Sedimentary Geology 294 (2013) 315–327

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Sedimentary Geology
journal homepage: www.elsevier.com/locate/sedgeo

A genetic model for Na-carbonate mineral precipitation in the Miocene

Beypazarı trona deposit, Ankara province, Turkey
Javier García-Veigas a,⁎, İbrahim Gündoğan b, Cahit Helvacı b, Eva Prats a
a
CCiTUB, Scientific and Technological Centers, Universitat de Barcelona, 08028 Barcelona, Spain
b
Dokuz Eylül Üniversitesi, Mühendislik Fakültesi, Jeoloji Mühendisliği Bölümü, Tınaztepe Yerleşkesi, 35160 Buca-İzmir, Turkey

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

Article history: The Miocene Beypazarı trona deposit in Central Anatolia (Turkey), with estimated reserves of 250 million of tons
Received 17 May 2013 of soda ash (sodium carbonate), is the second largest Na-carbonate deposit in the world. Petrographic observa-
Received in revised form 28 June 2013 tions of sodium-carbonate evaporites from basin-center cores show that the evaporites and associated minerals
Accepted 30 June 2013
underwent significant early diagenetic mineral transformations in the Beypazarı Basin.
Available online 6 July 2013
Trona, pirssonite and nahcolite are the major evaporite minerals, with subordinate bradleyite, shortite and
Editor: B. Jones thenardite. Pirssonite occurs in organic-rich muds (oil shales). Pirssonite is not a primary mineral but rather
appears to have formed diagenetically from displacive gaylussite. Trona precipitated subaqueously (in lake
Keywords: waters) and as interstitial phase in playa muds. Nahcolite is a later diagenetic mineral replacing both trona
Trona and pirssonite beds. Evaporite minerals are closely related to pyrite in oil shales and are also associated
Gaylussite with diagenetic silicates (Mg-rich smectites, zeolites, K-feldspar, searlesite, and idiomorphic quartz) formed
Pirssonite by reaction of alkaline brines with pyroclastic deposits.
Nahcolite The proposed sedimentary model involves an alkaline lake in which water depth fluctuated from deep, pe-
Shortite
rennial, meromictic (stratified) stages to shallow, ephemeral, playa lake stages. Lake margin clastic deposits
Bradleyite
are absent in the center of the basin wherein Na-carbonate minerals were formed, suggesting the prevalence
of a groundwater regime during drawdown events.
© 2013 Elsevier B.V. All rights reserved.

1. Introduction Tiercelin, 1994) to more concentrated, ephemeral lakes (e.g., Lake

Magadi and Lake Natron, Kenya; Eugster, 1980). Geysers and perennial
Sedimentary Na-carbonates are an evaporite mineral group hot springs in these alkaline lake systems are fed by deep groundwaters
formed in alkaline lakes (also known as soda lakes) with pH typically coming from marginal streams that disappear in alluvial fans before
between 9 and 12. Na-carbonates occur in endorheic depressions re- they reach valley centers and are more likely derived from deep seated
lated to volcaniclastic (tuff) deposits, hydrothermal activity and high hydrothermal systems (Renaut et al., 2013). Trona, called “magadi” in
concentrations of extreme organisms. In these settings, lake waters East Africa, is the main Na-carbonate mineral precipitated in some of
are characterized by relative enrichment in HCO− 3 + CO3
2−
with re- these modern soda lakes. Lake Magadi has become the prototype for al-
2+ 2+ 2+
spect to Mg + Ca . During evaporation, after Mg and Ca2+ kaline lakes (Baker, 1958, 1963; Surdam and Eugster, 1976; Jones et al.,
are almost exhausted during calcite, magnesite, and dolomite precip- 1977; Eugster, 1980; Monnin and Schott, 1984).
itation, Na-carbonate rich waters form. In addition, non-evaporite A second well-known Na-carbonate deposit is from Pleistocene
minerals, including authigenic silicates, also form in alkaline lakes in Searles Lake (California) (Smith, 1962, 1979, 2009). More than twenty
volcaniclastic terrains. Formulas of evaporite minerals discussed in Na-bearing evaporite minerals are present including carbonates, chlo-
this article are listed in Table 1. rides, sulfates, borates and borosilicates (Smith and Haines, 1964;
Although modern alkaline lakes exist in arid zones throughout the Eugster and Smith, 1965). Na-rich minerals (halite, trona, hanksite
world, the major Na-carbonate lakes occur along the East African Rift and borax) are chiefly found in saline units whereas Na–Ca-rich min-
System. Tectonic and climatic controls on rift escarpments and bedrock erals (gaylussite and pirssonite) occur predominate in muddy intervals.
geology dominated by Na-rich trachyte lavas supplied by recent volca- In spite of the high alkalinities of these lacustrine settings, they are,
nism led to the establishment of a large number of highly alkaline lakes in some cases, extremely productive because of high ambient tempera-
with variable salinity, depth and chemical composition, ranging from tures and light intensities, and unlimited supplies of CO2. Soda lakes are
perennial, meromictic lakes (e.g., Lake Bogoria, Kenya; Renaut and considered to be among the most productive aquatic environments in
the world (Grant and Tindall, 1986; Grant, 2004; Sorokin et al., 2011).
⁎ Corresponding author. Tel.: +34 934021701; fax: +34 934021398. In all cases, the microbial population is alkaliphilic or alkali-tolerant
E-mail address: garcia_veigas@ub.edu (J. García-Veigas). but with microbial diversity unique for each lake.

0037-0738/$ – see front matter © 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.sedgeo.2013.06.011
316 J. García-Veigas et al. / Sedimentary Geology 294 (2013) 315–327

Table 1 regime during the Late Miocene and Early Pliocene. The lower and middle
Chemical formulas for Na-carbonates, sulfates and borates cited in parts of the Miocene Beypazarı succession interfinger with pyroclastic
this article. Minerals marked with asterisk are those found in the
Beypazarı boreholes.
(tuff) and basaltic lava flows of the Teke Volcanics.
The Hırka Formation grades laterally and overlaps the Çoraklar For-
Carbonates mation (Helvacı, 1998). The studied borehole sections contain evapo-
Trona* Na3(HCO3)(CO3)·2H2O rites, oil shales, tuffs and mudstones but no alluvial or fluvial deposits.
Nahcolite* Na(HCO3) Based on borehole data, the Na-carbonate deposit of the Hırka
Shortite* Na2Ca2(CO3)3
Formation extends of approximately 8 km2 and is divided into two
Pirssonite* Na2Ca(CO3)2·2H2O
Gaylussite* Na2Ca(CO3)2·5H2O lensoidal bodies (Helvacı, 1998; Gündoğan and Helvacı, 2005; Helvacı,
Bradleyite* Na3Mg(PO4)(CO3) 2010). A total of 33 saline beds were identified, 16 in the ‘Lower Trona
Northupite Na3Mg(CO3)2Cl Unit’, and 17 in the ‘Upper Trona Unit’ (Helvacı, 1998). Maximum min-
Eitelite Na2Mg(CO3)2 eralized thicknesses are 60 m in the lower unit and 40 m for the upper
Dawsonite NaAl(OH)2CO3
unit. Individual Na-carbonate beds are commonly 0.4 to 2 m thick.
Sulfates These beds grade laterally into dolomite-bearing mudstones at the
northern margin of the basin, and to the south they are sharply truncated
Thenardite* Na2(SO4)
Mirabilite Na2(SO4)·10H2O by the Zaviye fault (Fig. 1).
Glauberite Na2Ca(SO4)2
Burkeite Na4(SO4)(CO3) 3. Material and methods
Gypsum Ca(SO4)·2H2O
Hanksite Na22K(SO4)9(CO3)2Cl
Sulfohalite Na6(SO4)2FCl
For mineralogical and petrological studies, a total of 138 core samples
were collected from eight exploratory boreholes drilled by the Etimine
Borates Works General Management of Turkey with support of the Scientific
Borax Na2(B4O5(OH)4)·8H2O and Technological Research Council of Turkey (Tübitak) and the General
Searlesite* NaBSi2O5(OH)2 Directorate of Mineral Research and Exploration (MTA) between 1982
and 1985 in the vicinity of the Beypazarı village (40° 10′ N; 31° 56′ E). Ad-
ditional hand samples from the upper trona unit were collected in mining
Geothermal activity, expressed as hydrothermal springs, plays an galleries. Synthetic logs and a correlation scheme of the studied boreholes
important role in early maturation of microbial organic matter and are shown in Fig. 3. Core samples were cut in half with a diamond wire
also in formation of evaporite minerals (Renaut and Tiercelin, 1994; saw and then polished for mineral identification under an environmental
Earman et al., 2005). scanning electron microscope (ESEM) coupled with backscattered elec-
The Eocene Green River Formation (Wyoming, Colorado and Utah, tron (BSED) and X-ray energy dispersive (EDS) detectors. In order to con-
USA) is the largest and best preserved Na-carbonate deposit. This firm the mineralogy of minerals with the same chemical components
giant lacustrine formation occurs in several sedimentary basins with (gaylussite, pirssonite, and shortite; trona and nahcolite), selected sam-
large volumes of oil shales and economically important Na-carbonate ples were powdered or microdrilled and then analyzed by X-ray diffrac-
deposits (Fahey, 1962; Bradley, 1964; Bradley and Eugster, 1969; tion (52). Thin sections (34) were prepared for optical observation with
Eugster and Surdam, 1973; Dyni, 1996; Smith et al., 2008). a polarizing microscope.
Nahcolite, not trona, is stable at high values of dissolved CO2
(Eugster and Smith, 1965). Based on primary nahcolite textures in the 4. Results
Green River Formation, Piceance Creek Basin (Colorado), and assuming
CO2 equilibrium between brine and atmosphere, an elevated carbon 4.1. Mineral occurrences
dioxide level for the early Eocene atmosphere was estimated by
Lowenstein and Demicco (2006). At present, trona is the main Na- The major mineral of the soda beds in Beypazarı is trona. Nahcolite
carbonate in ephemeral Lake Magadi (Kenya), meanwhile nahcolite and pirssonite are locally abundant and the main minerals in some
precipitates in Malha crater lake (Sudan), probably as a result of high bio- beds. Minor Na-carbonate minerals are shortite and bradleyite. Searlesite,
genic CO2 (Mees et al., 1991). The use of Na-carbonates to infer changes a Na-borosilicate, is abundant at the base of the lower unit. Although
in past atmospheric CO2 requires knowing the timing of mineral forma- sulfate minerals are essentially absent, traces of thenardite occur locally.
tion: (1) subaqueously in holomictic or meromictic lakes, (2) intersti- Pyrite, dolomite and quartz are abundant in almost all the soda beds.
tially from connate brines, or (3) diagenetic as replacements. Analcime and authigenic K-feldspar are chiefly related to tuff layers.
A detailed geological study of the Beypazarı deposit was done by Trona is by far the most common sodium carbonate mineral in
Helvacı (1998, 2010). The aim of this paper is to carry out a mineral- Beypazarı boreholes and forms decameter-thick trona beds. Four different
ogical and petrological characterization of the Beyparı trona deposit crystalline textures were recognized in the present work: ‘grass-like’,
by means of electron and optical microscopes, and to propose a plau- ‘massive’, ‘radiating-prismatic’ and ‘unoriented’. In all of them, trona crys-
sible genetic model for alkaline mineral precipitation. tals are prismatic or acicular and range from decimetric to millimetric in
length.
2. Geological setting Grass-like trona consists of vertically oriented crystals arranged
in fan aggregates (Fig. 4A). Rarely, upward- and downward-oriented
The Beypazarı trona deposit was discovered during exploratory fans were developed although those oriented upwards are more com-
drilling for lignite deposits in the Neogene Beypazarı Basin, in central mon and longer. Massive trona consists of submillimetric, unoriented
Anatolia, 100 km northwest of Ankara (Fig. 1) (Helvacı et al., 1989; crystals with scarce matrix (Fig. 4B). Radiating-prismatic trona consists
İnci, 1991). A Miocene succession, about 1200 m in thickness, rests of millimeter- to centimeter-sized aggregates of bladed crystals orga-
on metamorphic, ophiolitic, carbonate and clastic basement rocks nized in nodules grown in unconsolidated mud (Fig. 4C). Unoriented
ranging in age from Paleozoic to Eocene. The Miocene succession crystalline trona consists of millimeter- to centimeter-sized crystals
(Fig. 2) is divided into seven sedimentary formations by Helvacı scattered in mud and arranged in bundles (Fig. 4D).
(1998, 2010). Na-carbonate beds occur in the Hırka Formation. Pirssonite occurs in almost all the Beypazarı studied boreholes except
The Beypazarı Basin evolved from an extensional tectonic regime dur- in the most marginal ones (SJ35 and SJ17A). This Ca–Na-carbonate is
ing the Middle–Late Miocene time to a single-direction compressional mainly abundant in the Lower Trona Unit where it is the major evaporite
 J. García-Veigas et al. / Sedimentary Geology 294 (2013) 315–327 317

Fig. 1. Geological map of the Beypazarı Basin with location of the Beypazarı trona mine.
After Helvacı (2010).

mineral (Fig. 3). Pirssonite occurs in two principal crystalline textures: pirssonite-bearing oil shales, and trona beds (Fig. 6B). Despite the
(1) macroscopic (visible) crystals disseminated in oil shales that com- high organic matter content, saline sediments do not contain fossils or
monly form laterally continuous beds (Fig. 5A), and (2) fine-grained, microbialite carbonates. Barren mudstones overlying Na-carbonate
pirssonite laminated with oil shales and tuffs (Fig. 5B). Macroscopic beds, are partly or completely replaced by dolomite (Fig. 6D).
pirssonite crystals show faceted prismatic and pseudohexagonal sections Thenardite is rare and occurs as discontinuous, millimeter-thick
often exhibiting dissolution outlines. layers in the trona beds that are made up of micrometric crystals. No
Nahcolite is scarce and occurs at the base and/or top of some of the Ca-bearing sulfate minerals (gypsum and glauberite) were identified.
studied borehole sections. In mine galleries, the uppermost mineralized Pyrite is abundant in Beypazari. It consists of subhedral to euhedral
levels are completely formed by nahcolite. Nahcolite occurs in two cubic crystals and radiating clusters of bladed crystals disseminated in
forms: (1) pure, massive beds made up of interlocking, centimeter- oil shales. Pyrite replaces calcite, dolomite, trona and pirssonite but
sized, colorless, anhedral crystals (Fig. 5C), and (2) macroscopic crystals never nahcolite. Framboidal pyrite was not observed.
disseminated in oil shales (Fig. 5D). Searlesite in Beypazarı soda beds occurs as spherulites (Fig. 7A),
Bradleyite is a minor phase only present in the central borehole radiating fibers and displacive prismatic crystals in mud layers, and
sections (SJ-7, SJ-31 and SJ-6) of the Upper Trona Unit. This Mg- as a replacement of pirssonite and trona (Fig. 7B). Searlesite accom-
bearing, anhydrous carbonate-phosphate mineral previously only panied by analcime is abundant as filling voids and cementing tuffs.
recognized in the Green River Formation, occurs as tiny, isolated K-feldspar is the major authigenic silicate in the Beypazarı succes-
prismatic inclusions within trona crystals, or as submillimeter radial sion. K-feldspar crystals are micrometric in size and arranged in
aggregates in grain boundaries between them. random clusters to form discontinuous millimeter-thick layers in
Dolomite and calcite occur as macroscopic to submillimeter-sized, mudstone and oil shale beds (Figs. 4C, 7C). K-feldspar crystals show
euhedral crystals scattered in the barren mudstones which overlie skeletal prismatic habits with empty cores (Fig. 7D). Under crossed
the soda beds (Fig. 6A and C). In the Na-carbonate beds, euhedral, nicols, these crystals are quasi-isotropic. Authigenic Na-feldspars
micrometer-size dolomite crystals are abundant in intercalated tuff, were not observed.
318 J. García-Veigas et al. / Sedimentary Geology 294 (2013) 315–327

Fig. 2. Generalized stratigraphic succession (not to scale) of the Beypazarı Basin.

After Helvacı (2010).

Analcime and minor chabazite-K are the most common zeolite min- and pore water systems before ultimately changing to the most stable
erals. They occur as micrometric crystals filling voids and replacing thin phases (e.g., pirssonite). Furthermore, in ancient deposits, important dif-
layers of ash within oil shale intervals. ferences can be found between present-day and original (primary) min-
Quartz is ubiquitous as euhedral crystals in the Beypazarı soda de- eral associations. Therefore, it is necessary to document possible mineral
posit and chiefly abundant in oil shale beds where this mineral grew transformations that occurred during the various stages of diagenetic al-
authigenically. Idiomorphic quartz crystals commonly replace saline teration, especially those that took place before significant compaction.
minerals (trona and pirssonite). In Beypazarı, groups of macroscopic pirssonite crystals show
homogeneous extinction indicating they are pseudomorphs after
4.2. Mineralogical transformations involving Na-carbonate minerals another mineral replaced by pirssonite. In the same way, successive
pirssonite laminae extinct at once suggesting millimeter-sized
The common use of mineral identification exclusively by means of pirssonite crystals replacing adjacent layers originally made up by
XRD techniques in both recent and ancient Na-carbonate deposits, with- another mineral (Fig. 8A and B).
out complementary petrographic analysis, can lead to contradictory in- Backscattered electron images reveal solid inclusions of a higher
terpretations of the original mineral phases. For example, in modern hydrated Ca–Na-carbonate mineral in some pirssonite and trona
environments, metastable mineral (e.g., gaylussite) can form in lake pseudomorphs. Backscattered signals of these solid inclusions are
 J. García-Veigas et al. / Sedimentary Geology 294 (2013) 315–327 319

Fig. 3. Lithological log correlation of boreholes based on distribution of Na-carbonate minerals in the center of the Beypazarı Basin.

darker (lower average atomic number) than those of the neighboring Although shortite, the anhydrous Na–Ca-carbonate, was previously
pirssonite (Fig. 9A). These solid inclusions are interpreted as relicts of reported as macroscopic, interstitial crystals in oil shale beds of the
primary gaylussite now replaced by pirssonite and trona. Beypazarı deposit (Suner, 1994), such textures were not found in this
320 J. García-Veigas et al. / Sedimentary Geology 294 (2013) 315–327

Fig. 4. Trona lithofacies: A/grass-like trona lithofacies (Upper Trona Unit, hand sample U3A, Beypazarı trona mine); B/massive trona lithofacies (Upper Trona Unit, core sample
EL-2-24 at 256.9 m in depth); C/radiating-prismatic texture of the interstitial trona lithofacies (Upper Trona Unit, hand sample U6, Beypazarı trona mine); D/unoriented texture
of the interstitial trona lithofacies. White arrow indicates a layer of authigenic K-feldspars (Upper Trona Unit, hand sample D11B, Beypazarı trona mine).

study. Instead isolated shortite prisms replace pirssonite crystals in areas Macroscopic disseminated nahcolite crystals in some oil shale beds
related to hydrocarbon migration (Fig. 9B). show homogeneous extinction and suggest that they also replace a
In Beypazarı, nahcolite preserves solid inclusions of dolomite previous phase (pirssonite). In any case, textural evidence of primary
outlining the original grain boundaries of trona (Fig. 9C and D). nahcolite formation was not recognized.

Fig. 5. Pirssonite and nahcolite lithofacies: A/macroscopic texture of the pirssonite-bearing oil shale lithofacies (Lower Trona Unit, core sample SJ-31-25 at 342.5 m in depth); B/
laminated texture of the pirssonite-bearing oil shale lithofacies (Upper Trona Unit, core sample SJ-22-6 at 365.0 m in depth); C/massive nahcolite lithofacies (Upper Trona Unit,
core sample SJ-22-5 at 361.8 m in depth); D/macroscopic nahcolite lithofacies (Upper Trona Unit, core sample SJ-31-3 at 276.6 m in depth).
 J. García-Veigas et al. / Sedimentary Geology 294 (2013) 315–327 321

Fig. 6. Dolomite and calcite occurrences in dolomite-bearing mudstone lithofacies: A/macroscopic euhedral dolomite crystals scattered in the barren mudstone lithofacies (hand
sample from the outside of the Beypazarı trona mine); B/submillimeter-sized dolomite crystals in grain boundaries between acicular trona crystals (photomicrograph with normal
light, Upper Trona Unit, hand sample U4A, Beypazarı trona mine); C/macroscopic calcite crystals in barren mudstones (barren mudstone on top of the Upper Trona Unit, core sam-
ple SJ-6-8 at 236.0 m in depth); D/micritic dolomite crystals (dark gray) growing in a mudstone matrix (light gray) and replacing macroscopic calcite (white) crystals (SEM-BSE
image, barren mudstone on top of the Upper Trona Unit, core sample SJ-35-2 at 134.4 m in depth).

5. Discussion role in controlling sulfate, carbonate and bicarbonate concentrations.

Most of the minerals present in recent and ancient Na-carbonate de-
Many factors control the mineral stability fields in Na+–Ca2+– posits show textural relations suggestive of partial to complete re-
− −
CO2− 2−
3 –CO3H –Cl –SO4 type of brines. In many instances, mineral crystallization processes.
assemblages are controlled by the activities of H2O and of CO2 at The use of evaporitic mineral assemblages as indicators of the
any pressure and temperature (Eugster and Smith, 1965). Moreover, chemical conditions in the original sedimentary environment re-
biologic activity, mainly in bottom sediments, can play an important quires knowledge of the timing of mineralogical transformations

Fig. 7. Searlesite and authigenic K-feldspar occurrences: A/searlesite spherulites in the barren mudstone lithofacies (Lower Trona Unit, core sample SJ-6-44 at 437.5 m in depth); B/searlesite
spherulite replacing thin-layered pirssonite (photomicrograph with normal light, Upper Trona Unit, core sample SJ-31-16 at 308.5 m in depth); C/unoriented trona crystals in the interstitial
trona lithofacies, arrows point towards an authigenic K-feldspar layer (Upper Trona Unit, hand sample U3D, Beypazarı trona mine); D/SEM image, authigenic K-feldspar crystals (Upper Trona
Unit, hand sample U3D, Beypazarı trona mine).
322 J. García-Veigas et al. / Sedimentary Geology 294 (2013) 315–327

Fig. 8. Mineralogical transformations involving pirssonite: A and B/homogeneous extinction of a megascopic pirssonite replacing laminae of some previous evaporite mineral
(photomicrograph with normal light (A) and crossed nicols (B), Upper Trona Unit at 344.9 m in depth); C/unoriented trona replacing an isolated pirssonite crystal (dotted line)
(photomicrograph with normal light, Upper Trona Unit, core sample SJ-6-27 at 355.0 m in depth); D/radiating-prismatic trona replacing laminated secondary pirssonite (photomicrograph
with crossed nicols, Upper Trona Unit, core sample SJ-31-5 at 285.5 m in depth).

during early diagenesis (penecontemporaneously with sedimenta- to propose precise chemical models for ancient soda lakes. In addi-
tion). The high solubility of sodium carbonates and their dependence tion, geochemical reactions in alkaline lakes may be dominated by
on temperature, salinity, activity of H2O, pH–Eh, and CO2 partial pres- non-equilibrium processes resulting in precipitation of stable, unsta-
sure, together with complex fluid flow processes, make it difficult ble and metastable minerals.

Fig. 9. Mineralogical transformations involving trona after secondary pirssonite, shortite after pirssonite, and nahcolite after trona: A/pirssonite (pseudomorphic) crystals replaced
by trona. Arrows point towards solid inclusions of probably primary gaylussite in trona (Lower Trona Unit, core sample SJ-31-26 at 345.7 m in depth); B/shortite prismatic crystal
(arrow) replacing pirssonite and embedded by kerogen (photomicrograph with normal light, Lower Trona Unit, core sample SJ-31-31 at 377.1 m in depth); C and D/massive
nahcolite replacing trona crystals outlined by micrometric dolomite (photomicrographs with normal light (C) and crossed nicols (D), Upper Trona Unit, core sample SJ-35-12 at
219.7 m in depth).
 J. García-Veigas et al. / Sedimentary Geology 294 (2013) 315–327 323

5.1. Mineral genesis Unlike the abundant trona in the recent Magadi and Searles lakes,
natural Na-bicarbonate does not precipitate as readily in lake brines.
5.1.1. Na-carbonates In both settings nahcolite has been only reported in drill cores as inter-
From the mineralogic point of view, one unresolved question is stitial crystals grown in oil shale intervals (Walther, 1922; Foshag,
the timing of formation of Na–Ca-carbonates (gaylussite, pirssonite 1940). In the Eocene Green River Formation of the Piceance Creek
and shortite) in mud and oil shale layers in recent and ancient Basin (Colorado), discontinuous concretions, scattered crystals, nodules
deposits. Among them, only the most hydrated phase (gaylussite) and both microcrystalline and coarse-crystalline layers of nahcolite
seems to be formed in modern alkaline lakes (Bischoff et al., 1991). occur in oil shales (Ertl, 1947; Cashion, 1967; Dyni, 1981, 1996;
Occurrences of Na–Ca-carbonates in modern evaporite lakes are Lowenstein and Demicco, 2006; Brownfield et al., 2010).
reported as interstitial growths of individual crystals in organic-rich Nahcolite is less soluble than sodium carbonate by a factor of 3 or
muds prior to complete compaction. Apparently, they never form as 4. However, this mineral is only predicted to be formed at elevated
subaqueous precipitates on the bottom of the lake or within the CO2 pressure in water, higher that is currently in equilibrium with
brine body. Although some chemical parameters (temperature, H2O the present-day atmosphere (Eugster and Smith, 1965).
activity and NaCl content) have been studied in the gaylussite– Nahcolite in the Green River Formation was originally interpreted
pirssonite–shortite transitions (Bury and Redd, 1933; Fahey, 1962; to be formed in unconsolidated sediments as an authigenic mineral
Eugster and Smith, 1965; Bradley and Eugster, 1969), virtually by migration of interstitial brines enriched in CO2 by degradation of
nothing is known about the precise precipitation mechanisms involv- organic matter (Eugster, 1980; Smith, 1983). On the basis of textural
ing these minerals in natural environments. evidence, Lowenstein and Demicco (2006) suggested that some of the
Gaylussite was first found at Lagunilla Lake (Venezuela) and later nahcolite crystals of the Colorado deposit precipitated in the water–
reported in muddy sediments of Searles Lake, and Mono Lake in air interface of a perennial lake. According to these authors, nahcolite
California (Pratt, 1896; Haines, 1959; Bischoff et al., 1991; Thomas was formed in equilibrium with high carbon dioxide concentrations
and Farmer, 2005). At Lake Magadi, it occurs in unconsolidated sur- in the early Eocene atmosphere.
face beds as clear crystals up to 5 mm in length (Eugster, 1980). In Beypazarı, nahcolite shows evidence to be late diagenetic after
Gaylussite is the main soda mineral reported in the anoxic mud of trona and pirssonite and probably related to fluids enriched in CO2.
modern Lake Bogoria (Renaut and Tiercelin, 1994). In this regard, high levels of atmospheric CO2 during Middle Miocene
The solubility of gaylussite varies strongly with temperature. cannot be suggested.
According to Bischoff et al. (1991), gaylussite in Mono Lake pre-
cipitates during the winter months but is subsequently replaced by
5.1.2. Sulfates (thenardite) and sulfides (pyrite)
aragonite by incongruent dissolution. In Searles Lake, gaylussite
In spite of low sulfate concentration in modern Na-carbonate lakes,
is abundant accompanying pirssonite in the upper muddy intervals
minor amounts of Na-sulfate minerals, chiefly thenardite, have been re-
but disappears at depth where the lesser hydrated phase (pirssonite)
ported in association with Na-carbonate minerals (Foshag, 1933; Smith
occurs. Gaylussite has never been reported in ancient deposits,
and Haines, 1964; Eugster and Smith, 1965; Gac et al., 1979; Smith et al.,
suggesting it has been replaced by other minerals, mainly pirssonite.
1987). Lake Magadi is depleted in dissolved sulfate with respect to
Pirssonite crystals in oil shale beds of the Beypazarı deposit are
the inflow waters, probably because of bacterial sulfate reduction
secondary after a previous phase. According to crystalline habits,
(Eugster, 1980). No sulfate minerals are preserved in the Eocene Green
the presence of solid inclusions, and the prevalence of gaylussite
River Formation although casts of saline minerals, probably glauberite,
in modern alkaline lakes, we propose that pirssonite replaces gaylussite.
were described by Bradley (1931).
Shortite is the most abundant Na–Ca-carbonate mineral in the
In contrast to the scarcity of sulfate minerals in soda lakes, sulfide
Green River Formation of Green River (Wyoming) and Uinta (Utah)
minerals (mainly pyrite) are common. Spherulites and isolated
basins (Fahey, 1962). However, this mineral has never been reported
euhedral pyrite crystals are abundant in saline beds and muddy inter-
in the Piceance Creeck Basin (Colorado). The origin of shortite in
vals from Searles Lake (Smith, 1979) as well as in oil shale beds of
the Green River Formation of Wyoming is under debate. According
the Green River Formation (Bradley, 1931). In both cases pyrite is
to Fahey (1962), shortite nucleated and grew interstitially in
interpreted as result of hydrogen sulfide produced through the
organic-rich muds as individual crystals before complete com-
break-down of organic matter.
paction and was subsequently replaced by pirssonite, trona and
We suggest that most of the reduced sulfur source required for
northupite. In contrast, according to Bradley and Eugster (1969),
pyrite formation in Beypazarı soda beds was provided by bacterial
shortite was diagenetically formed at burial by reaction of pirssonite
sulfate reduction and by degradation of microbial organisms in the
and calcite at temperatures about 90 °C. Jagniecki et al. (2009, 2013)
deepest part of the lake (monimolimnion), which remained anoxic.
proposed that gaylussite precipitated in the lake and was replaced at
burial by pirssonite at about 40 °C, and then subsequently shortite
was formed from pirssonite above 52 °C. 5.1.3. Authigenic silicates (smectite, K-feldspar, zeolites, searlesite
Petrographic observations documenting the progressive dehydra- and quartz)
tion of Na–Ca-carbonates during burial and illustrating the complete Neoformation of silicates results from chemical reactions of the orig-
transition gaylussite → pirssonite → shortite have not been observed inal material, mainly volcanic glass, with the alkaline brines they come
in Beypazarı. in contact with. The general sequence of volcanic glass → authigenic
Trona precipitates in the shallow brines of Lake Magadi (Kenya) clay → zeolite (analcime) → K-feldspar is well established in alkaline
(Eugster, 1980) and Owens Lake (California) (Friedman et al., 1976; lakes with increasing pH (Jones et al., 1967; Surdam and Eugster,
Smith et al., 1987). Trona precipitation has also been reported in the 1976; Surdam, 1977; Surdam and Sheppard, 1978; Hay and Guldman,
bottom sediments of the deeper Lake Bogoria (Kenya) (Renaut and 1987; Hall, 1998; Sheppard and Hay, 2001).
Tiercelin, 1994). Smectite is commonly reported in sediments of alkaline lakes
The grass-like fabric of trona, similar to the vertically oriented resulting from either direct precipitation in lake waters or by the trans-
gypsum (selenite) textures in evaporitic environments, is interpreted formation of other precursor clay minerals (Khoury et al., 1982; Cuevas
as a lake-floor precipitated. The massive (matrix-free) trona suggests et al., 2003; Correia-Furquim et al., 2008; Larsen, 2008). In Beypazarı,
subaqueous precipitation. In contrast, both radiating-prismatic and Mg-rich smectite clays (Helvacı et al., 1988) are interpreted as being
unoriented textures are interpreted as displacive interstitial growths formed by direct precipitation from lake waters due to the absence of
below the water–sediment interface. detrital precursors.
324 J. García-Veigas et al. / Sedimentary Geology 294 (2013) 315–327

K-feldspar authigenic crystals in saline beds never replace trona or 5.2.3. Massive trona (shallow-water, saline lake)
pirssonite and do not show evidence of replacing any ash precursor. Massive trona is the most abundant lithofacies in Beypazarı. It con-
Petrographic evidence indicates that K-feldspar crystals precipitated sists of thick, mud-free, whitish, poorly-bedded masses. Coarse-grained
directly from pore waters although transformation of previously detrital sediments are not observed and only disseminated clay material,
formed silica gels cannot be ruled out. displaced by the crystal growth, suggests sedimentary layering. We in-
Distribution of zeolites (mainly analcime) in Beypazarı Na- terpret this lithofacies in the same manner as Fahey (1962), who consid-
carbonate beds suggests that they were formed by alteration of the ered massive trona as a subaqueous precipitate directly formed in a
fine-grained volcaniclastic components via reaction with alkaline shallow alkaline lake.
waters.
Millimeter-thick ash layers in oil shale and saline beds are re- 5.2.4. Grass-like trona (ephemeral, saline lake)
placed by isolated prisms and spherulites of searlesite and idiomorfic Grass-like trona precipitation is reported on the floor of the presently
quartz. Both minerals are considered early diagenetic replacements of active Lake Magadi when the brine is no more than a few centimeters
Na-carbonate minerals; displacive growth within muds is an alterna- deep (Eugster, 1980). According to this paper, trona occurs as long,
tive origin. pointed blades attached to the substratum growing radially upwards
and as a thin film of rafts floating on the brine surface. These trona
5.2. Sedimentary lithofacies and depositional environments rafts inhibit evaporation and increase the brine temperature to ≥60 °C.
Subsequent evaporation causes the brine level to fall below the base of
We identified five major lithofacies, on the basis of lithologic fea- the newly formed trona bed; trona precipitates from those brines as
tures, in the central (evaporitic) part of the Beypazarı trona deposit: intercrystalline cement. In Magadi, successive grass-like trona beds are
(1) dolomite-bearing mudstone, (2) pirssonite-bearing oil shales, separated from each other by thin bands of windblown dust. These cou-
(3) massive trona, (4) grass-like trona, and (5) mudstone with inter- plets are assigned to seasonal fluctuations of the brine volume in an
stitial trona. Pirssonite-bearing oil shales mainly occur at the base of ephemeral, periodically dried saline lake.
the Lower Trona Unit. Massive trona is the most abundant lithofacies Unlike Lake Magadi, in Beypazarı, grass-like trona beds occur as
in all trona beds. Grass-like and mudstone with interstitial trona tex- bladed crystals covered by mud. The lack of successive grass-like
tures are restricted to the upper parts of the Lower and Upper Trona trona beds is interpreted to result from complete dissolution of previ-
Units. Grass-like trona beds in mine galleries extend for several hun- ously precipitated trona during each new flooding event.
dred meters and grade laterally to interstitial textures.
Each lithofacies can be linked to specific mineralogical processes and 5.2.5. Mudstone with interstitial trona (dried, saline lake)
sedimentary environments. Relationships between these lithofacies Radiating-prismatic and unoriented textures of trona are geneti-
allow us to propose a sedimentary model for the Beypazarı lake which cally related and differ from each other in crystal orientation and ma-
underwent large fluctuations in alkalinity, salinity and water depth. trix content. They probably formed when brine levels fell down below
the bottom of the lake during complete desiccation stages or in the
surrounding playa at the time when grass-like trona precipitated on
5.2.1. Dolomite-bearing mudstone (deep-water lake) the lake floor.
Na-carbonate beds grade laterally and underlie olive-green Replacements of pirssonite by interstitial trona probably occurred
dolomite-bearing mudstones which consist mainly of Mg-rich smec- during sub-aerial exposure of previously formed pirssonite-bearing
tite clays. No primary sedimentary structures such as lamination, oil shale beds by reaction with Na-carbonate-rich interstitial brines.
mudcracks, wave-ripples, root structures or burrows were observed.
Coarse detrital intervals are almost absent in the studied area al- 5.3. Water depth in alkaline lakes
though they are abundant towards the basin margins (Helvacı,
1998, 2010). Several tuff intervals are intercalated with mudstones. Alkaline lakes are not restricted to playa-lake settings. For exam-
The absence of current-formed sedimentary structures and the ple, Lake Van in western Turkey is the world's largest soda lake.
lack of biogenic shallow-water carbonates suggest that barren Lake Van is a non-meromictic lake located at an altitude of 1500 m,
dolomite-bearing mudstones were formed in the center of a deep, and an area of 3522 km2, a maximum water depth of 450 m, and
moderately alkaline, perennial saline lake, far away from near- more than 600 m of unconsolidated sediments (Kempe et al., 1991;
shore wave action. Landmann et al., 1996; Reimer et al., 2009). Today, sediment deposi-
tion in Lake Van mainly consists of clays and organo-detritus during
5.2.2. Pirssonite-bearing oil shales (moderately deep-water, meromictic lake) winter and spring, and carbonate (calcite and aragonite) muds in
Oil shale intervals with pirssonite consist of well layered, kerogen- summer and autumn. In the past, dolomite precipitated during re-
rich beds containing fine-grained, altered tuffs. Despite the high gressive events and Mg-rich neoformed smectites formed by reaction
organic content, neither diatoms nor other fossil remnants were of diatoms with alkaline brines on the lake floor (Reimer et al., 2009).
found in these oil shales suggesting that life was limited to extremo- Despite its high alkalinity, no soda minerals precipitate in the lake
phile microbes. Degradation of plant debris, algae and microbes to because saturation conditions were probably never reached but
produce organic-rich mud points to anoxic conditions in a meromictic thermonatrite, trona and burkeite have been reported as ephemeral
(stratified) lake. crusts on the lake margins during summers (Helvacı, 2003).
Trona, or other exclusively sodium evaporite minerals are absent The main controversy in the interpretation of ancient Na-carbonate
or scarce in oil shale beds, and where trona occurs it is a secondary deposits concerns the water depth, in particular during oil shale sedi-
replacement of Ca–Na-carbonates (pirsonnite and gaylussite). This mentation. All modern soda lakes in which Na-carbonate minerals pre-
fact suggests significant calcium concentrations in brines during cipitate can be considered as playa lakes. Most of them are ephemeral,
deposition of these organic-rich intervals. becoming completely dried up at least once every few years.
In summary, oil shale intervals are characterized by high organic The Green River Formation is an example of this dichotomy: it was
contents, interstitial precipitation of salts, and limited coarse-grained first regarded to be deposited in deep, perennial, stratified lacustrine
sediment influx. They probably represent moderately deep, stratified- basins (Picard, 1955; Bradley, 1964; Bradley and Eugster, 1969), later
water periods that took place between deposition of barren mudstones interpreted as shallow-water, playa lakes (Eugster and Surdam, 1973;
in perennial, deep-water lakes and deposition of trona beds in ephem- Surdam and Wolfbauer, 1975; Surdam and Stanley, 1979), and then
eral, periodically desiccated lakes. reinterpreted as dynamic lakes changing repeatedly from deep to
 J. García-Veigas et al. / Sedimentary Geology 294 (2013) 315–327 325

shallow conditions (Boyer, 1982; Picard, 1985; Pietras and Carroll, or by further dissolution. Mineral precipitation first occurred in
2006). Recently, trona beds in Wyoming were assigned to a density unconsolidated sediments, in which macroscopic, authigenic
stratified lake (Jagniecki and Lowenstein, in press). crystals (probably gaylussite) grew displacively. Bacterial sulfate
The Hırka Formation was initially interpreted by Helvacı (1998) to reduction and degradation of microbial organisms led to early
have been deposited in a playa-lake environment. This interpretation diagenetic (penecontemporaneous) replacement of evaporite
was based on: (1) the presence of shallow, saline lithofacies (grass-like minerals by pyrite in oil shale beds. Subsequently, gaylussite
trona) in the saline beds, (2) the prevalence of mudstones, (3) the was replaced by pirssonite.
distribution of coarse-grained fluvial deposits, intraformational con- (3) When restriction increased, water level fell, disrupting the
glomerates, and sedimentary current and desiccation structures in the chemocline and ending anoxic conditions at the bottom. Salinity
laterally equivalent Çoraklar Formation. In this sense, the Beypazarı was raised enough to achieve supersaturation with respect to
Lake model could be compared to modern, ephemeral, alkaline lakes some evaporite minerals in the shallow or moderately-deep
such as Lake Magadi or Searles Lake. However, all evidence points to im- brine body. Calcium concentration was low because, (1) condi-
portant fluctuations in water depth throughout the time of deposition tions were alkaline, and (2) calcium exhaustion occurred during
of the Hırka Formation in the center of a lacustrine basin. previous gaylussite precipitation within oil shale beds. Therefore,
the Na-carbonate mineral, trona, started to precipitate and sank
6. Conclusions: a genetic model for Na-carbonate precipitation in to the bottom of the lake-forming massive trona beds.
the Beypazarı trona deposit (4) Major brine drawdown converted the lacustrine basin in a playa
lake system, which periodically accommodated an ephemeral,
In the center of the Beypazarı Basin, repetitive successions of deep saline water body wherein grass-like trona was formed. At the
(dolomite-bearing mudstones and pirssonite-bearing oil shales) and same time, in the surrounding saline mudflat, and during com-
shallow (trona beds) deposits are interpreted to reflect periods of plete desiccation of the lake, interstitial growth of radiating-
lake expansion and contraction, respectively. Lake drawdown, with prismatic and unoriented trona beds precipitated from ground-
reduced water volume and increasing salinity, and the corresponding water brines.
basin-center depositional cycle in the center could be represented as
follows (Fig. 10): Gaylussite conversion to pirssonite probably occurred during early
diagenesis by partial dehydration when temperature increased.
(1) Undisrupted mudstone was deposited in a deep, poorly- Widespread dehydration to shortite during burial was not achieved.
oxygenated but well-mixed and slightly alkaline lake. Mg-rich Late diagenetic conversion of trona and pirssonite beds to nahcolite
smectite precipitated directly on the lake floor from the dissolved was made by means of CO2-rich, probably hydrothermal waters.
silica derived by hydrolysis of detritals and pyroclasts at the In summary, the Beypazarı soda beds formed in the central part of
shore. a closed basin lake and can be compared with the lake-level fluctuat-
(2) With increasing salinity, a chemocline formed and the lake be- ing model proposed by Renaut and Tiercelin (1994) for Lake Bogoria
came stratified (meromictic) with development of a stagnant, (Kenya). Cyclic transitions from organic-rich mud deposition contain-
cold-water, anoxic brine at the bottom favoring oil shale preser- ing gaylussite (later replaced by pirssonite), to shallow and dried
vation. Although saturated conditions for some evaporite min- stages dominated by trona precipitation may be related to regional
erals were reached in the bottom brine, they did not form, climatic changes influenced by local tectonics rather than global cli-
probably because of metastability in supersaturated solutions matic factors.

Fig. 10. Schematic drawing showing the mineralogical succession in the central part of the Beypazarı Basin where Na-carbonate beds formed following episodic drawdown.
326 J. García-Veigas et al. / Sedimentary Geology 294 (2013) 315–327

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This study was supported by projects: 1) CGL2009-11096 of the Beypazarı trona deposit, Middle Miocene, Turkey. 44–45 (IESCA-2005, İzmir
Spanish Government; 2) 2009-SGR1451 of the Catalan Government; (Turkey), Abstracts book).
Haines, D.V., 1959. Core logs from Searles Lake, San Bernardino Country, California. U.S.
3) TBAG-685 of TÜBİTAK (The Scientific and Technological Research Geological Survey Bulletin 1045, 139–317.
Council of Turkey); and 4) 03.KB.FEN.015 of the Dokuz Eylül Univer- Hall, A., 1998. Zeolitization of volcaniclastic sediments: the role of temperature and pH.
sity (İzmir, Turkey). Borehole logs were studied by the permission of Journal of Sedimentary Research 68, 739–745.
Hay, R.L., Guldman, S.G., 1987. Diagenetic alteration of silicic ash in Searles Lake. Clays
Etimaden (Etimine Works General Management) and MTA (General and Clay Minerals 35, 449–457.
Directorate of Mineral Research and Exploration). The authors are in- Helvacı, C., 1998. The Beypazarı trona deposit, Ankara province, Turkey. Wyoming
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Helvacı, C., 2003. Doğu Anadolu'nun bor potansiyeli ve Van Gölü soda oluşumları. Doğu
Maria Barba (CCiTUB, Universitat de Barcelona) for their technical
Anadolu Endüstriyel Hammadde Çalıştayı (Van). Proceedings, pp. 46–47 (in Turkish).
support. We would like to thank Federico Ortí and Laura Rosell Helvacı, C., 2010. Geology of the Beypazarı trona field, Ankara, Turkey. In: Helvacı, C.
(GPPG Department, Universitat de Barcelona), and to Tim Lowenstein (Ed.), Tectonic Crossroads: Evolving Orogens of Eurasia–Africa–Arabia (33 pp.).
(Binghamton University) for their discussions and suggestions during Helvacı, C., Yılmaz, H., İnci, U., 1988. Beypazarı (Ankara) yöresi Neojen tortullarının kil
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