperature Chatelier's Principle any factor which causes the equilibrium reaction
(though calcite solubility decreases with rising temperature). shown in Eq. (13) to shift towards the right (such as degassing of CO2
The ion activity product (IAP) for calcite can be calculated using or addition of calcium ions) will cause supersaturation of an already
Eq. (11): saturated solution and precipitation of calcite.
2þ 2−
IAP ¼ aCa :aCO3 ð11Þ 2þ −
Ca þ 2HCO3 ↔CaCO3 þ CO2 þ H2 O ð13Þ
The saturation index (SI) for calcite in a given solution at a given
temperature is thus dependent on the activities of calcium and Continued addition of calcium ions does not result in an indefinite
carbonate ions in the solution (Eq. (12)). solution pH rise: the excess Ca2+ ions will neutralise available HCO− 3
ions, and calcite precipitates until equilibrium is restored (Eq. (13)).
2þ 2− This reaction cannot easily be driven too far to the right since carbonic
SI ¼ aCa :aCO3 =Ksp ð12Þ
acid is produced to react with the calcite. Given sufficient supply of
Consequently by adding calcium and carbonate or bicarbonate calcium and carbon dioxide then groundwater pH is buffered by this
ions to a solution, (Eq. (12)) or increasing its temperature, SI values equilibrium reaction.
222 A.T. Brasier / Earth-Science Reviews 104 (2011) 213–239

Fig. 4. Quaternary pedogenic calcrete from central Greece. Atmospheric dust trapped around plants has supplied the calcium. This calcium-rich dust is dissolved at the top of the soil
profile by carbonic and organic acids produced by vascular plants and associated organisms. Calcite has precipitated lower down in the profile because soil waters became
supersaturated here through the evaporation, CO2 degassing and local effects around plant roots. The first (highest) precipitates formed an unconsolidated powder, followed lower
down by nodular growth and finally by coalesced nodules forming a ‘plugged’ horizon. Such zoned profiles are usually found in fine-grained sediments that accumulated through
trapping by vegetation and may usually require vascular plant involvement to form.

4.2. Calcite precipitation models including carbonic acid-rich, high
pCO2 soils
Waters percolating through organic-rich high pCO2 soil zones
above caves from the Middle Devonian onwards can be expected to
have dissolved mainly biogenic CO2 and become acidic (Eq. (5);
Fig. 3A), enabling dissolution of the calcium carbonate bedrock. When
such drip waters reach a lower pCO2 cave atmosphere they degas CO2
and become supersaturated with respect to calcite which then
precipitates (Fig. 3A; see also Holland et al., 1964; White, 1976; Bar-
Matthews et al., 1991). A similar process causes the distinct vertical
horizonation of pedogenic calcrete-containing soil profiles, where
carbonate is leached from the upper parts of the profile by high pCO2
waters, and re-precipitated lower down when supersaturation is
reached (Fig. 4; see Esteban and Klappa (1983) for further examples).
Similarly, some groundwater calcrete precipitation (e.g. Fig. 5 and
Goudie, 1996; Nash and Smith, 2003), and calcite precipitation at
springs (see Fig. 6 and Bono et al., 2001; Andrews, 2006) is caused by
equilibration of relatively CO2-rich waters with the lower pCO2
atmosphere.
Prior to the first land plants in the Ordovician (or perhaps the
development of deep plant roots in the Middle Devonian), conditions
in caves may well have been different. In conditions of high
atmospheric pCO2 that arguably pertained through much of the
Proterozoic to Ordovician (see Section 3.1 and Retallack, 1997),
reaction of atmospheric CO2 with cold water would readily have
allowed dissolution of limestone or dolomite bedrock until the waters
themselves became saturated (Fig. 3B). However these waters would
not degas and precipitate carbonate minerals unless they reached a
lower pCO2 environment. This leads us to an important conclusion: a
high pCO2 atmosphere in a pre-Silurian world would not be enough by
itself to cause bedrock dissolution and re-precipitation as speleothem.
4.3. Calcite precipitation mechanisms without high pCO2 soils
There are mechanisms capable of causing non-marine calcite
precipitation without aide from vascular plants. These processes must
have been responsible for many of the Silurian and older deposits
listed in Table 1.
4.3.1. Degassing mechanisms: temperature rise
Water in modern cold and high altitude climates may hold
sufficient CO2 to produce the necessary carbonic acid (see Section 4.1)
without need for soil zone CO2 input (Dreybrodt, 1982; Atkinson,
1983; Frisia and Borsato, 2010), yet the deposits that result are
volumetrically much less impressive than those formed under
 A.T. Brasier / Earth-Science Reviews 104 (2011) 213–239
Fig. 5. Quaternary groundwater calcretes in alluvial fan sediments, central Greece.
Calcium was mainly supplied via wind-blown dust and from carbonate bedrock clasts
in the conglomerates. Calcrete (upper arrow) has precipitated in the less well-drained
finer grained facies because waters percolate more quickly through coarser clast-
supported channel conglomerates (lower arrow). Boundaries of groundwater calcretes
are generally sharply defined and they lack the vertical horizonation of pedogenic
forms (see Fig. 3). Similar groundwater calcretes do not require vascular plant
involvement in their formation, and supersaturation is commonly achieved through
mixing of groundwaters (i.e., the common-ion effect).
warmer soils providing more biogenic CO2 (see for example Frisia and
Borsato, 2010). Degassing of CO2 following temperature rise can cause
calcite to precipitate (Dreybrodt, 1982). In this model, waters beneath
glaciers at temperatures of ~ 0 °C, are able to dissolve calcite. When
percolating through cavities in limestone bedrock, these waters warm
up, and can eventually precipitate calcite owing to its decreasing
solubility with increasing temperature (Fig. 3C). This can happen at
rates of up to 10− 3 cm yr− 1 under modern atmospheric conditions
(Dreybrodt, 1982). For such a process to work, dissolution must
occur in open system conditions, waters must be warmed by several
degrees and cave air pCO2 must be similar to that of the free
atmosphere. This mechanism can also work in the absence of
vegetation, such as when waters at 0 °C enter warm caves during the
winter. Warm waters entering cooler caves may dissolve calcite in
the summer, but probably at slower rates than winter deposition
proceeds (Dreybrodt, 1982). Warming of waters also causes CO2
degassing and calcrete precipitation in sub-arctic soils where
relatively warm temperatures at shallow depths favour precipitation
close to the surface in the summer (Swett, 1974; Dijkmans et al., 1986).
4.3.2. Degassing mechanisms: deep-sourced CO2
Speleothem or SSL calcium carbonates may also precipitate in the
absence of vegetation if CO2 is provided by volcanic or other deep
sources such as CO2 outgassed during metamorphism of sediments
(Fig. 3D; e.g. Duliński et al., 1995; Pentecost and Viles, 1994;
D'Alessandro et al., 2007). However speleothems in modern volcanic
settings seem to be rare (Forti, 2005), and seemingly require the
223
presence of an organic-rich soil above the cave. Tuccimei et al. (2006)
suggest periodic outgassing of deep-sourced CO2 can inhibit spe-
leothem precipitation because waters become too acidic. However
this could only be the case where supply of calcium ions is too low for
the reaction to be buffered (see Eq. (13)). Degassing of deep-sourced
CO2 can also cause carbonate precipitation around springs (e.g.
‘thermogene travertine’ of Pentecost and Viles, 1994; D'Alessandro et
al., 2007) without causing carbonate precipitation through high water
temperatures (e.g. Yoshimura et al., 2004) and might explain some
Palaeoproterozoic hot spring carbonate mounds (Melezhik and
Fallick, 2001).
4.3.3. Degassing mechanisms: turbulence
One of the most important mechanisms for carbonate precipita-
tion around modern rapids and waterfalls (Fig. 6) is degassing of CO2
due to turbulence. Zhang et al. (2001) and Chen et al. (2004)
suggested that calcium carbonate preferentially builds up at waterfall
sites as a result of “sudden hydrological changes”, including enhanced
air–water contact and enhanced flow velocities, thereby resulting in
more rapid CO2 degassing than is found along stretches of streams
with more shallow gradients. Carbon dioxide degassing influenced by
turbulence can occur from springs and spring-fed lakes (Coxon, 1994)
but is limited where pCO2 in the lake and atmosphere are close to
equilibrium (Fig. 6). Environments where degassing is encouraged
through turbulence (such as waterfalls) also tend to be quite dynamic,
with low potential for preservation of any resulting deposit on
geological timescales.
4.3.4. Evaporation
Evaporation causes precipitation by concentrating ions in the
remaining solution. This is well known as a factor in precipitation of
evaporites such as gypsum and “exotic” carbonates (Atkinson, 1983;
Harmon et al., 1983) like huntite (Mg3Ca(CO3)4) as well as calcite and
aragonite (Thrailkill, 1971) in caves. So long as evaporated water can
be transported out of the system, mineral precipitation through
evaporation can occur when cold air blowing through the cave is
heated by the warmer walls (e.g. Harmon et al., 1983). Evidence for
this process is provided by speleothems that are orientated in the
direction of strong air flow. Even so, the ability of evaporation to
produce significant amounts of speleothem is questionable (Harmon
et al., 1983).
Calcite supersaturation resulting from evaporation has been
suggested for precipitation of much carbonate from lakes (e.g. Müller
et al., 1972), often from very shallow and playa lake settings (for
example Eugster and Hardie, 1975; Risacher and Eugster, 1979; White
and Youngs, 1980; Southgate et al., 1989). Candy et al. (2006) reported
calcrete nodules from the Middle Pleistocene of eastern England,
demonstrating that the requirement for calcrete formation by
evaporative processes is not just aridity but strong seasonality, with
periods of evaporation exceeding rainfall (perhaps in the summer) and
vice-versa in the winter. In some vadose zones of alluvial fans, ‘gully-
bed cements’ (Mack et al., 2000) preferentially coat the undersides
of clasts in channel-fill conglomerates, suggesting they form by
evaporation of bicarbonate-rich run-off. Once the interstices in conglo-
merates are cemented, a laminar calcrete sheet forms across the top.
Mack et al. (2000) suggest gully-bed cements form in the absence of
plants. Evaporation and evapotranspiration (see Section 4.4.3 below)
may not be so important for some groundwater calcretes precipitated
well below the surface (e.g. Nash and Smith, 2003).
4.3.5. Common-ion effect
The common-ion effect occurs in polymineralic systems with
calcite and gypsum or calcite and dolomite where solutions are
initially saturated with respect to calcite (Fig. 3E). Incongruent
dissolution of dolomite or dissolution of gypsum adds extra calcium
ions to the solution, which then becomes supersaturated with respect
224 A.T. Brasier / Earth-Science Reviews 104 (2011) 213–239

Fig. 6. Carbonate deposition in fluvial settings in the absence of vascular plants (based on the perched springline model of Pedley et al., 2003). Rain and snow falling on high ground
percolate down through sediments until they reach an impermeable horizon which then causes groundwaters to flow along the contact until emerging at a spring. In modern
settings, groundwaters have high pCO2 levels as a result of contact with organic-rich soils, and thus much degassing and calcite precipitation occurs at springs. Prior to the Silurian,
soils were thinner and less organic-rich, and atmospheres often had higher pCO2, such that degassing and travertine deposition at springs is likely to have been less significant than
found in Quaternary examples. Trees frequently provide obstacles to flow, thereby increasing turbulence (and hence CO2 degassing) leading to formation of barrages and upstream
ponding of waters to give rise to paludal facies. Prior to vascular plants, such barrage formation is likely to have been less frequent and paludal facies may well have been absent.
Nevertheless cyanobacteria may have produced travertine screens similar to those of Quaternary examples (see Andrews and Brasier, 2005; Brasier et al., in press). With time,
cascade tufas tend to become incised by the down-cutting streams and then abandoned. Travertine precipitation may resume lower down the valley. Such deposits are most likely to
be preserved and recognised as microbial carbonate clasts in conglomerates).

to calcite, causing the latter to precipitate (Eq. (13); see also Wigley,
1973a,b; Lohmann, 1988). Clear examples of this process, which can
produce quite substantial deposits, are found where calcite has
precipitated in gypsum caves (Calaforra et al., 2008) and where
carnotite (K2(UO2)2V2O8.3H2O), which will not form in the presence
of carbonate ions, is found in calcrete. In the latter case, the presence
of carnotite indicates carbonate ions had been efficiently stripped
from groundwaters by precipitating with the excess calcium (Carlisle,
1983; see further calcrete examples in Arakel and McConchie, 1982;
Arakel, 1986; Spötl and Wright, 1992; Nash and McLaren, 2003; Nash
and Smith, 2003; Jutras et al., 2007). The common-ion effect has also
been suggested as a cause of precipitation of Pleistocene lake tufas in
Mono Lake, California, USA (Dunn, 1953) and calcite precipitation in
the presence of gypsum from cold springs in ‘dominating Polar
conditions’ of the Canadian Arctic (Omelon et al., 2006; see also
Grasby, 2003) as well as hot spring carbonates (Pentecost, 1995). In
an oxic atmosphere, oxidation of sulphides such as pyrite (FeS2) can
produce both gypsum and sulphuric acid which may lead to karst
dissolution (e.g. van Everdingen et al., 1985; Hill, 1990) coupled with
calcite precipitation via the common-ion effect.
4.3.6. Freeze-out
Freezing of water (Fig. 3C) can also cause calcite (or aragonite; e.g.
Aharon, 1988) supersaturation and precipitation because calcium
preferentially partitions into the remaining liquid. This happens from
low ionic strength solutions where ice melts and refreezes below and
within glaciers sliding over limestone bedrock (e.g. Hallet et al.,
1978; Sharp et al., 1990; Fairchild et al., 1993) and from sea ice. In the
latter case calcium carbonate precipitates at just below − 1.9 °C,
followed by sodium sulphate (− 8.2 °C) and calcium sulphate at
− 10 °C (Richardson, 1976; Anderson and Jones, 1985; Papadimitriou
et al., 2004). Aharon (1988) suggested that weathering of calcium
silicates by carbonic acid (Eq. (1)) was the source of calcium and
bicarbonate ions for aragonite precipitation below Antarctic ice.
Killawee et al. (1998) and Papadimitriou et al. (2004) suggested
degassing of CO2 bubbles aides calcite precipitation. From caves, Žák
et al. (2004) reported loose, uncemented ‘cryogenic cave calcite’
crystals from the Pleistocene of Central Europe, and Žák et al. (2008)
suggest slower freezing produces larger crystals (up to 20 mm
diameter) than fast freezing. Cryptocrystalline carbonate powders
have been reported from the surface of ice stalagmites and stalactites
(e.g. Lacelle et al., 2009), but it seems amounts of modern precipitate
produced are often quite small, and carbonate flowstones, stalagmites
and stalactites are not likely to be formed by this process.
Freeze-out occurs in modern lakes including those of Antarctica (e.g.
Matsubaya et al., 1979) and Canada (e.g. Renaut and Long, 1987), and
may have caused vaterite (CaCO3 polymorph) precipitation from an
Arctic spring (Grasby, 2003). Canfield et al. (1983) who studied lakes in
Iowa, USA, reported that alkalinity which had risen due to this ‘freeze-
out’ effect fell immediately after ice melting, proving the two were
linked. Further, Cerling (1984) has suggested this process can cause
calcite precipitation in soils. Courty et al. (1994) later reported
laminated pendant calcite cements formed by freeze-out below coarse
clasts in fluvio-glacial sediments, and Vogt and Corte (1996) found
coatings on grains resulting from melting and re-freezing of permafrost
with calcium supplied by wind-blown dust. Studies of stable carbon
isotopes have been used to illuminate this process, including the study
of Cerling (1984) who postulated that modern soil carbonates
precipitated from freezing soils show δ13C values strongly influenced
by atmospheric compositions because biological respiration rates are
low. However this assumes the carbonate precipitates in equilibrium
with surrounding dissolved inorganic carbon and CO2. Clark and Lauriol
(1992) showed cryogenic calcite can be significantly enriched in 13C as a
result of kinetic effects. They reported values of up to +17‰ (PDB). But
an important conclusion here is that little or no biological influence is
required to precipitate soil carbonates within the freezing zone.
4.3.7. Precipitation from boiling springs
Boiling water is implicated in deposition of some hydrothermal
carbonates since boiling (in addition to the high temperature and thus
low calcite solubility) brings about degassing of CO2 (for example
Arnórsson, 1989). Even so, hot springs can often deposit calcite at
 A.T. Brasier / Earth-Science Reviews 104 (2011) 213–239 225

Table 2
Petrographic changes in spring, stream or lacustrine (‘SSL’) carbonates, calcretes and speleothems through time. For further speleothem fabrics see Frisia and Borsato (2010). This
table shows many of the fabrics found in non-marine carbonates and indicates likely maximum ages, particularly where biological involvement is required. Recognising pre-
Devonian non-marine carbonates may be hindered by the absence of fabrics considered diagnostic in more recent deposits, such as rhizoliths and rhizolites.

Fabric Spring, Stream and Description Diagram Organism Likely maximum age Reference(s)
Lake (SSL), Calcrete involvement? for example(s)
or Speleothem

Nodules/glaebules Calcrete Spherical to irregular indurated Abiological argillo- Origin of smectite Wieder and
concentrations of carbonate, pedoturbation clays (Archaean) Yaalon (1974)
generally mm to several cm in size

1 cm

Abiogenic laminar Calcrete Laminar calcrete crusts from a few Abiological Origin of calcretes Arakel (1982)
crusts mm to several centimetres thickness (Archaean)

1 cm

Tepees Calcrete Antiformal structures produced by Abiological Origin of calcretes Assereto and
buckling during expansion (Archaean) Kendall (1977)

1 cm
Floating grain fabric Calcrete Silt and sand sized grains floating Abiological Origin of calcretes Esteban and
in a micritic matrix where the matrix (Archaean) Klappa (1983),
appears to be supporting the grains Tandon and
Friend (1989)

1 cm
Circumgranular Calcrete Non-tectonic fractures around grains Abiological Origin of clay Esteban and
cracking produced by shrinking and swelling minerals (Archaean) Klappa (1983)
of clay minerals during desiccation
and hydration

1 mm
Crystallaria Calcrete Calcite-filled cracks, mostly formed Abiological Origin of calcretes Wright and
through desiccation and expansion (Archaean) Tucker (1991)

1 mm
Clay cutans Calcrete Ooid-like coatings of clay around a Abiological Origin of clay Esteban and
grain nucleus minerals (Archaean) Klappa (1983)

1 mm
Mosaics Calcrete Mosaics of calcite crystals of Abiological Origin of calcretes Wright and
different sizes (Archaean) Tucker (1991)

1 mm
Peloids Calcrete SSL Rounded micrite pellets, various Abiological (but see Origin of authigenic Tucker and
origins also faecal peloids) precipitates Wright (1990)
(Archaean)

500 µm

(continued on next page)

226 A.T. Brasier / Earth-Science Reviews 104 (2011) 213–239

Table 2 (continued)
Fabric Spring, Stream and Description Diagram Organism Likely maximum age Reference(s)
Lake (SSL), Calcrete involvement? for example(s)
or Speleothem

Pisoliths Calcrete SSL Concentrically laminated Abiological argillo- Origin of authigenic Esteban and
sphaeroids N 2 mm diameter pedoturbation and precipitates Klappa (1983),
down slope (Archaean) Tandon and
movement Friend (1989)

2 mm
Ooids Calcrete SSL Concentrically laminated Abiological argillo- Origin of authigenic Tucker and
sphaeroids b 2 mm diameter pedoturbation precipitates Wright (1990)
(Archaean)

1 mm
Columnar calcite SSL Elongate crystals wider than Abiological Origin of Kendall and
ten microns speleothems Broughton (1978),
(Archaean) Brasier et al.
(in press)

1 mm

Cave popcorn Speleothem Nodules found on smooth Abiological Origin of Thrailkill (1976)
flowstone, stalagmite or other speleothems
speleothem often containing (Archaean)
near-hemispherical laminations
which thin away from the axis
200 µm

Paper-thin rafts SSL (hot springs) Rafts of crystals with flat upper Abiological Origin of hot Guo and Riding
surfaces produced by rapid springs (Archaean) (1998), Chafetz
precipitation at the water surface et al. (1991)

5 cm

Coated bubbles SSL (hot springs) Millimetre to centimetre-sized Abiological Origin of hot Chafetz et al.
bubbles preserved by rapid springs (Archaean) (1991), Guo and
precipitation of calcite or aragonite Riding (1998)
in hot spring settings, often found
on undersides of rafts

5 cm

Ray/Feather crystals SSL (hot springs) Coarse elongate crystals oriented Abiological (Guo Origin of hot Chafetz and Folk
perpendicular to the depositional and Riding, 1992) springs (Archaean) (1984), Guo and
surface, sometimes forming Riding (1992)
conical radiating patterns

Crystal shrubs SSL (hot springs) Dendritic shrub-like crystals Bacteria (often in hot Origin of bacteria Chafetz and Folk
composed of upward radiating spring environments) (Archaean) (1984), Pentecost
branches (1990)

Sparry calcite fans SSL Speleothem Fan-shaped calcite crystals Abiological Origin of non- Love and Chafetz
(neomorphic marine carbonates (1988), Freytet and
or primary) (Archaean) Verrecchia (1998);
Brasier et al.,
in press)
 A.T. Brasier / Earth-Science Reviews 104 (2011) 213–239 227

Table 2 (continued)
Fabric Spring, Stream and Description Diagram Organism Likely maximum age Reference(s)
Lake (SSL), Calcrete involvement? for example(s)
or Speleothem

Needle Fibre Calcite Calcrete SSL Acicular calcite crystals with Abiological (strong Origin of non- Verrecchia and
lengths at least four times the evaporation, high marine carbonates Verrecchia (1994)
width: monocrystalline supersaturation) (Archaean)
micro-rods and polycrystalline
chains of Verrecchia and
Verrecchia (1994)
0.3 µm
Non-marine SSL Laminar microbial carbonates Cyanobacteria Origin of Andrews and
stromatolites formed in non-marine settings cyanobacteria Brasier (2005),
(Archaean) Irion and Muller
(1968)

3 mm

Micrite coated SSL (Cyano)bacterial sheaths coated Bacteria (including Origin of bacteria Freytet and
filaments in calcite. Organic materials often cyanobacteria) (Archaean) Verrecchia (1998)
decayed, leaving an external mould.

20 µm

Sparry calcite fans SSL Speleothem Fan-shaped calcite crystals Cyanobacteria Origin of Freytet and
cyanobacteria Verrecchia (1998)
(Archaean)

1 mm

Spherulites Calcrete “Calcitic fibro-radial spherulitic Cyanobacteria Origin of bacteria Verrecchia et al.
polycrystals” (Verrecchia et al., and bacteria (Archaean) (1995), Wright
1995) found in laminar crusts et al. (1996)

30 µm

Oncoliths SSL Layered, unattached carbonate Cyanobacteria Origin of Tucker and Wright
coated grain with a cortex of and algae cyanobacteria (1990), Nickel
non-concentric, partially (Archaean) (1983)
overlapping laminae

2 mm
Needle Fibre Calcite Calcrete SSL Acicular calcite crystals with Fungi, lichen Origin of fungi Verrecchia and
lengths at least four times the (Mesoproterozoic?) Verrecchia (1994)
width: coupled rod forms of
Verrecchia and Verrecchia
(1994)

Pisoliths Calcrete SSL Concentrically laminated Fungi, lichen Origin of fungi Beier (1987)
sphaeroidsN 2 mm diameter (Mesoproterozoic?)
composed of Needle Fibre
Calcite

2 mm
(continued on next page)
228 A.T. Brasier / Earth-Science Reviews 104 (2011) 213–239

Table 2 (continued)
Fabric Spring, Stream and Description Diagram Organism Likely maximum age Reference(s)
Lake (SSL), Calcrete involvement? for example(s)
or Speleothem

Lichen stromatolites Calcrete Laminar calcretes formed Lichen Origin of lichens Klappa (1979)
through repeated cycles (Neoproterozoic?)
of lichen action (both biophysical
and biochemical) on bedrock 1 cm
Coated macrophyte SSL External moulds of vascular Vascular plants, Origin of bryophytes Pedley (1990)
stems plant stems bryophytes (Ordovician) and
vascular plants
(Silurian)

1 cm
Faecal peloids Calcrete SSL Rounded micrite pellets Faeces of Origin of terrestrial Esteban and Klappa
resulting from invertebrate invertebrates invertebrates (1983)
defaecation in the soil (Silurian)

500 µm
Insect cocoons Calcrete Calcified insect cocoons Insects Origin of insects Esteban and Klappa
(Silurian) (1983)

1 cm
Rhizoliths Calcrete Organosedimentary Vascular plants Origin of vascular Klappa (1980)
structures produced by roots plant roots (Middle
Devonian)

30 cm
Laminar crust Calcrete Laminar calcrete crusts Calcification of Origin of vascular Wright et al.
rhizolite exhibiting ‘tubular fenestrae’ root mats plant roots (Middle (1988), Alonso-
Devonian) Zarza (1999)

2 mm
Alveolar septal Calcrete ‘Cylindrical to irregular pores, Vascular plant roots Origin of vascular Esteban and
fabric which may or may not be filled and mycorrhizae plant roots and Klappa (1983),
with calcite cement, separated mycorrhizal fungi Wright and
by a network of anastomosing (Middle Devonian?) Tucker (1991)
micrite walls’ (Esteban and
Klappa, 1983).
0.2 mm
Microcodium b Calcrete Calcified plant root cells Vascular plant roots Carboniferous Alonso-Zarza
(Kabanov, et al., et al. (1998)
2008)

0.3 mm
Microcodium Calcrete Calcite crystals resembling Plant roots (Klappa, Cretaceous Klappa (1978),
biological ‘cells in palisades 1978) or ‘mycelial (Kabanov, et al., 2008) Kabanov et al.
around small nucleii’ saprotrophic organism’ (2008)
(Kabanov et al., 2008)

0.5mm

much lower temperatures (e.g. 73 °C maximum reported by Fouke et from Italy), so this process seems responsible for few terrestrial
al., 2000, for Mammoth Hot Springs, Yellowstone, USA; 95 °C deposits today. Hyperthermophile archaebacteria are able to tolerate
maximum reported by Chafetz and Folk, 1984, for travertines of the temperatures up to ~120 °C and may therefore have been involved in
western USA; 39 °C reported by Guo and Riding, 1994, for hot springs precipitation of some hydrothermal carbonates (see, for example
 A.T. Brasier / Earth-Science Reviews 104 (2011) 213–239 229

Fig. 7. Middle Proterozoic redbeds and associated carbonates at Nipigon, Ontario, Canada. (A) Calcite which has replaced gypsum crystals in red mudstones. (B) Calcrete forming a
sheet with some lamination. (C) Stromatolite found in terrestrial (lacustrine) facies. (D) Overview of outcrop at Nipigon, Ontario, showing red mudstones at base, overlain by
silicified stromatolitic limestones with collapse breccias, buff marls and red mudstones with ptygmatic folding and buff-coloured calcitic mudstones with vugs formerly occupied by
gypsum. This section is cut by a dolerite sill (arrowed). Person for scale. (E) Conceptual model for the Nipigon section, with stromatolites around a lacustrine shore, surrounded by
aeolian and fluvial muds containing calcretes and gypsum nodules.

Chafetz and Folk, 1984; Guo et al., 1996; Fouke et al., 2000). Some
authors, on the basis of petrography, suggest that up to 90% of some
hydrothermal travertines are directly or indirectly produced by
bacteria (e.g., Chafetz and Folk, 1984). However a realistic biogeo-
chemical mechanism through which bacteria could cause precipita-
tion has not been detailed.
4.4. Biological influences on non-marine carbonates
Cyanobacteria, fungi, lichens and vascular plants all influence non-
marine carbonate build-up, and have likely altered physical appear-
ances of these carbonates through time.
4.4.1. Cyanobacteria
Photosynthentic uptake of CO2 by cyanobacteria (e.g. Merz, 1992;
Spiro and Pentecost, 1991), algae (e.g. McConnaughey, 1991) and
bryophytes may not be important in fast-flowing streams (e.g.
Pentecost, 1981) but it can lead to tufa precipitation (Eq. 13) in less
turbulent settings such as those found in some lakes (e.g. Ohlendorf
and Sturm, 2001). Warm lake waters may aide calcite precipitation in
such cases (for example Hodell et al., 1998). Cyanobacteria make
another important contribution to SSL carbonate precipitation by
producing extracellular polymeric substances (EPS), known to
promote calcite crystal nucleation in solutions of low ionic strength
(for example Emeis et al., 1987; Riding, 2000; Rogerson et al., 2008;
Pedley et al., 2009). In some cases carbonate build-up at waterfall sites
may not be possible without a cyanobacterial substrate to hold the
precipitate in place (for example Brasier et al., 2010).
4.4.2. Fungi and lichens
Fungi are not only responsible for release of calcium from silicates
(Section 3.2), but also have an important role in calcite formation in
non-marine environments. Calcium oxalate crystals such as whewel-
lite (CaC2O4·H2O) and polyhydrated weddellite (CaC2O4·2H2O in its
230 A.T. Brasier / Earth-Science Reviews 104 (2011) 213–239
simplest form; see Verrecchia et al., 1993) are found in mycorrhizal
mats (see Cromack et al., 1979; Verrecchia et al., 1993) and around
lichen thalli (e.g. Syers et al., 1967; Klappa, 1979; Burford et al., 2003)
where they are produced by reaction of biogenic oxalic acid with
calcium. Significantly, they promote rhizolith formation in soils
(Cromack et al., 1979). Dehydration of weddellite to whewellite
followed by transformation to calcite under the influence of bacteria
(Cromack et al., 1977) was supported as a viable mechanism by
Verrecchia et al. (1993) and Verrecchia and Dumont (1996).
4.4.3. Vascular plants
Vascular plants have affected spring, stream and lacustrine
carbonate facies by providing stable substrates for calcification. Facies
models of Pedley (1990), Pentecost and Viles (1994) and Pedley et al.
(2003) demonstrate cases of logs initiating barrage build-up by
increasing turbulence (and hence CO2 degassing) and providing a
substrate, as well as calcification of substrates provided by overhang-
ing branches and mosses. Many SSL carbonate facies (such as barrages
and curtains — see Pedley, 1990) are more likely to form in the
presence of bryophytes and vascular plants because of these effects.
An important effect of the arrival of vascular plants for soil
carbonates was the entrapment and binding of sediment (e.g. Cotter,
1978). Because many pedogenic calcretes source their calcium from
wind-blown dust, not chemical weathering of silicate bedrock (for
example Machette, 1985; Capo and Chadwick, 1999), the binding of
sediment would not only produce more alluvial overbank mud host
materials (e.g. Cotter, 1978; Dunagan and Driese, 1999; Davies and
Gibling, 2010), but also allow build-up of wind-blown calcium
favouring increased calcrete precipitation.
Enhanced capillary action due to plants drawing up groundwater
(Davies and Gibling, 2010) is unlikely to have significantly increased
pedogenic calcrete precipitation because most such calcretes are not
formed by capillary rise of underlying groundwaters (see Wright and
Tucker, 1991). However vascular plants allow evapotranspiration
rather than evaporation which might enhance rates of calcrete
deposition. For example, evapotranspiration can cause local calcite
supersaturation around roots (e.g. Calvet et al., 1975) leading to the
formation of calcite sheaths. Hsieh et al. (1998) examined oxygen
isotopic compositions of Hawaiian soil waters. They deduced that
increasing annual rainfall and decreasing temperature caused water
loss by evaporation to decrease and water loss by transpiration to
increase. Thus when temperatures cool and humidity increases
transpiration still operates and (at least in tropical regions) vascular
plants increase soil water loss.
Rhizoliths (organosedimentary structures produced by roots;
Klappa, 1980) are obvious features found in many pedogenic calcretes
that would not be expected without vascular plants (see Table 2).
Some rhizoliths form when calcium levels in soil solutions are high
and exceed the requirements of the plant. In this way calcium (and
hence calcite; Eq. (13)) accumulates in the rhizosphere (Hinsinger,
1998; Hinsinger et al., 2006). Plant roots that maintain their charge
balance by taking up protons or releasing bicarbonate ions when they
take up more anions than cations (see Sections 3.1 and 3.2) may also
create local supersaturation with respect to calcite (e.g. Klappa, 1980).
Interestingly, Wright et al. (1995) claimed that some calcretes are
“almost completely the result of root activity”, forming through
intracellular and extracellular calcification as well as through root
involvement in peloid formation. Such rocks have been termed
rhizolites (Klappa, 1980; Wright et al., 1988, 1995). Furthermore,
Jaillard (1984) reported that calcified roots may locally form up to a
quarter of the soil mass. Intracellular calcification may have produced
Microcodium (see Table 2) in many Moscovian to early Permian and
latest Cretaceous to Palaeogene (ages from Kabanov et al., 2008)
paleosols (Klappa, 1978; Jaillard et al., 1991; Wright et al., 1995;
Alonso-Zarza et al., 1998; Košir, 2004), although Kabanov et al. (2008)
suggest on morphological grounds that a ‘mycelial saprotrophic
organism’ not plants, roots or root-associated mycorrhizae was
responsible. Horizontal root mats and their calcification may also
lead to laminar crusts (Wright et al., 1988), which can be inferred
from the presence of tubular pores formerly occupied by the plant
rootlets as well as by a ubiquitous alveolar septal structure (see
Table 2). In addition to this process, laminar calcite can also form by
calcification of root medullas (probably formed during the life of the
root). In these cases, extracellular calcite forms crusts around the
cortex, and may be accompanied by post-mortem calcified mucilag-
inous sheets of probable fungal origin (Alonso-Zarza, 1999). It should
not be forgotten that many other laminar calcrete crusts are the result
of non-root-associated biological processes, including structures
produced by cyanobacteria (e.g. Verrecchia et al., 1995) and lichens
(Klappa, 1979), and other laminar crusts can be explained by
abiological processes such as precipitation from groundwaters
ponded on impermeable surfaces.
4.5. Temporal changes in non-marine carbonate precipitation up to the
Devonian
In the absence of thick high pCO2 soils prior to the Devonian, some
precipitation of non-marine carbonates is both possible and expected.
It is true that some of the processes outlined above, such as freeze-out,
only cause relatively minor and local carbonate accumulations today.
It is also true that all of the described processes can occur in different
places at the same time. Even so, some notable events might have
altered the relative importance of these processes through the course
of Earth history (Fig. 2).
For example, it can be argued that hydrothermal surface and near
surface springs may have been more prevalent in Archaean and
Palaeoproterozoic times (as suggested by Walter, 1996) than today, in
part because of the higher heat flow on the hot young earth. If so, then
one might predict that more hot springs meant more carbonate
precipitated by boiling processes than is found at present. Archaean
marine hydrothermal carbonates are well known (e.g. Lindsay et al.,
2005), but preserved terrestrial deposits seem rarer. Hydrothermal
travertine is currently not known until ~ 2.2 Ga (Melezhik and Fallick,
2001) and ~ 1.79 Ga (Rainbird et al., 2006).
Aside from the apparent lack of preserved Archaean terrestrial
environments, atmospheric pCO2 levels were probably very high until
at least ~2.3 billion years ago (e.g. Bekker et al., 2004). So an apparent
lack of preserved Archaean terrestrial spring carbonates might also
reflect less precipitation, due to less vigorous equilibration of deep-
sourced CO2 with the higher pCO2 atmosphere. Further predictions
are that some CO2 degassing due to turbulence might have led to
precipitation of carbonate in Archaean and Palaeoproterozoic braided
streams (e.g. Buck, 1980), and degassing through temperature rise
could have caused some minor precipitation in the shallow subsurface
of cold regions, though there is currently no evidence of the latter.
Marine carbonate platforms, known from ~ 2.6 Ga onwards
(Grotzinger, 1989), can present sources of calcium and bicarbonate
ions for non-marine carbonate precipitation when subaerially exposed
and eroded. But the apparently sparse record means any suggestion
that the origin of the carbonate platform was significant for calcrete
production is at best unproven. The oldest reported possible calcretes
are also found at around ~ 2.6 Ga (Watanabe et al., 2000; see Fig. 2 and
Table 1). In this case, Watanabe et al. (2000) suggest calcium was
derived from nearby granites, and HCO− 3 from the atmosphere.
Precipitation was caused by evaporation in a semi-arid setting.
The Huronian glaciation (e.g. Evans et al., 1997) must have
lowered global sea level and exposed some of these marine platform
carbonates. This is likely to have produced terrestrial environments
where palaeokarst surfaces and associated terrestrial carbonates
might be found. Carbonates of possible lacustrine origin in the
Espanola Formation of Ontario may be an example of this (e.g.
Bernstein and Young, 1990; Veizer et al., 1992).
 A.T. Brasier / Earth-Science Reviews 104 (2011) 213–239
Oxygenation of the Earth's atmosphere (e.g. Bekker et al., 2004)
must surely have influenced non-marine carbonate precipitation?
First, this atmospheric revolution seemingly allowed accumulation of
some of the first calcium sulphates in sabkha sediments by ~ 2.1 Ga
(Tulomozero Formation, Onega basin, Fennoscandia; Melezhik et al.,
2005a,b). With increasing local abundance of gypsum and anhydrite,
and their consequent dissolution to give groundwaters locally
enriched in calcium ions and sulphuric acid (the latter causing further
release of calcium ions through carbonate bedrock dissolution; see
van Everdingen et al., 1985), the relative importance of the common-
ion effect as a non-marine carbonate precipitation mechanism is likely
to have risen. The common-ion effect is able to produce relatively
large amounts of carbonate, and taken together with falling
atmospheric pCO2 levels (thereby favouring CO2 degassing processes),
an overall increase in non-marine carbonate (particularly speleothem
and groundwater calcrete) abundance would be expected in the rock
record at this time.
However the timing and scale of production of the first marine
sulphates is questioned by Kah et al. (2004), who suggest on the basis of
sulphur isotope modelling that atmospheric oxygen and marine
sulphate levels may initially have remained quite low (the latter being
5–15% of modern levels), only rising gradually to 75% of modern marine
sulphate levels by the end of the Proterozoic. If this scenario is correct
and the decline in atmospheric pCO2 levels was not initially rapid, then
groundwater calcretes and speleothems produced by the common-ion
effect, as well as through CO2 degassing, might not have been of any
great volume until the Meso- or Neoproterozoic. It is interesting to note,
with extremely limited data, that the oldest reported speleothem is not
found until ~1.2 Ga (Table 1; Glover and Kah, 2006; Skotnicki and
Knauth, 2007), which might support this view.
One might expect that some non-marine carbonates should have
formed from processes like ‘freeze-out’ at the time of the Cryogenian
‘snowball earth’ glaciations around 710–630 Ma (Kirschvink, 1992),
perhaps in sediments like those with permafrost sand wedges
reported from Mauritania by Deynoux (1982) and from Norway by
Edwards (1975). Non-marine carbonates which have been reported
from this time interval include microbially influenced calcretes
(Bertrand-Sarfati and Moussine-Pouchkine, 1983). Praekelt et al.
(2008) suggested South African palaeokarst of late Neoproterozoic to
early Cambrian age was related to glacio-eustatic sea level fall with
consequent subaerial exposure of carbonate bedrock, yet no spe-
leothems are described.
A problem related to these Cryogenian sediments concerns the
apparent lack of non-marine carbonates immediately following the
glaciations, when ‘cap carbonates’(see Shields, 2005, for a review)
were widely deposited in marine environments. Some cap carbonate
models (e.g. Higgins and Schrag, 2003) invoke extreme alkalinity
fluxes from terrestrial to marine environments, brought about by
rapid rates of carbonate and silicate weathering, so non-marine
carbonates are surely to be expected. A counter argument – that
generally high atmospheric pCO2 meant acidic terrestrial ground-
waters at a time of only weak CO2 degassing (hence few non-marine
carbonates) – does not seem to favour this model of cap carbonate
formation (see Shields, 2005).
Later subaerial exposure of the Cryogenian cap carbonates must
have provided further opportunities for bedrock dissolution and non-
marine carbonate precipitation: palaeokarst surfaces associated with
exposure of cap carbonates from the Marinoan glaciation in
northwestern Canada are described by James et al., 2001, and
calcretes of similar age and occurrence are described from the Lesser
Himalaya by Jiang et al., 2003.
Biological innovations during the late Neoproterozoic are also
likely to have exerted a major influence upon terrestrial carbonate
deposition. The hypothesised arrival of fungi and lichen at around this
time, with their microborings and biologically produced calcium
oxalates, likely influenced calcrete micromorphology (Table 2),
231
especially where precipitation took place within millimetres or
centimetres of the ground surface.
Warm, shallow, continent-flooding epeiric seas (Irwin, 1965)
during the Cambrian and Ordovician, combined with the Cambrian
innovation of marine organisms with carbonate skeletons, produced
much marine carbonate bedrock. Subsequent subaerial exposure of
such marine carbonates during the Cambrian likely provided both
calcium and bicarbonate ions for terrestrial carbonates like calcretes
associated with palaeokarst in the Hawker Group of Australia (James
and Gravestock, 1990) and calcretes in upward-shallowing peritidal
cycles of the Cambrian La Flecha Formation, Argentine Precordillera
(Keller et al., 1989; Buggisch et al., 2003).
The first firm evidence for land plants comes in the form of trilete
spores, possibly of terrestrial bryophytes (e.g. Strother et al., 1996;
Wellman and Gray, 2000). These are first known from the Llanvirn
(Middle Ordovician). As potential substrates for calcification around
springs, streams and lakes, and by initiating evapotranspiration, it can
be argued that these first plants probably influenced SSL carbonate
morphology and occurrence, but where are the examples? A lack of
roots may have restricted the influence of these first plants on silicate
weathering (Algeo et al., 2001). Production of thin organic-rich soils
likely started to accelerate in the Ordovician, a process which is
perhaps reflected in the production of some Ordovician karst-
associated cements (e.g. Read and Grover, 1977; Grover and Read,
1978; Tobin and Walker, 1994) and palaeokarst surfaces (Jia-yu and
Johnson, 1996; Ryu et al., 2005). Glaciation-related eustatic sea level
fall at the end of the Ordovician (e.g. Hambrey, 1985) is believed to
have exposed much Ordovician carbonate bedrock to karstification
(e.g. Jia-yu and Johnson, 1996).
While a few Silurian calcretes are known (e.g. Wright et al., 1992;
Davies et al., 2005), Silurian SSL carbonates and speleothems have
gone as yet unreported. This might reflect lack of preservation, or lack
of detection. One can speculate that cyanobacterial influence upon
lacustrine and fluvial carbonate precipitation (Fig. 6) is likely to have
decreased during the Silurian in response to increased competition
from early plants for growing space and increased grazing by
herbivores (see Shear, 1991).
A common feature of many (though not all) pre-Devonian calcretes
is their occurrence in alluvial fan facies rather than floodplain sediments
(for example Elmore, 1983; Aspler and Donaldson, 1986; Kalliokoski,
1986; De Ros et al., 1994). This may be because alluvial fans were
more widespread than floodplain environments before the stabilising
effect of plant roots (e.g. Cotter, 1978; Algeo et al., 2001; Davies and
Gibling, 2010). Terrestrial carbonate production is inferred to have
accelerated when plants with deep roots, their symbionts, and resulting
thick organic-rich soils became established in the Middle Devonian
(e.g. Alonso-Zarza and Tanner, 2010; Davies and Gibling, 2010).
5. Recognising Silurian and older non-marine carbonates
As shown above and in Table 1, the emergence of vascular plants
(though important) was not a prerequisite for terrestrial carbonate
precipitation. Many other and earlier events are likely to have
influenced terrestrial groundwater alkalinity and non-marine car-
bonate abundance during the course of Earth history (Fig. 2). If this is
true, then such deposits should have a record that stretches far
beyond the Devonian. The following therefore provides a preliminary
overview of the likely physical appearance of such non-marine
carbonates in ‘deep time’.
5.1. Petrographic changes of non-marine carbonates through time?
SSL carbonate, calcrete and speleothem are all influenced by a
variety of biological and environmental factors, each of which has
varied through time. It follows that petrographic features of non-
marine carbonates are also likely to have changed through time.
232 A.T. Brasier / Earth-Science Reviews 104 (2011) 213–239
Wright and Tucker (1991) usefully divided calcretes into those with
biological β fabrics and those with abiological α fabrics. β fabrics,
which include features like alveolar septal fabric, are mostly linked to
the influence of vascular plants and fungi. In contrast, α fabric features
such as circumgranular cracking are often the result of the displacive
and replacive nature of calcrete growth, and need not require biology.
Because the timings of major biological innovations and of major
environmental changes are relatively well constrained, it is possible to
ascribe a likely maximum age and (where applicable) a minimum age
to petrographic features found in terrestrial carbonates (see Table 2).
This table is intended to show how Silurian and older non-marine
carbonates might be expected to appear. Table 2 can also be compared
with Table 1 which shows many of the features of currently accepted
examples.
Data assembled in Tables 1 and 2 reveal that many features of
speleothems, SSL carbonates and calcretes found in post-Silurian rocks
should be recognisable in older rocks, from the late Archaean onward.
Calcareous nodules ought to be amongst the oldest kinds of
carbonate to be found in terrestrial deposits on Earth, though reported
examples are quite rare. Plausible examples include those reported
from Canadian Palaeoproterozoic fluvial and lacustrine sands: these are
spherical to elliptical and up to 5 cm diameter, of likely groundwater
origin, and (unlike many modern pedogenic nodules) are absent from
the finer grained alluvial faces (Aspler and Donaldson, 1986).
Mesoproterozoic pedogenic calcrete nodules from Michigan described
by Kalliokoski (1986) are much smaller, up to 3 mm diameter and are
oval in shape. They are found in association with carbonate coated
siliciclastic clasts, floating grain fabric and tepee structures. From the
same area, Kalliokoski and Welch (1985) described layers of nodules,
the latter being each up to 3 cm diameter, together with mudstones
exhibiting crystallaria (Table 2). From a Middle Cambrian supratidal
environment, Post and Long (2008) illustrated a structureless carbon-
ate bed a few tens of centimetres in thickness which probably formed
through coalscence of calcrete nodules. Ordovician argillaceous
palaeosols have also been found to contain ‘common small yellow’
carbonate nodules (Retallack, 2001). From this admittedly meagre list,
it can be argued that calcrete nodules are neither confined to nor
indicative of Devonian and younger alluvial floodplain sediments.
Similarly, it can be argued that laminar crusts were present in non-
marine deposits from the earliest times. Rare examples from the
Palaeoproterozoic include those from Fennoscandia (e.g. Melezhik et
al., 2004). About a billion years younger are the laminated, silicified,
haematite-rich crusts of the ~1.2 Ga Mescal Limestone of Arizona, USA
(Beeunas and Knauth, 1985). Younger still are the layered orbicular
crusts reported from the Neoproterozoic of Mali (Bertrand-Sarfati and
Moussine-Pouchkine, 1983). These possible calcretes consist of
alternating dark and clear microspar layers, associated with oncoids
and sediment-filled cavities.
Early Palaeozoic laminar crusts are also uncommon in the literature.
From a middle Cambrian evaporitic playa lake dry mud flat setting,
Southgate et al. (1989) have reported dolomite crusts represented by
discontinuous rinds of 0.1 to 2 mm thickness, with sharp tops and
gradational bases. A laminated calcrete clast of Cambrian to Ordovician
age was also illustrated from alluvial fan and braided fluvial sediments
by De Ros et al. (1994). The latter cases illustrate, at least, that ancient
calcrete laminar crusts may be found in ancient terrestrial deposits.
Further ancient calcrete fabrics, such as pisoids, have been
documented from pre-Devonian rocks. For example, in the Argentine
Precordillera (Keller et al., 1989), Cambrian pisoidal calcretes are
described as up to 1 metre thick. The pisoids comprise alternations of
white and brown micritic layers, surrounded by clays. These clay
layers might be interpreted as pedogenic cutans (Table 2). Mudcracks
and tepees are also associated with these La Flecha Formation
calcretes. Older examples of pisoliths have been reported from the
Mesoproterozoic Kanuyak Formation of NW Canada (Pelechaty and
James, 1991; Pelechaty et al., 1991), where beds are similarly of metre
thickness and also reverse-graded. Here, pisoids are cemented into
clusters of ‘grapestones’, suggesting cementation took place in situ
(Pelechaty and James, 1991). Pisoliths are present in the Kuetsjärvi
Sedimentary Formation of Fennoscandia, of Palaeoproterozoic age
(Melezhik et al., 2004). It is possible that such ancient pisoliths formed
through an abiotic process of shrinking and swelling of clays (e.g.
Tandon and Friend, 1989) and through downslope transport of grains
(e.g. Arakel and McConchie, 1982).
Some Recent pisoliths are themselves composed of Needle Fibre
Calcite (e.g. Beier, 1987; see Wright and Tucker, 1991), a term which
refers to acicular crystals with lengths at least four times the width
(see James, 1972; Verrecchia and Verrecchia, 1994; Table 2). Needle
Fibre Calcite has been explained by both fungal influence and
abiological processes (both types described in Verrecchia and
Verrecchia, 1994). In turn, this raises questions about microbial
participation in the formation of very ancient pisoliths like those
mentioned above. Interestingly, however, Needle Fibre Calcite is
seemingly unknown before the Carboniferous (Wright, 1984). It
remains unclear whether pisoliths which lack Needle Fibre Calcite
require microbial involvement to form.
Carbonate coated macrophyte stems might be theoretically
expected from rocks of Ordovician age onward, following the advent
of bryophyte-like organisms at that time (e.g. Wellman and Gray,
2000). It seems, however, that they have not been reported from rocks
older than Lower Carboniferous (e.g. Rex and Scott, 1987; Scott and
Galtier, 1988). As the siliceous Rhynie Chert of Lower Devonian age
has shown, mineral-precipitating springs can preserve excellent
records of early terrestrial life (e.g. Trewin and Rice, 1992). Hence
there are reasons to predict that Silurian, and even Ordovician
macrophytes were coated by carbonate in calcareous spring deposits
yet to be reported.
Rhizoliths are found abundantly in calcretes from the Upper
Devonian onwards (for examples see Klappa, 1980; Wright and
Tucker, 1991 and references therein; Balin, 2000). Like the coated
macrophytes, they are not yet reported from pre-Devonian examples
(Table 2). It could be that the absence of key macro-morphological
features such as rhizoliths, or indeed fabrics like calcified root mats,
alveolar septal fabric and Microcodium, has hitherto hindered the
recognition of many ancient SSL carbonates and calcretes. Interpreta-
tions until now have therefore had to remain very tentative. For
example, James and Gravestock (1990) and Post and Long (2008)
have been careful to describe only ‘possible’ Cambrian calcrete
examples. Hopefully this review will help to open up the search for
early terrestrial carbonates and their fabrics.
5.2. Further examples of Proterozoic terrestrial carbonates from North
America
The example illustrated in Fig. 7 displays Proterozoic calcretes
(Fig. 7B) and non-marine stromatolites (Fig. 7C) associated with
redbeds (Fig. 7A; D) of the Mesoproterozoic Sibley Group of the
Keweenawan Rift system which crop out at Nipigon, Ontario. Facies
include red coloured alluvial and wind-blown muds containing
gypsum pseudomorphs and laminated calcretes with tepee struc-
tures; stromatolitic limestones with evaporite solution collapse
breccias; and buff-coloured marls containing ptygmatic folds. These
facies point towards a semi-arid system with evaporite (and calcite?)
precipitation caused by high evaporation.
Stromatolites are likely to have developed around the margins of
ephemeral lakes, where it is likely that some of these cyanobacte-
rially-influenced carbonate build-ups formed through of a combina-
tion of biological and chemical processes. The availability of calcium
from dissolution of calcium sulphates and wind-blown sources may
have led to some groundwater calcrete precipitation via the common-
ion effect, coupled with assistance from evaporation and perhaps
some actinobacterial or even fungal encouragement where
 A.T. Brasier / Earth-Science Reviews 104 (2011) 213–239
precipitation occurred within a few centimetres of the ground surface,
although petrographic evidence of the latter (e.g. Needle Fibre Calcite;
see Table 2) has not yet been found and might not have been
preserved.
Related Keweenawan non-marine carbonates associated with
alluvial fan and braided fluvial facies have been reported by Elmore
(1983) from the Copper Harbor Conglomerate of Michigan, USA. Their
reports of gypsum moulds and desiccation cracks are both consistent
with a semi-arid setting. The presence of stromatolites plus sparry
calcite fans as well as ooid grains (Table 2) is similarly consistent with
their formation in short-lived lakes of this age (Elmore, 1983 and
Table 2). Kalliokoski (1986) also studied calcrete cements from
Keweenawan conglomerates of Michigan, and likewise concluded
that evaporation was an important factor in their formation.
Petrography of these calcretes is consistent with a shallow ground-
water origin, and with the age of the rocks, based on features
described in Table 2. It is now interesting to consider whether pre-
Silurian non-marine carbonates contain a valuable record of pre-
Silurian land surface biotas.
5.3. Do non-marine carbonates contain a record of pre-Silurian land
surface habitation?
There has been much speculation of pre-Silurian terrestrial land
cover (e.g. Campbell, 1979; Golubic and Campbell, 1979; Wright,
1985; Shear, 1991; Prave, 2002; Knauth and Kennedy, 2009). Biota
from 1 Ga onwards have been suggested to include protists, mosses,
fungi, liverworts and (from 600 Ma) lichens (Knauth and Kennedy,
2009). If these authors are correct, evidence might be found in the
micro-fabrics of pre-Ordovician calcretes. However Needle Fibre
Calcite which might indicate the presence of fungi or lichens in fossil
deposits (e.g. Carboniferous examples in Wright, 1984) could be
dismissed as abiogenic (e.g. James, 1972) or modern overprint unless
petrography proves otherwise (see Freytet and Verrecchia, 2002).
Other structures which might be looked for include microborings,
such as those reported from modern feldspar and hornblende grains
by Jongmans et al., 1997. Studies of Palaeoproterozoic calcretes have
not hitherto found any unequivocal biological fabrics but Bertrand-
Sarfati and Moussine-Pouchkine (1983) believed some laminar
fabrics in calcareous soils of the younger (700–600 Ma) Sarnyéré
Formation of Mali to be microbial in origin.
Lichen-like fossils and possible fungal hyphae of the ~ 551–
635 Ma Doushantuo Formation, China (Yuan et al., 2005) are not
known from carbonates, but from marine phosphorites. However
Horodyski and Knauth (1994) reported fossil bacteria preserved in
cherts associated with palaeokarst surfaces of the ~ 1.2 Ga Mescal
Limestone, Arizona, USA, and Kenny and Knauth (2001) suggest
“secondary carbonate” associated with the karst is depleted in 13C
relative to other parts of the section by up to 11‰ (vs PDB) which
they attribute to input of light 12C from photosynthesising commu-
nities on the karst surface. Upfold (1984) reported tufted calcitic
stromatolites from the Stoer Group, but these have since been re-
interpreted as thin layers of secondary carbonate interlayed with
thin layers of mud containing evaporitic fabrics (Prave, personal
communication, 2010).
Proterozoic non-marine stromatolites (Fig. 7C) which might be
considered terrestrial microbial carbonates (see Table 2) include
lacustrine stromatolites of the ~1 Ga Copper Harbor Conglomerate,
Michigan, USA (Elmore, 1983) and ~1.3 to ~ 1.8 Ga stromatolites in
alluvial conglomerates of the Murky Formation, Northwest Canada
(Hoffman, 1976) as well as putatively lacustrine stromatolites of the
Tumbiana Formation of the Pilbara Craton, Australia (Awramik and
Buchheim, 2009). Late Ordovician soil of the Juniata Formation,
Pennsylvania, USA, contains carbonate-sheathed burrows, and Retal-
lack (1985) speculated the carbonate might be of fungal origin.
233
5.4. Are Silurian and older non-marine carbonates usually recognised
and reported?
It is clear from Table 2 that many of the features associated with
calcretes and SSL carbonates are produced or influenced by terrestrial
organisms. Comparatively few examples of non-marine carbonate are
reported from pre-Devonian rocks; the literature study of Davies and
Gibling (2010) indicates nodular calcretes are more frequently
reported from Siluro–Devonian age alluvial settings than from older
(Cambro-Ordovician) deposits. Whether this apparent sudden in-
crease in reports of soil carbonate is really due to the arrival of
vascular plants (Alonso-Zarza and Tanner, 2010; Davies and Gibling,
2010) or whether older non-marine carbonates are under-reported
must be considered. So might non-marine carbonates have been
overlooked?
5.4.1. Cave carbonates
There is a strong literature bias towards studies of Quaternary
speleothems because they can be dated by U–Th radiometric methods
and used in palaeoclimatic reconstructions (see Fairchild et al., 2006).
It is predicted that speleothem fabrics ought to be associated with
examples of karst solution (for some examples see Table 1), unless
calcium was routinely transported away by acidic, undersaturated
solutions in the past. Yet while mention of pre-Silurian palaeokarst is
relatively common (for example James and Gravestock, 1990;
Pelechaty et al., 1991; Horodyski and Knauth, 1994; Gutzmer and
Beukes, 1998; Kenny and Knauth, 2001; Ryu et al., 2005; Yuan et al.,
2005; Post and Long, 2008; Keller and Lehnert, 2010) reference to
‘speleothem’ is rare (Pelechaty et al., 1991; Glover and Kah, 2006;
Skotnicki and Knauth, 2007). This suggests that a lack of reference to
ancient speleothem deposits is not due to a lack of preservation of
exposure surfaces. It may be that preserved examples are seen as
secondary, post-depositional features (not part of the primary
depositional story), so referred to as ‘calcareous cement’ or ‘secondary
carbonate’ (e.g. Kenny and Knauth, 2001).
5.4.2. Spring, stream and lacustrine deposits
If pre-Devonian groundwaters were predominantly alkaline, with
the highest pH values in the Middle Ordovician (Jutras et al., 2009),
one might expect more pre-Devonian SSL deposits than currently
reported (Table 1). But while reports of terrestrial microbial deposits
are rare, reports of marine stromatolites (e.g. Riding, 2000) are
common, so it is possible to speculate that some terrestrial microbial
carbonates have been mis-identified as marine: the difficulty of
distinguishing lacustrine from marine successions in the absence of
incontrovertible fossil evidence is illustrated by the disagreement
over the Tumbiana Formation (see Awramik and Buchheim, 2009, and
references therein). Confusion with later diagenetic calcite cements is
problematic, and early diagenetic processes, such as aggrading
neomorphism (Love and Chafetz, 1988, but see also Brasier et al., in
press) and micritisation, might hinder the recognition of ancient SSL
carbonates. Examples of SSL carbonate are known from the Permian
(Szulc and Cwizewicz, 1989; Stworzewicz et al., 2009), but Devonian
and Carboniferous reports are still as rare as those from preceding
times, and this might reflect small amounts of deposition in
environments unlikely to be preserved.
5.4.3. Calcretes
The lack of Silurian and older calcretes observed by Davies and
Gibling (2010) might be partly due to their definition: “accumulations
of nodular carbonate in mudstones”. Consequently laminar fabrics are
seemingly not included in their assessment. ‘Typical’ calcrete-
containing soil profiles formed in the organic-rich modern terrestrial
world may be highly variable from place to place, but are easily
recognised (e.g. Esteban and Klappa, 1983) whereas the significance
of cements in alluvial fans (e.g. the Proterozoic Copper Harbor
234 A.T. Brasier / Earth-Science Reviews 104 (2011) 213–239
Conglomerate; Elmore, 1983) might easily be overlooked. Retallack
(1986) highlights that while weakly developed post-Ordovician soils
may be identified by the presence of “fossil roots or trace fossils”, these
will be lacking in equivalent weakly developed Precambrian examples. In
some cases, closer examination reveals that calcrete fabrics might easily
have gone un-noticed, such as “microscopic concretions” or “micro-
nodules” which are “similar to pedogenic carbonate” in Proterozoic soils
of NW Scotland (Retallack and Mindszenty, 1994).
Many pre-Devonian alluvial fans (e.g. the Cambrian White Point
Conglomerate; Daily, 1980) are known, so depositional environments
do not seem to have been lacking. Some of these alluvial fans might be
found to contain calcrete cements on further inspection, but
unfavourable climatic conditions for deposition or preservation (too
wet or too dry) could also be responsible. This might be true in cases
where calcrete fabrics have clearly been looked for and not found (e.g.
rarity of calcretes in some Canadian Palaeoproterozoic alluvial fans
noted by Aspler and Donaldson, 1986; lack of calcretes in Cambrian
peritidal carbonates of the Appalachians, USA, reported by Osleger
and Read, 1991).
There also seems to have been a paucity of studies centred on
calcretes from pre-vascular plant times. For example, numerous
articles have been published on terrestrial clastic sediments of the
Ringerike Group of Norway (such as Turner and Whitaker, 1976;
Turner, 1974; Davies et al., 2005, 2006), but these contain only limited
mention of ‘concretions’ and nodules interpreted as calcrete by Davies
et al. (2005) and Davies and Gibling (2010). Similarly Gutzmer and
Beukes (1998) reported Palaeoproterozoic haematitic laterites from
South Africa, but associated calcretes (Gutzmer, personal communi-
cation, 2010) have apparently never been worked on.
6. Conclusions
A first conclusion from this study is that some definitions currently
applied to Quaternary terrestrial carbonates are hard to apply to
ancient ones. The terms ‘tufa’ and ‘travertine’ imply circumstances
which cannot be easily verified in ‘deep time’ such as locally elevated
water temperatures, and in cases where depositional conditions are
unclear, might be avoided in favour of more descriptive terminology.
Alternative phrasing such as ‘spring carbonate’, ‘stream carbonate’
and ‘lacustrine carbonate’ is less restrictive than ‘tufa’ and ‘travertine’
and relevant to discussions of deposition in different terrestrial
settings in this review (e.g. Section 4 and Table 2).
Fungi, like those known to release calcium from apatite, might be
older than vascular plants with roots. The origin of fungi was likely an
important event for chemical weathering of bedrock and non-marine
carbonate precipitation. However it is probable that the development
of vascular plants with large root systems and symbionts in the
Middle Devonian resulted in acceleration of silicate weathering. Low
pH levels in the rhizosphere from organic and carbonic acids surely
caused increased dissolution of carbonate bedrock. Clay minerals
produced during silicate weathering probably only provide a short-
lived barrier to chemical weathering.
Thick, organic-rich soils (strongly influenced by vascular plants)
are today involved in the precipitation of significant volumes of
speleothem, SSL carbonate and calcrete by encouraging carbonic acid
production leading to carbonate bedrock solution and consequently
re-precipitation of calcite in terrestrial environments. In the absence
of high pCO2 soils, terrestrial carbonates could still have precipitated
by several mechanisms, which may each have varied in their relative
importance through time. Boiling is likely to have been more
important on a young Earth with higher heat flow, yet deposits are
seemingly unknown; CO2 degassing is likely to have been less
vigorous at times of high atmospheric pCO2; evaporation has likely
always been an important factor in surface and shallow environ-
ments; the common-ion effect might have increased in importance
through time, particularly with precipitation of calcium sulphates as
the atmosphere became oxic; freeze-out (today a seemingly minor
process) may have been slightly more important during the colder
phases of Earth history. It is also possible that carbonic acid played a
lesser role in the distant past; for example, some surface ground-
waters may locally have become quite acidic following oxygenation of
the atmosphere and oxidation of sulphides in the Palaeoproterozoic.
The origin of vascular plants and earlier bryophytes was clearly
significant for terrestrial carbonate precipitation. These plants, together
with their symbionts, produced thick organic-rich soils and enhanced
both evapotranspiration and trapping of calcium-rich wind-blown dust.
Some other events which may also have been important include the
origin of carbonate-precipitating microbes in the Archaean; formation
and exposure of marine carbonate platforms from the late Archaean;
oxygenation of the atmosphere in the Proterozoic, leading to more
vigorous degassing of CO2 from groundwaters to the lower pCO2
atmosphere, production of H2SO4, CaSO4 and calcite precipitation via the
common-ion effect; formation and exposure of the Cryogenian ‘cap
carbonates’; the origin of fungi, which produce calcium oxalates and
release calcium from minerals from the late Proterozoic; and carbonate
production by marine organisms since the Cambrian.
Because organisms associated with non-marine carbonates have
changed through time, the physical appearances of non-marine
carbonates have also changed through time (Table 2). Known
examples of calcretes, SSL carbonates and speleothems formed in
‘deep time’ (Table 1) fit the predicted patterns of appearance based
on likely depositional processes and influential organisms according
to age and setting; a further example of this is provided by Pro-
terozoic calcretes and lacustrine stromatolites of the Keweenawan
rift system.
Terrestrial carbonates record some evidence of pre-Silurian land
colonisation in the form of stromatolitic cyanobacterial build-ups in
lacustrine strata, perhaps as long ago as the Archaean. Microbial
fabrics have been reported from Neoproterozoic calcretes, and calcite
which might be attributed to fungi from Ordovician soils.
There is annecdotal evidence that speleothems, SSL carbonates and
calcretes from Silurian and older times are under-reported. Possible
reasons for this include an assumption that many or most calcite
cements are of late diagenetic origin; confusion of terrestrial for
marine deposits; or destruction of original textures through early
diagenesis or metamorphism.
Acknowledgements
Helpful comments on an early draft of this manuscript were
provided by Tony Fallick (SUERC), IGME gave permission to work in
Greece. Tony Prave (St Andrews) and Martin Brasier (Oxford). Mike
Simmons and Richard James (Neftex Petroleum) suggested some
formations which might contain non-marine carbonates for Table 1.
Dineke Brasier assisted with proof reading. The journal editors and
reviewers provided helpful comments. ATB is supported by NERC
grant NE/G00398X/1.
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