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REE geochemistry of the recent playa sediments from the Thar Desert, India:
An implication to playa sediment provenance

Article  in  Chemie der Erde - Geochemistry · May 2007

DOI: 10.1016/j.chemer.2005.01.006

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 ARTICLE IN PRESS

Chemie der Erde 67 (2007) 55–68

www.elsevier.de/chemer

REE geochemistry of the recent playa sediments from the Thar Desert,
India: An implication to playa sediment provenance
P.D. Roya,b, W. Smykatz-Klossa,
a
Institute of Mineralogy and Geochemistry, University of Karlsruhe, 76131 Karlsruhe, Germany
b
Division of Earth Sciences, Physical Research Laboratory, Navrangpura, Ahmedabad 380 009, India

Received 1 November 2004; accepted 31 January 2005

Abstract
The playas (saline lakes) situated in the Thar Desert, north-west India, provide prominent examples of alkaline brine
and varying assemblages of detrital and evaporite mineralogy. The eastern margin of the desert is relatively semi-arid,
whereas the central to western region is arid to hyper-arid in nature. Rare earth elements (REEs) systematics in the
sediments of nine different playas of the Thar Desert were studied to understand the provenance of the sediments and
the intensity of chemical weathering in the region. Based on the REE patterns, fractionation of light REE (LREE)
(La/Sm)N and heavy REE (HREE) (Gd/Yb)N, and Eu anomaly (Eu/Eu*), the upper continental crust normalised
playa sediments are divided into two different groups. The eastern margin playa sediments show homogeneous REE
contents, relatively positive Eu anomaly and depleted HREE values, whereas the western arid core playa sediments
have highly variable REE contents, relatively negative Eu anomaly and similarly fractioned LREE and HREE
patterns. The dissimilarity in the degree of HREE fractionations both in the eastern and western playa sediments is
attributed to the differential distribution of minerals, depending upon their resistance to chemical weathering. It is
believed that the relatively higher abundance of REE bearing heavy minerals and the presence of higher amounts of
evaporites influence the large variation of REE distribution and enriched HREE in the western playa sediments. Apart
from the relatively higher abundance of heavy minerals, the presence of rock fragments of variable petrographic
character and roundness mirror the lower rock–water interaction in the arid western region. The presence of well-
rounded metamorphic rock fragments and minerals, sourced from the eastern margin Aravalli mountains, indicates
that the playas of the entire desert get the detrital and dissolved material mainly from the Aravalli mountains.
Additionally, the western playas receive sediments from their surrounding Proterozoic and Mesozoic formations. This
interpretation is supported by the presence of angular rock fragments of basalt, rhyolite and limestone in the western
playas.
r 2005 Elsevier GmbH. All rights reserved.

Keywords: REE geochemistry; Provenance; Playa lakes; Evaporites; Thar Desert; India

Corresponding author. Institute of Mineralogy and Geochemistry, University of Karlsruhe Kaiserstraße 12, 76131 Karlsruhe, Germany.
E-mail addresses: [email protected] (P.D. Roy), [email protected] (W. Smykatz-Kloss).

0009-2819/$ - see front matter r 2005 Elsevier GmbH. All rights reserved.
doi:10.1016/j.chemer.2005.01.006
 ARTICLE IN PRESS
56 P.D. Roy, W. Smykatz-Kloss / Chemie der Erde 67 (2007) 55–68

1. Introduction various sediment–geochemical processes that led to their

differential distribution.
The playas of the Indian Thar Desert are present
throughout western Rajasthan, specifically in the region
west of the Aravalli mountains, i.e. the region in the rain
shadow for the south-west monsoon. The physical and 2. Regional settings
chemical evolutions of these playas are attributed to
favourable geomorphologic, tectonic and climatic con- The Indian part of the Thar Desert is situated between
ditions. These highly saline playas are characterised the Aravalli mountains in the east and Pakistan in the
by alkaline brines, centripetal drainage and absence west (Fig. 1). The eastern margin of the desert receives
of any outflow. In some playas, the salinity rises as an annual precipitation of 500 mm and the precipitation
high as 376 g/l of TDS. When the size of most of these decreases gradually towards the west (100 mm). The
playas range from 10 to 50 km2, the Sambhar playa mean maximum temperature in the region ranges
located next to the Aravalli mountains has a surface between 40 and 45 1C and the minimum temperature
area of 225 km2. These playas are economically very fluctuates between 3 and 10 1C. The Luni River is the
important as some thousands of tons of salts are only integrated drainage network which presently flows
produced every year from their brine. The assemblage from the western slopes of the Aravalli mountains to the
of evaporite mineralogy and hydro-geochemistry char- Arabian sea. But the presence of a number of palaeo-
acterises the playas of the eastern desert margin to be of channels throughout the desert (Bakliwal and Grover,
the Na-Cl-SO4 type, whereas the western arid core 1999) suggests the existence of a former fluvial system in
playas are of the Na-(Ca)-Cl-SO4 type. The isotopic the region. The lack of proper drainage led to the
studies on these playa brines (Ramesh et al., 1993; accumulation of the rainwater in the various large and
Yadav, 1997) have confirmed their meteoric origin and small natural depressions (playas), which later got saline
related the higher salinity to the prevalence of evapora- during the time of higher evaporation in the region. Due
tive conditions. to the relatively higher precipitation, the playas of the
Geomorphological, sedimentological and archaeolo- eastern desert margin are fed by seasonal rivers and
gical studies relate the physical evolution of most of the streams. During the three monsoonal months (July–-
Thar playas to ancient fluvial regimes (Kar, 1990; Rai, September) along with rainwater, these streams carry
1990; Rai and Sinha, 1990; Sundaram and Pareek, 1995; detrital fractions and dissolved constituents into the
Deotare et al., 1998). Apart from the tectonic origin playas.
(Sinha-Roy, 1986; Roy, 1999), it is also suggested that The geological and geochemical observations in the
during the late Pleistocene excessive siltation at the river region indicate the presence of metamorphic rocks of
confluence (Ghosh, 1964; Ghosh et al., 1977) and varying petrographic character, intrusions of pegma-
formation of sand dunes across the river channels tites, volcanics and sedimentary rocks under the thick
(Agarwal, 1957; Singhvi and Kar, 1992) led to the cover of Quaternary sand (Sen and Sen, 1983; Dassar-
formation of these shallow (1–3 m depth) closed basin ma, 1988; Bakker and Mamtani, 2000; Abu-Hamatteh,
playas. The palaeo-channels discovered in their sur- 2002). Rocks of several groups belonging to the
roundings were once feeding these playas. All these Archaean (3.3 Ga) and Proterozoic (0.75 Ga) ages
geomorphological and sedimentological observations constitute the Aravalli mountain system. The Archaean
along with the isotopic composition of the playa brine granites, gneisses, amphibolites and pegmatites are
refute their marine connection and suggest that they are overlain by the metamorphic rocks of the Aravalli
replenished by rainwater and surface runoff. supergroup and Delhi supergroup. The highly folded
In the present study, we report the rare earth element metamorphosed rocks of the Delhi supergroup form the
(REE) systematics in the playa sediments of the Thar main part of the mountains and consist of quartzite,
Desert and their implication to weathering and prove- mica schist and gneiss (Singh et al., 1972; Biswas et al.,
nance studies. As the REE concentrations in the 1982; Misra, 1982; Wasson et al., 1984; Rai and Sinha,
sediments are controlled by the competing influence of 1990; Sundaram and Pareek, 1995; Rai and Absar,
provenance, intensity of chemical weathering, miner- 1996). A wide spread volcanic event at the end of the
alogical distribution and aqueous geochemistry of the Proterozoic is marked by the isolated exposures of the
inflow precipitating the chemical sediments, we investi- Malani igneous suite. This igneous suite consisting of
gated the REE geochemistry of playa sediments from basalt and rhyolite is overlain by the sandstone and
nine different playas located in the different climatic limestone of the Marwar supergroup. The Palaeozoic
zones of the Thar Desert. Along with the distribution of Bap boulder bed along with dolomite and minor shale
detrital mineralogy and rock fragments, the fractiona- overlie the Marwar rocks. Both the Malani and Marwar
tion of the REEs in these playa sediments were studied rocks are exposed in western Rajasthan (Rai, 1990;
to understand their source and the possible effects of Deotare et al., 1998).
 ARTICLE IN PRESS
P.D. Roy, W. Smykatz-Kloss / Chemie der Erde 67 (2007) 55–68 57

Fig. 1. Location map of the Thar Desert and the investigated playa lakes in the western Rajasthan, India. The annual precipitation
(dotted lines) shows a gradual decrease from the eastern margin (Aravalli mountains) to the west.

3. Methods ELEMENTAL ICP-MS. For a few samples total

digestions were carried out on the carbonate leached
Sediment samples collected for an earlier study (Roy, fractions to find out the effect of carbonates on REE
2004) were investigated for REEs, major oxides and mobility. For the analysis of carbonate leached frac-
trace elements, primary and trace minerals. Prior to the tions, bulk samples were treated with 1 M cold dilute
geochemical analysis, the samples were air dried at HCl before their digestion as prescribed by Tripathi and
50 1C, homogenised and ground to 200 mesh sizes. Rajamani (1999). The REEs were measured against the
REEs were measured in seven sediment samples from ICP-MS multi-elemental standard B certified by the
the four eastern desert margin playas (Didwana, Kucha- National Institute of Standard and Technology. The
man, Phulera and Sambhar) and 11 sediment samples CaO contents in the silicate phase (carbonate leached
from the five western arid core playas (Bap-Malar, samples) and trace element concentrations were mea-
Pokhran, Pachapadra, Thob and That) (Fig. 1) after sured from the powdered specimen using Cu and Pd
digesting the samples completely with HF, HNO3 and filters by Spectrace 5000 EDXRF against the soil
HClO4 in Teflon crucibles. Before the treatments, these standard GXR-2 (Govindaraju, 1994). All other major
crucibles were properly cleaned with a mixture of HCl elements including CaO(total) were measured from the
and HNO3 (3:1). For the digestion, 50 mg of each fused glass discs by SRS 303 AS WDXRF against Be-N.
sample was heated and simultaneously treated with 1 ml Mineralogical investigations were carried out in the
of 65% HNO3 for organic carbon removal, with 2 ml of crushed sediments using XRD analysis and in uncrushed
40% HF and 2 ml of 70% HClO4 to dissolve the sediments using both electron microscopy and microp-
silicates. This procedure was followed at least three robe analyses. For the XRD analysis, powdered bulk
times till the silica gel showed no trace of colour. Then sediments were run on a Siemens D500 diffractometer
the residues were dissolved with 1 N HCl and the volume using Cu target from 31 to 631 at a speed of 0.51/min
was made to 50 ml and measured by AXIOM VG with a step width of 0.01. Thin sections were prepared
 ARTICLE IN PRESS
58 P.D. Roy, W. Smykatz-Kloss / Chemie der Erde 67 (2007) 55–68

++++++
from nine sediment samples after desalting them. The
composition of individual grains were analysed with an

+++
Tt5b

++++++ ++
SX50 Cameca electron microprobe analyser in the

+
+
+

+
Laboratory of Electron Microscopy (Faculty of Physics,
University of Karlsruhe) after studying their optical
properties.

That

Tt5a

+
++++ ++++++

++++ ++++
4. Results

Thob

T1a

+
+

++++ +

+
4.1. Mineralogy

Pa1g

++
+
+

+
++++++
The investigated samples have different proportions

Pachapadra
of detrital and evaporitic minerals. The bulk mineralogy

+++

+++
Pa1a

++
identified from the XRD analysis is presented in Table 1.

+
+
+

+
In the detrital fraction, quartz is the most abundant,

++++++ ++++++
followed by plagioclases and K-feldspars. Micas (bio-

+++
+++

+++
tite), Fe-chlorites and amphiboles are present in trace

Po6l

+
+
+

+
amounts. The sharp XRD peaks of mica and chlorite
indicate their well-ordered crystal structure. Apart from

+++

+++
the primary minerals, trace amounts of pyroxenes,

Po6g

++
+
+

++++++ +
garnets, ilmenite, magnetite, titano-magnetite, rutile,
sphene, lawsonite, allanite, monazite, xenotime, zircon

++++
and epidote, which could not be detected in XRD

Po6d

++

++++++, 440%; +++++, 30–40%; ++++, 20–30%; +++, 10–20%; ++, 5–10%; +, o5%.
Bulk mineralogy of the playa sediments analysed for rare earth element geochemistry

charts, were identified from their compositions and

+
+

+
++++++
optical properties. A comparison of accessory minerals
Pokhran

present in the eastern and western playa sediments is

+++

++++ +++
Po6a

shown in Table 2. Garnets, amphiboles, zircon and +

+
+

++++ +
Western playa sediments

micas (biotite) are present in relatively higher abundance

+++
++

++
in the western playa sediments compared to the eastern
B4d

+
+
+

+
playas. Again pyroxenes, epidote, ilmenite, magnetite,
++++++
Bap-Malar

titano-magnetite, rutile, xenotime and monazite are

identified only in the sediments of western playas. Apart
++
++

++
B4a

+
+
+

+
from that, highly rounded metamorphic rock fragments
++++

+++ ++++
+++

+++

(quartzite, mica schist, epidote–zoisite–muscovite schist,

S2d

+
+
+
+

gneiss) and angular fragments of rhyolite, basalt and +

Sambhar

+++

limestone are also identified from the western playa

++
++

++

+++++ ++
S2a

+
+

sediments. These are 0.2–0.5 mm in diameter. Micro-

++++

photographs of some of the rock fragments are shown in

+++
++

Fig. 2. In the evaporitic fraction, samples have variable

P3g

+
+

abundances of halite (NaCl), calcite (CaCO3), dolomite

++++++

(CaMg(CO3)2), thenardite (Na2SO4), anhydrite (CaSO4)

Phulera

+++

and gypsum (CaSO4  2H2O). Samples P3g, S2d and B4d

++

++
P3a

+
+
+

are enriched in carbonates (calcite and dolomite),

Kuchaman

sample Po6d is gypsum rich and sample Tt5a is halite

++++
++++
++++

++++

rich (Table 1).

++

++
K3a

+
+
+

+
+++++
Eastern playa sediments

4.2. Major and trace elements

+++

++

++

++
D1e

+
+
+

+
+++++

The major oxides were measured from the molten

++++
Didwana

+++

glass discs and trace element concentrations in the

++
D1a

+
+
+

powdered sediment samples. Table 3 presents the major

(CaSO4.2H2O)
(CaMg(CO3)2

and trace element concentrations in the investigated

Table 1.

Amphibole
Plagioclase

Thenardite
K-feldspar

Anhydrite

(Na2SO4)
Dolomite
(CaCO3)

Gypsum
(CaSO4)
Chlorite

playa samples. It is worth mentioning that sample Tt5a

Quartz

(NaCl)
Calcite

Halite
Mica

could not be measured for its major oxides because of its

 ARTICLE IN PRESS
P.D. Roy, W. Smykatz-Kloss / Chemie der Erde 67 (2007) 55–68 59

Table 2. Comparison of accessory minerals present in eastern playa sediments are very similar to UCC, with en-
and western playa sediments riched light REEs (LREEs), depleted heavy REEs
(HREEs) and similarly pronounced negative Eu anom-
Minerals Western playas Eastern playas
aly (Fig. 3). But in abundance they differ among
Amphiboles ++ + themselves and to that of UCC. The analysis of an
Garnets ++ + unleached sample (P3g) and its carbonate leached
Zircon ++ + counter part do not show any significant difference in
Biotite ++ + their patterns (Fig. 4), but they show some characteristic
Ilmenite + differences in the elemental abundance. The untreated
Magnetite + sample exhibits enriched HREE compared to the
Titano-magnetite +
carbonate leached sample.
Hematite +
Epidote +
Based on their REE patterns and relative enrichment
Rutile + and deficiencies of different elements, the UCC normal-
Monazite + ised sediments are divided into two different groups.
Xenotime + Table 4 presents the UCC normalised REE ratios and
Lawsonite + the absolute concentration of REEs in the playa
Pyroxenes + sediments. The sediments of the eastern desert margin
Allanite + playas (Didwana, Kuchaman, Phulera and Sambhar)
Rock fragments + show an enriched LREE (La/Sm ¼ 0.74–0.98), and
++, relatively higher; +, traces.
depleted HREE (Gd/Yb ¼ 1.48–1.95) pattern, with a
homogeneous Eu anomaly (Eu/Eu* ¼ 0.96–1.07)
(Fig. 5). Except D1a and S2d, all the other samples
from eastern playas have relatively higher concentration
very high concentration of halite that caused problem in of Eu compared to UCC. The sediments of the western
preparing the molten glass disc. The eastern playa desert core playas (Bap-Malar, Pokhran, Pachapadra,
sediments have low but homogeneous concentration of Thob and That) show similarly fractionated LREE (La/
Th, whereas the western sediments show a larger Sm ¼ 0.85–1.13) and HREE (Gd/Yb ¼ 1.03–1.30) pat-
variation. Many of the western sediments have much tern and a variable negative Eu anomaly (Eu/
higher concentration of Th than the eastern sediments. Eu* ¼ 0.69–0.99) (Fig. 6). The western playa sediments
The detrital-rich samples show enriched values of SiO2, are relatively less depleted in HREE (Gd/Yb) compared
Al2O3, K2O, TiO2, Fe2O3, Zn, Rb, Cr, Ni, Ba and Zr. to the eastern playas. All the samples have similarly
Similarly, the samples containing calcite and dolomite fractionated REE contents; for eastern playa sediments
have higher abundances of Cu, Sr, CaO, MgO, and the La/Yb ranges from 1.29 to 2.09 and for western playa
gypsum-rich sample shows enriched value of CaO. sediments La/Yb varies from 0.95 to 1.93.
To understand and measure the extent of chemical Another characteristic feature which differentiates the
weathering of the playa sediments, the chemical index of sediments of the eastern playas from those of the
alteration (CIA) was calculated for carbonate leached western playas is their total REE (TREE) concen-
samples using the formulae of Nesbitt and Young trations (for absolute concentration see Table 4). The
(1984): REE contents (TREE) in the western playa samples
show a large variation and many of them have higher
CIA ¼ ðAl2 O3 Þ=ðAl2 O3 þ CaO þ Na2 O þ K2 OÞ  100;
concentration than the eastern playa samples (halite-rich
where CaO* is the CaO in silicate minerals and the other Tt5a, carbonate-rich B4d and gypsum-rich Po6d are
oxides were recalculated again to 100% taking CaO* exceptions). According to the mineralogy, the playa
instead of CaO(total). samples are also grouped into two different groups;
The playa sediments have a CIA value of 6971, (a) rich in detrital minerals (D1a, D1e, K3a, P3a, S2a,
which is just below the average shale (70–75). The B4a, Po6a, Po6g, Pa1a, Pa1g, T1a and Tt 5b) and (b)
average upper continental crust (UCC) has a CIA value rich in evaporitic minerals (P3g, S2d, B4d, Po6d and
of 50 and the weathered residual clay has a CIA value Tt5a). In spite of the diluting effect of quartz, the REE
close to 100. contents are higher in the samples rich in detrital
minerals than the samples rich in evaporites (carbonates,
4.3. Rare earth elements sulphates and chlorides). Feldspars and accessory
minerals, e.g. zircon, monazite, allanite and garnets,
The REE distributions in the playa sediments of might be contributing to the relatively higher REE
the Thar Desert were measured to identify their abundances in the detrital-rich sediments. The carbo-
provenance and to study their relationship with average nate-rich samples have an intermediate REE abundance.
UCC. The chondrite normalised patterns of the They are also characterised by the relatively low
 ARTICLE IN PRESS
60 P.D. Roy, W. Smykatz-Kloss / Chemie der Erde 67 (2007) 55–68

Fig. 2. Microphotographs showing (a) rounded fragment of schist containing epidote, zoisite (20  , XPL), (b) rounded mica schist
fragment and a quartz grain with secondary fluid inclusions (20  , XPL), (c) rounded quartzite and angular quartz, feldspars and
garnet (10  , XPL), (d) rounded gneiss (upper right) with microcline and plagioclases (10  , XPL), (e) angular basaltic fragment
containing labradorite, pyroxene and magnetite (20  , XPL).

depletion of HREE. The UCC normalised carbo- correlation, and Rb, Ba and TiO2 show significant
nate-rich samples (S2d, B4d, Po6l and Pa1g) show a correlation with all the REEs and TREE. Zr influences
positive Ce anomaly. The UCC normalised REE pattern only the light rare earths (LREE). Constituents like
of the gypsum-rich sediment is similar to that of CaO, MgO and Sr show negative correlation with the
carbonate-rich samples. The gypsum-rich sample Po6d REEs (not shown in Table 5). The significant relation-
is also showing a positive Ce anomaly. The REE ships between Al2O3, K2O, Fe2O3, Cr, Ni and the
abundance is lowest in the sample (ThatI-5A) rich in middle rare earths (MREE) indicate that Fe-bearing
halite (NaCl). sheet silicates (biotite and chlorite) also contribute to the
REE geochemistry.
Based on the linear pair coefficients of correlation
4.4. Statistical analysis between the major elements, trace elements and REEs
concentration, a hierarchic dendrogram is constructed
Table 5 presents the coefficient of correlation between (Fig. 7). Sample Tt5a was excluded from the analysis
the REEs and different major and trace elements at 95% because it lacks the major element data. This diagram
significant level. Among the compositional variables of clearly differentiates the western arid core playa sedi-
the sediments, Y and Th show a strong positive ments from the eastern playas. Apart from grouping the
 ARTICLE IN PRESS
P.D. Roy, W. Smykatz-Kloss / Chemie der Erde 67 (2007) 55–68 61

Table 3. Major oxides (mass %) and trace elements (ppm) concentration in the investigated playa sediments

Eastern playa sediments Western playa sediments

Didwana Kuchaman Phulera Sambhar Bap-Malar Pokhran Pachapadra Thob That

D1a D1e K3a P3a P3g S2a S2d B4a B4d Po6a Po6d Po6g Po6l Pa1a Pa1g T1a Tt5a Tt5b

SiO2 59.37 52.23 75.63 65.64 37.30 43.82 41.20 65.22 35.82 56.43 21.46 52.20 67.33 49.42 43.22 45.89 — 67.88
Al2O3 12.85 14.13 10.40 9.68 7.13 14.74 8.63 10.18 8.19 14.48 5.38 13.70 9.03 12.99 14.48 6.29 — 9.99
K2 O 2.59 2.86 1.99 2.00 1.28 2.55 1.70 2.16 0.66 3.12 1.22 2.96 1.54 1.89 2.24 0.90 — 1.40
TiO2 0.61 0.60 0.49 0.47 0.35 0.60 0.39 0.48 0.32 0.60 0.24 0.64 0.32 0.62 0.65 0.32 — 0.52
MnO 0.08 0.10 0.06 0.06 0.07 0.11 0.07 0.07 0.07 0.08 0.03 0.07 0.05 0.10 0.10 0.04 — 0.05
MgO 4.02 5.05 1.75 3.49 11.91 3.72 10.82 4.75 11.59 3.07 1.18 3.77 1.28 3.29 4.26 1.25 — 1.78
CaO 5.34 6.16 3.20 5.66 12.57 5.65 11.65 4.23 10.10 4.49 18.70 6.22 7.91 7.31 6.36 4.68 — 4.56
P2O5 0.19 0.19 0.10 0.16 0.17 0.16 0.13 0.14 0.16 0.17 0.08 0.18 0.06 0.16 0.16 0.05 — 0.09
Fe2O3 4.79 5.77 3.17 3.47 3.24 6.71 3.84 3.66 3.40 5.80 2.34 5.63 2.68 5.61 7.01 1.77 — 3.05
Cu 23 33 16 19 22 16 35 14 32 26 12 26 12 33 44 78 11 23
Zn 47 76 35 39 52 49 57 54 106 74 33 67 29 76 95 36 27 62
Rb 75 113 74 70 64 68 63 72 67 109 47 117 57 119 138 47 34 72
Sr 382 704 233 496 2911 218 1528 160 1198 173 302 245 176 228 226 204 426 252
Y 20 22 18 19 13 12 12 17 15 28 13 29 17 27 25 17 14 19
Zr 192 133 168 185 110 66 87 174 89 163 75 191 126 142 105 179 110 147
Ba 309 388 327 357 314 211 269 406 333 386 167 383 372 367 344 218 177 319
Cr 62 93 47 60 64 40 54 50 49 71 27 64 28 77 96 25 3 42
Ni 29 56 19 31 31 19 32 29 28 37 17 34 14 45 56 8 0 16
Th 9 9 8 8 7 5 7 16 11 15 8 21 8 19 20 15 2 15

1000 D1a
D1e
K3a
P3a
P3g
100 S2a
Sediment /Chondrite

S2d
B4a
B4d
Po6a
10 Po6d
Po6g
Po6l
Pa1a
Pa1g
1 T1a
Tt5a
Tt5b
UCC

0.1
La Ce Pr Nd Sm Eu Gd Tb Dy Ho Er Tm Yb Lu

Fig. 3. Chondrite normalised REE diagrams of the playa sediments and upper continental crust (UCC). All the playa samples are
showing very similar patterns characterised by LREE enrichment and negative Eu anomaly.

samples with respect to their inorganic chemistry, this 5. Discussion

cluster analysis is very helpful in exhibiting the closely
associated samples within each group. The detrital The playa sediments from the Thar Desert consist of
enriched western playa sediments show two different varying assemblages of detritals, derived from the
groups: Pa1a-Pa1g-Po6a-Po6g and T1a-Po6l-Tt5b-B4a. weathering of the catchments, and authigenic evapor-
Similarly, S2a-D1e-P3a-K3a-D1a is the cluster for the ites, precipitated from the saline playa brine. The
detrital enriched eastern playa sediments and P3g-S2d- detritals and ions necessary for evaporites have been
B4d-Po6d is the association of evaporite-rich samples transported into the playas both by aeolian processes
from both the eastern and western Thar Desert. (wind transportation of quartz) and fluvial processes
 62

Table 4. Concentration of rare earth elements (ppm) and upper continental crust (UCC) normalised REE ratios

Eastern playa sediments Western playa sediments

Didwana Kuchaman Phulera Sambhar Bap-Malar Pokhran Pachapadra Thob That

D1a D1e K3a P3a P3g S2a S2d B4a B4d Po6a Po6d Po6g Po6l Pa1a Pa1g T1a Tt5a Tt5b

La 32.43 29.26 25.81 26.59 22.15 15.09 16.55 39.46 20.88 34.19 16.24 45.83 24.32 42.32 42.73 32.92 3.39 36.16
Ce 64.95 59.97 51.98 52.59 43.13 31.54 42.04 67.11 46.49 72.75 37.68 91.82 53.04 85.63 95.68 62.95 6.98 72.54
Pr 6.90 5.92 5.20 5.61 4.84 3.24 4.66 8.05 4.90 8.52 3.98 10.25 5.72 9.23 9.99 7.35 0.73 7.81
Nd 23.84 22.12 18.07 19.56 16.63 11.44 16.55 28.29 18.16 31.07 14.91 37.73 20.75 34.04 36.86 26.20 2.65 27.35
Sm 4.96 4.87 4.02 4.06 3.42 2.45 3.38 5.23 3.52 6.52 2.88 7.67 4.10 6.27 6.70 5.09 0.53 5.40
Eu 0.90 0.94 0.76 0.80 0.65 0.46 0.59 0.87 0.63 1.07 0.47 1.16 0.69 1.05 1.09 0.69 0.06 0.90
Gd 3.82 3.71 2.95 3.04 2.61 1.90 2.49 3.78 2.73 4.84 2.16 5.72 2.98 4.51 4.87 3.27 0.28 3.42
Tb 0.50 0.54 0.44 0.43 0.39 0.29 0.36 0.53 0.40 0.68 0.30 0.78 0.44 0.67 0.71 0.47 0.04 0.47
Dy 2.93 3.24 2.56 2.69 2.34 1.72 2.21 3.51 2.63 4.98 2.07 5.69 3.10 4.73 4.94 3.33 0.30 3.32
Ho 0.45 0.50 0.41 0.44 0.40 0.29 0.37 0.64 0.51 0.94 0.41 1.08 0.62 0.90 0.94 0.62 0.07 0.64
Er 1.44 1.54 1.20 1.31 1.14 0.85 1.11 1.72 1.33 2.33 1.01 2.51 1.41 2.03 2.27 1.40 0.11 1.53
Tm 0.17 0.18 0.15 0.16 0.15 0.11 0.14 0.23 0.19 0.35 0.16 0.41 0.23 0.33 0.35 0.22 0.02 0.22
Yb 1.14 1.24 1.02 1.13 1.02 0.73 0.94 1.68 1.42 2.63 1.10 3.02 1.67 2.29 2.47 1.59 0.13 1.60
Lu 0.15 0.17 0.14 0.15 0.14 0.10 0.13 0.22 0.19 0.33 0.15 0.40 0.23 0.31 0.33 0.21 0.02 0.21
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TREE 144.57 134.20 114.69 118.54 99.00 70.21 91.50 161.31 103.99 171.21 83.54 214.07 119.29 194.30 209.95 146.31 15.31 161.60
(La/Sm)N 0.98 0.90 0.96 0.98 0.87 0.92 0.74 1.13 0.89 0.79 0.85 0.90 0.89 1.01 0.96 0.97 0.96 1.00
(Gd/Yb)N 1.95 1.73 1.67 1.56 1.48 1.51 1.53 1.30 1.11 1.06 1.14 1.10 1.03 1.14 1.14 1.19 1.26 1.23
(La/Yb)N 2.09 1.72 1.86 1.73 1.59 1.52 1.29 1.72 1.08 0.95 1.09 1.11 1.07 1.35 1.27 1.51 1.93 1.65
Eu/Eu* 0.97 1.04 1.03 1.07 1.02 1.01 0.96 0.92 0.96 0.90 0.89 0.82 0.93 0.93 0.90 0.80 0.69 0.99
P.D. Roy, W. Smykatz-Kloss / Chemie der Erde 67 (2007) 55–68
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P.D. Roy, W. Smykatz-Kloss / Chemie der Erde 67 (2007) 55–68 63

100.00
P3g
Decarb P3g

Sediment/Chondrite
10.00

1.00
La Ce Pr Nd Sm Eu Gd Tb Dy Ho Er Tm Yb Lu

Fig. 4. Chondrite normalised REE patterns of a carbonate enriched sample (P3g) and its carbonate leached counter part (Decarb
P3g).

2.00
D1a
D1e
K3a
1.50 P3a
P3g
Sediment/UCC

S2a
1.00 S2d

0.50

0.00
La Ce Pr Nd Sm Eu Gd Tb Dy Ho Er Tm Yb Lu

Fig. 5. Upper continental crust (UCC) normalised REE patterns of eastern desert margin playa sediments.

(seasonal streams). The presence of well-ordered mica due to their low resistance against the chemical
(biotite), Fe-rich chlorite and amphiboles in the playa dissolution processes (interactions with rain, ground
sediments mirror the weak rock–water interaction in the and pore waters). This feature is also reflected by the
region. This feature is also supported by the inter- absence of trace minerals and rock fragments in the
mediate values of the calculated CIA. But the spatial eastern playas as well (Table 2).
distribution of annual precipitation and the abundance The mineralogical and geochemical observations in
of primary and trace minerals mirror the difference in the two above-mentioned regions are also supported by
the degree of chemical weathering in different parts of the REE geochemistry. The homogeneous REE patterns
the desert. The relatively lower abundance of the (Fig. 5) in the eastern playa sediments can be explained
primary minerals (pyroxenes, amphiboles and garnets) by the higher chemical weathering in the eastern desert
in the eastern desert margin playas indicates a relatively margin. But the relatively arid western playa sediments
higher degree of chemical weathering than in the arid exhibit a highly variable REE pattern (Fig. 6).
western ones. The western arid desert core playas have Additionally, they are also enriched in TREE (Table
relatively higher abundance of these primary minerals. 4). In order to understand the different REE abun-
These minerals have disappeared in the eastern playas dances and patterns in the sediments of both the eastern
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64 P.D. Roy, W. Smykatz-Kloss / Chemie der Erde 67 (2007) 55–68

2.00

B4a
B4d
1.50 Po6a
Po6d
Sediment/UCC Po6g
Po6l
1.00 Pa1a
Pa1g
T1a
Tt5a
Tt5b
0.50

0.00
La Ce Pr Nd Sm Eu Gd Tb Dy Ho Er Tm Yb Lu

Fig. 6. Upper continental crust (UCC) normalised REE patterns of western playa sediments.

Table 5. Coefficient of correlation between rare earth elements (REE) and different major and trace elements at 95% significant
level

Al2O3 K2O Fe2O3 TiO2 Th Rb Y Zr Ba Cr Ni

La — — — 0.62 0.93 0.70 0.84 0.65 0.60 — —

Ce 0.52 — — 0.64 0.94 0.79 0.89 0.53 0.57 0.55 0.50
Pr — — — 0.58 0.96 0.72 0.87 0.57 0.57 — —
Nd — — — 0.58 0.96 0.75 0.88 0.52 0.56 0.50 —
Sm 0.53 — — 0.63 0.92 0.77 0.93 0.60 0.60 0.53 —
Eu 0.65 0.59 0.52 0.74 0.81 0.85 0.95 0.61 0.74 0.70 0.62
Gd 0.60 0.57 0.52 0.67 0.87 0.82 0.94 0.58 0.65 0.61 0.56
Tb 0.62 0.55 0.55 0.68 0.88 0.86 0.95 0.52 0.66 0.65 0.60
Dy 0.54 — — 0.59 0.91 0.80 0.93 — 0.60 0.53 0.50
Ho — — — 0.49 0.92 0.74 0.88 — 0.54 — —
Er 0.57 0.51 0.51 0.61 0.89 0.82 0.92 — 0.65 0.58 0.55
Tm — — — 0.49 0.91 0.74 0.88 — 0.53 — —
Yb — — — — 0.90 0.71 0.86 — 0.53 — —
Lu — — — — 0.90 0.71 0.86 — 0.52 — —
TREE 0.51 — — 0.62 0.95 0.77 0.89 0.56 0.59 0.53 —

and western region, UCC normalised LREE (La/Sm), depending upon their resistance to weathering. The
HREE (Gd/Yb) and TREE (La/Yb) fractionations are enriched REE concentrations in the western playa
taken into consideration. The eastern and western playa sediments are attributed to the presence of REE bearing
sediments do not show any LREE fractionation (Fig. 8), heavy minerals (Taylor and McLennan, 1985; McLen-
whereas they show varying degrees of HREE fractiona- nan, 1989; Singh and Rajamani, 2001). The presence of
tion (Fig. 9). The western playa sediments are enriched monazite enriches the western playas in LREEs. This
in HREE compared to the eastern sediments. This interpretation is supported by the fact that many of the
feature is also similar for the TREE fractionation western playa sediments have higher concentration of
(Fig. 10). So the difference in the REE patterns between Th (Table 3). Similarly, a relatively larger amount of
the eastern and western groups of playa sediments is garnets explains the higher concentration of HREEs in
caused mainly by the variation in the (Gd/Yb) ratios the western playas (Table 2). Due to the absence of any
(Fig. 11). This dissimilarity in the degree of fractiona- significant relationship between Zr and HREE (Table
tion of HREE for both the eastern and western playa 5), the influence of zircon on HREE composition has
sediments indicates differential distribution of minerals, been ruled out. Apart from all this, the relationships
 ARTICLE IN PRESS
P.D. Roy, W. Smykatz-Kloss / Chemie der Erde 67 (2007) 55–68 65

2.0

1.5
Distance

1.0

0.5

0.0
Pa1g Pa1a Po6g Po6a T1a Po6l Tt5b B4a Po6d B4d S2d P3g S2a D1e P3a K3a D1a

detrital western evaporite rich detrital eastern

Fig. 7. Hierarchic dendrogram of the investigated playa sediments using the correlation matrix of chemical contents in the
sediments. This diagram is showing three different clusters: the detrital-rich western playa sediments, detrital-rich eastern playa
sediments and evaporitic-rich sediments.

1.5 western playas western playas

2.5
eastern playas eastern playas

2.0

1.0
(La / Sm)N

(Gd / Yb)N

1.5

1.0
0.5

0.5

0.0 0.0
0.0 0.5 1.0 1.5 2.0 0.0 0.5 1.0 1.5
(La)N (Yb)N

Fig. 8. Lighter rare earth elements (LREEs) fractionation of Fig. 9. Heavy rare earth elements (HREEs) fractionation of
the playa sediments with changing REE content. the playa sediments with changing REE content.

between TiO2 and REE (Table 5) are significant enough UCC normalised western sediments is one of the
to consider the influence of Ti-bearing biotite, rutile, characteristic features, which separates them from
sphene, ilmenite and titano-magnetite on the REE eastern desert margin playas. In the arid environment
geochemistry. Except biotite, all other above-mentioned of western playas, the higher abundance of amphiboles,
trace minerals were detected only from the western pyroxenes, garnets and sphene might have masked the
playas. This has also been the reason behind the influence of feldspars on Eu anomaly and have caused
higher concentrations of REE in the detrital-rich this negative Eu anomaly. Similarly, the relatively
western playa sediments. In many of these samples, positive Eu anomaly in semi-humid eastern playa
the rare earths are up to 1.5 times the UCC concentra- sediments can be attributed to the absence of these
tions (Fig. 6). Again the negative Eu anomaly in the minerals.
 ARTICLE IN PRESS
66 P.D. Roy, W. Smykatz-Kloss / Chemie der Erde 67 (2007) 55–68

3.0 western playas leading to the enrichment of HREE in the sediments

eastern playas precipitated from the brine. This positive Ce anomaly
and increasing REE concentrations with increasing
atomic number has also been observed in the alkaline,
2.0
carbonate rich, low temperature waters of Lake Van,
Turkey (Möller and Bau, 1993) and Sassykkul depres-
(La/ Yb)N

sion, East Pamir (Volkova, 1998). So it is believed that

the varying abundance of primary, trace and evaporitic
minerals control the variable REE distributions and
1.0 anomalies in the playa sediments of the Thar Desert.
Due to the lower rock–water interaction, rock
fragments are present only in the western playa
sediments. Besides the angular fragments of rhyolite
0.0 and basalt, there is also a second type of rock fragments
0.0 0.5 1.0 1.5 2.0 occurring in the western playa sediments. This type is
(La)N different from the first type in its degree of roundness
and petrographic character: it is well rounded and
Fig. 10. Total rare earth elements (TREEs) fractionation of metamorphic (mica schist, epidote-bearing schist, gneiss
the playa sediments with changing REE content. and quartzite) in origin (Fig. 2). These rocks have their
source in the eastern desert margin (Sen and Ramalin-
gam, 1976; Biswas et al., 1982; Misra, 1982; Rai and
2.5 western playas Sinha, 1990; Rai and Absar, 1996; Sinha and Raymaha-
eastern playas shay, 2004). The perfect degree of roundness mirrors an
intensive mechanical influence on the grains due to
2.0
relatively long transportation. The distance from the
Aravallis to the western playas is 200 km with a
(Gd / Yb)N

1.5 regional slope from east to west (i.e. Sambhar playa is

situated at an elevation of 500 m and Pokhran playa at
200 m). This favours the transportation of the rock
1.0
fragments from east to west. Although the Luni River is
the only present day integrated drainage network, the
0.5 presence of a number of palaeo-rivers (Bakliwal and
Grover, 1999) in the region indicates that this transpor-
0.0
tation mechanism existed in the past as well.
0.0 0.5 1.0 1.5 2.0 2.5 So from the REE geochemistry, mineralogy and
(La / Sm)N geology of the area, it can be concluded that the source
rocks of playa sediments of both the regions are mainly
Fig. 11. Distribution of upper continental crust (UCC) the metamorphic rocks of the Aravalli mountains,
normalised (La/Sm)N and (Gd/Yb)N in the playa sediments. variable in type and metamorphic grade. The relicts of
these rocks are observed in their well-rounded fragments
and a number of minerals typical for metamorphic rocks
Relatively lower REE contents in the evaporite- (epidote, zoisite, amphiboles, garnets, and well-ordered
enriched playa sediments can be explained by the mica and Fe-chlorite). Trace amounts of monazite and
diluting effect of evaporites on REE abundance (Table xenotime in the playa sediments indicate a part of the
4). The presence of a positive Ce anomaly in the source is igneous rocks, especially granitic pegmatites.
carbonate and gypsum-rich samples apparently results But the relatively higher water activity in the east and
from the stabilisation of carbonate and sulphate the lower degree of chemical weathering in the arid
complexes of Ce (IV) in solutions leading to increasing western playas play a major role in the different mineral
its residence time in the brine. Finally, the enrichment of distribution, which is mirrored by the REE geochem-
Ce is reflected in the (chemical) sediments which istry of the sediments. Additional to this, the western
precipitate from the brine. The enriched concentration playas, e.g. Bap-Malar, Pokhran, That, Thob and
of HREE in the carbonate enriched sample compared to Pachapadra, also receive sediments from the Proterozoic
its carbonate leached counterpart (Fig. 4) and the lower and Mesozoic formations comprising the Malani
depletion of HREE (Gd/Yb) in other carbonate-rich igneous suite (basalt and rhyolite), limestone, sandstone,
samples (Table 4) confirm the formation of stable shale and boulder beds located in their surroundings
HREE–carbonate complexes in the alkaline playa brines (Rai, 1990; Deotare et al., 1998). This interpretation is
 ARTICLE IN PRESS
P.D. Roy, W. Smykatz-Kloss / Chemie der Erde 67 (2007) 55–68 67

supported by the presence of angular rock fragments of (M.S. University, Baroda) for their help and support
basalt, rhyolite and limestone in the sediments of the during the fieldwork in India. Special thanks to Mrs.
western playas. Claudia Moeßner for ICP-MS measurements, Dr.
Georg Istrate for optical studies and Dr. Utz Kramar
for XRF measurements. Suggestions from Prof. Dr.
6. Conclusions Udo Haack helped in improving the quality of the
manuscript.
(1) The cumulative influences of source rock composi-
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