Download Distribution of rare earth elements in the inner shelf

Indian Journal of Geo Marine Sciences
Vol. 45 (12), December 2016, pp 1623-1630
Distribution of rare earth elements in the inner shelf sediments, off the
southwest coast of India
C. Jayaprakash1*, R. Sajeev2 & A. Anil Kumar3
2
1
Marine & Coastal Survey Division, Geological Survey of India, Kochi - 682037, India
Dept. of Physical Oceanography, Cochin University of Science and Technology, Kochi- 682 016, India
3
Marine & Coastal Survey Division Geological Survey of India, Mangalore- 575001, India
*[E-mail: [email protected]]
Received 23 September 2016 ; revised 29 November 2016
Shallow part of the seafloor adjoining the coast of Kerala is mostly covered by silty clay and clayey silt, from north of
Quilon to Kasaragod. Sand dominate the shallow seafloor south of Quilon as well as the deeper part of inner shelf from
Vizhinjam to Ponnani. Concentrations of Rare Earth Elements were determined in the surface sediments within the inner
shelf off the coast of Kerala. ΣREE content in surface sediments varies between 9.15 mg. kg-1 and 319.66 mg. kg-1 .
Distribution pattern suggests higher concentration of REE in the inner shelf sediments off southern Kerala, between Ponnani
and Vizhinjam. Sediments off northern Kerala have lower REE. ΣLREE ranges between 5.61 mg. kg-1 and 306.31 mg. kg-1
and is more in the southern sector. ΣHREE in inner shelf sediments is very low ranging between 2.91 mg. kg-1 and 36.8 mg.
kg-1 . REE in coastal sediments off Kerala is closely related to heavy mineral content. LREE is mostly contributed by
detrital monazite, apatite and sphene in the fine fractions and HREE by detrital zircon, garnet, amphibole and pyroxene.
Sediments from southern and central sectors show enrichment in ΣLREE compared to PAAS. There is a depletion in La, Ce
and Pr in the shelf sediments from the northern sector and remaining LREE in this sector show enrichment. HREE is
enriched in the central and northern sectors and depleted in the southern sector compared to PAAS.
[Keywords: Rare Earth Elements (REE), LREE, HREE, Kerala, Eu, Ce, Marine Sediments, West Coast, India.]
Introduction
Rare Earth Elements (REE) are a group of
15 elements of the Periodic Table that have
similar ionic radii and valency state. The REE
are relatively plentiful in the Earth’s crust
having an overall crustal abundance of 9.2 mg.
kg-1 1. Crustal abundance of individual REE
varies widely from Ce, the most abundant at
43 mg. kg-1 to Tm, the least abundant, at 0.28
mg.kg-1 2.
REE are usually grouped as Heavy Rare
Earth Elements (HREE) and Light Rare Earth
Elements (LREE) 3. La, Ce, Pr, Nd, Pm, Sm
and Eu are grouped as LREE while Gd, Tb,
Dy, Ho, Er, Tm, Yb and Lu form the HREE4.
REE have decreasing ionic radii with
increasing atomic weight from La (1.016 Å) to
Lu (0.85 Å) 5. They are mainly trivalent, with
the exception of Ce and Eu which are also
stable in the tetra and divalent oxidation states.
The decreasing ionic radii from La to Lu cause
different fractionation patterns in various
phases during geochemical processes6.
Due to their chemical coherence, the REE
are widely used as tracers of sources and
processes
controlling
trace
element
distribution in marine sediments7-12 and for
determining depositional processes and
sediment provenance2. REE present in
terrigenous grains are largely unreactive13 and
reflect the signature of hinterland source rocks.
REE distribution in sediments is largely
controlled by scavenging processes by Fe-Mn
oxides14-17, redox conditions of the overlying
water column18, composition of the terrigenous
source19-20 and anthropogenic inputs21.
In coastal areas, sediments deposited in
zones of oxidation with relatively higher
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INDIAN J. MAR. SCI., VOL. 45, NO. 12, DECEMBER 2016
exposure time are found to contain higher
concentration of REE. Present study attempts
to understand the distribution of REE in
surface sediments from the inner shelf off
Kerala and compare the role of mineralogy in
their enrichment.
Materials and Methods
The present study used 19 surface
sediment samples collected from the inner
continental shelf off Kerala for understanding
the distribution and enrichment of REE
(Fig.1). Since the outer boundary of the inner
shelf is vaguely defined, the study area is
restricted within the Territorial Water (TW)
limit, for exactly delineating the outer
boundary. The samples after drying and
homogenisation were washed repeatedly with
deionised water for salt removal, wet sieved
using 230 ASTM mesh and subjected to size
analysis22.
A portion of the samples was
powdered using a pulveriser and analysed for
ΣREE at Regional Chemical Lab, Hyderabad
using Varian-Agilent 7700X ICP-MS and also
at Central Geological Lab, CHQ, Kolkata
using Perkin Elmer SCIEX ELAN R
DRCTM–e Inductively Coupled Plasma Mass
Spectrometry technique. The ICP-MS is
calibrated by multi-element standard solution
to cover the mass range and generate the mass
response curve. Matrix matching with a
standard reference material (SRM) was used
for calibration. International standard GSD-10
and GSD-12 were used for the analysis. Alkali
fusion (mixture of lithium metaborate and
lithium tetraborate) is used to decompose the
fine powdered sediment samples. A Perkin
Elmer ELAN DRC (e) instrument, assembled
with a cross flow nebulizer Scott spray
chamber was used in this experiment. The
ICP-MS, located in a temperature-controlled
laboratory (25 ± 2 °C), was allowed to
stabilize before optimization procedures were
carried out.
Oxide ratio (CeO/Ce+) and
doubly charged ion ratio (Ba++/Ba+) was found
<3% under full optimum condition.
Results
Simplified sediment distribution map
within the inner shelf off Kerala is given in
Fig.2. The shallow part of the seafloor
adjoining the coast is mostly covered by silty
clay and clayey silt, from north of Quilon to
Kasaragod.
Sand dominate the shallow
seafloor south of Quilon as well as in the
deeper part of inner shelf from Vizhinjam to
Ponnani. Coarse fractions of these terrigenous
sediments contain detrital quartz as the
principal mineral component with feldspar and
heavy minerals such as ilmenite, sillimanite,
monazite, rutile, zircon, garnet, magnetite,
sphene, biotite, amphiboles and pyroxenes
besides
shell
carbonate
insubordinate
quantities23-27. Sample locations, sediment type
and REE content of the samples are given in
Table-1.
Fig. 1-Map showing sample location
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JAYAPRAKASH et al.: RARE EARTH ELEMENTS IN THE INNER SHELF SEDIMENTS
Table 1: The Sample Locations and REE Content of surface sediments.
Samp.
No
G-1
G-2
G-3
G-4
G-5
G-6
Location
Chandragiri
River mouth
KasaragodChandragiri
Chandragiri
River mouth
KasaragodChandragiri
Karingote
River mouth
Karingote
River mouth
Lat.
12.47
Long.
74.99
12.47
74.97
12.42
74.87
12.40
74.82
12.21
75.11
12.16
74.99
G-7
Cannanore
11.93
75.29
G-8
Cannanore
11.86
75.12
G-9
CalicutKallayi
11.24
75.46
G-10
G-11
G-12
G-13
G-14
G-15
G-16
CalicutKallayi
AzhikoduPeriyar
PonnaniBharatapuzha
PonnaniBharatapuzha
AzhikoduPeriyar
Alleppy
Alleppy
Depth(m)
Sedi.
Type
2.2
Clay
8.0
Clay
30.0
Clay
42.0
Clay
La
Nd
Eu
Gd
Tb
Dy
Ho
Er
Tm
Yb
Lu
ΣREE
ΣLREE
ΣHREE
21.35
Ce
40.62
Pr
6.90
34.11
2.97
Sm
8.59
11.89
1.81
10.03
1.96
5.25
0.79
4.41
0.66
151.34
114.54
36.80
35.53
70.26
7.76
24.98
1.09
5.87
6.57
0.89
4.93
0.93
2.67
0.50
2.68
0.50
165.16
145.49
19.67
9.21
27.00
2.10
7.53
0.44
1.62
1.56
0.28
1.65
0.32
1.08
0.20
1.28
0.21
54.48
47.90
6.58
32.14
61.54
7.18
21.71
0.99
5.43
6.07
0.83
4.70
0.90
2.59
0.50
2.61
0.50
147.69
128.99
18.70
3.1
Clay
28.9
Clay
8.0
Silty
Clay
34.74
66.90
7.53
24.88
1.06
5.62
6.21
0.86
4.80
0.92
2.69
0.50
2.75
0.50
159.96
140.73
19.23
37.5
Clay
32.87
62.13
7.18
22.07
1.06
5.49
6.16
0.85
4.75
0.90
2.58
0.50
2.56
0.50
149.60
130.80
18.80
7.0
Silty
Clay
33.25
63.97
7.48
22.55
1.05
5.51
6.25
0.85
4.71
0.91
2.57
0.50
2.58
0.50
152.68
133.81
18.87
31.5
Clay
31.89
59.94
6.98
21.09
0.93
5.16
5.45
0.71
3.96
0.76
2.23
0.50
2.34
0.50
142.44
125.99
16.45
29.5
Clay
44.60
82.86
9.58
35.30
1.26
6.88
6.86
0.88
4.60
0.87
2.46
0.50
2.41
0.50
199.56
180.48
19.08
9.8
Clay
53.87
102.07
11.51
39.73
1.54
8.32
8.03
1.00
5.15
0.95
2.67
0.50
2.61
0.50
238.45
217.04
21.41
31.4
Clay
21.77
40.01
4.02
13.89
0.50
2.63
2.01
0.50
0.77
0.50
0.50
0.50
0.50
0.50
238.45
82.82
5.78
13.5
Clay
49.30
91.86
10.70
37.84
1.44
7.76
7.69
1.00
5.17
0.96
2.68
0.50
2.60
0.50
220.00
198.90
21.10
1.08
2.16
0.43
1.56
0.06
0.32
0.58
0.09
0.79
0.18
0.68
0.13
0.93
0.16
9.15
128.99
3.54
38.80
70.25
6.84
23.45
0.47
3.84
3.15
0.45
2.08
0.37
1.11
0.19
1.21
0.20
152.41
143.65
8.76
11.18
75.63
10.17
76.02
10.68
75.89
10.63
75.78
10.18
76.11
9.52
76.25
15.0
Clay
49.70
93.51
10.93
37.30
1.44
7.60
7.63
0.98
5.20
0.97
2.72
0.50
2.65
0.50
221.63
200.48
21.15
76.14
37.0
Clay
42.32
78.54
9.20
32.01
1.21
6.54
6.61
0.84
4.41
0.84
2.33
0.50
2.34
0.50
221.63
169.82
18.37
9.45
Fig. 2-The sediment distribution map within the inner
shelf off Kerala (Modified after Sukumaran et al., 2010 28)
Fig.3- Contour Map showing distribution of ΣREE in the
surface sediments
ΣREE in the inner shelf sediments varies
between 9.15 mg. kg-1and 319.66 mg. kg-1 and
their distribution is depicted in Fig. 3 as
contour map. Sediments between Ponnani and
Vizhinjam show higher ΣREE (>200 mg. kg-1 )
whereas low ΣREE is observed in the northern
sector between Ponnani and Kasaragod.
ΣLREE in surface sediments within the
Territorial Waters off Kerala ranges between
5.61 mg. kg-1 and 306.31 mg. kg-1 and its
distribution is shown in Fig.4. La ranges
between 1.08 mg. kg-1 and 78.57 mg. kg-1 .
Sediment
sample
collected
off
Kaymkulam shows the highest concentration
of La whereas the sample collected from
Karingote river mouth, south of Kanhangad,
has analyzed the lowest. The sector between
Ponnani
and
Vizhinjam
show
high
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INDIAN J. MAR. SCI., VOL. 45, NO. 12, DECEMBER 2016
concentration of La. Ce content ranges from
2.16 mg. kg-1 to 143.21 mg. kg-1 and like La, it
also shows highest concentration off PonnaniVizhinjam sectors. The lowest concentration
of Ce is recorded in the offshore segment
between Kasaragod and Kanhangad.
Karingote river mouth to 0.66 mg. kg-1 off
Chandragiri river mouth. Its content in
sediments is extremely low all along Kerala
coast.
Pr, Nd and Sm range from 0.43 mg. kg-1 ,
1.56 mg. kg-1 and 0.32 mg. kg-1 in Karingote
river mouth to 15.6 mg. kg-1 , 55.68 mg. kg-1
and 10.28 mg. kg-1 respectively in the
sediments off Kayamkulam. Both Pr and Nd
show higher concentration in the offshore
sectors between Ponnani and Vizhinjam. Sm
content is higher in sediments off PonnaniVizhinjam sectors. Kasaragod-Kanhangad
offshore sector shows the lowest content of Pr,
Nd and Sm. Eu is low, ranging from 0.06 mg.
kg-1 recorded in the Karingote river mouth to
2.97 mg. kg-1 in the Chandragiri river mouth.
Lowest Eu is in the sediments off KasaragodKanhangad sector.
Distribution pattern of ΣHREE is shown in
Fig.5. Its content is very low and ranges from
2.91 mg. kg-1 to 36.8 mg. kg-1 .Gd and Tb
vary from 0.58 mg. kg-1 and 0.09 mg. kg-1 in
the Karingote river mouth to 11.89 mg. kg-1
and 1.81 mg. kg-1 in the Chandragiri river
mouth respectively. Sediments off PonnaniAlappuzha show relatively higher content of
these elements. Lowest Dy, Er and Yb
contents of 0.77 mg. kg-1 , 0.5mg. kg-1 and 0.5
mg. kg-1 is from the sediment sample off
Bharatapuzha mouth whereas the highest
contents of 10.03 mg. kg-1 , 5.25 mg. kg-1 and
4.41 mg. kg-1 are from Chandragiri river
mouth.
Sectors such as Kasaragod-Kanhangad,
Alappuzha-Trivandrum and Ponnani recorded
lower Dy, Er and Yb. Ho in the sediments
ranges from 0.18 mg. kg-1 in the Karingote
river mouth to 1.96 mg. kg-1 in Chandragiri
river mouth. Low concentration of Ho is found
off Kasaragod-Kanhangad and AlappuzhaTrivandrum sectors.
Lowest Tm of 0.13 mg. kg-1 is in the
sample from Karingote river mouth and the
highest of 0.79 mg. kg-1 is in the Chandragiri
river mouth. Yb is highest in Chandragiri
sediments (4.41 mg. kg-1 ) and lowest in
Bharatapuzha mouth (0.5 mg. kg-1 ). Highest
Tm recorded is in the sediments off
Someshwara. Lu ranges from 0.16 mg. kg-1 off
Fig.4- Contour Map showing distribution of ΣLREE
in surface sediments
In order to compare the ΣREE in sediments
with that of Post Archaean Australian Shale
(PAAS), REE data of sediments from
Kasaragod,
Ponnani
and
Vizhinjam
representing northern, central and southern
inner shelf were normalized using PAAS
(Fig.6).
Discussion
The shallow part of the seafloor adjoining
the Kerala coast is mostly covered by silty clay
and clayey silt, from north of Quilon to
Kasaragod.
Sand dominate the shallow
seafloor south of Quilon as well as from the
deeper part of inner shelf from Vizhinjam to
Ponnani. REE distribution pattern suggests
higher content along southern Kerala between
Ponnani and Vizhinjam and low content in
sediments off northern Kerala.
JAYAPRAKASH et al.: RARE EARTH ELEMENTS IN THE INNER SHELF SEDIMENTS
1627
Detrital monazite derived from the
hinterland contribute most of the REE in
shallow
marine
sediments
whereas
biogenic/authigenic processes control its
concentration in deep sea sediments29-30.
Monazite can contain about 55 wt.% of
ΣREE31. Accessory minerals such as garnet,
sphene, apatite, zircon, amphibole and
pyroxene are also known to concentrate and
fractionate ΣREE32-35.
Fig. 5-Contour map showing distribution of ΣHREE
in surface sediments
The sediments from Vizhinjam (southern
sector) and Ponnani (central sector) show
enrichment ΣLREE compared to PAAS. There
is a depletion in La, Ce and Pr in the shelf
sediments from Kasaragod whereas other
LREE are higher than PAAS. HREE is
enriched in the central and northern sectors
and depleted in the sediments off Vizhinjam
compared to PAAS.
REE/PAAS
10
1
0.1
La Ce Pr Nd Eu Sm Gd Tb Dy Ho Er Tm Yb Lu
REE (mg.kg-1)
Kasaragod
Ponnani
Vizhinjam
Fig. 6-PAAS normalized REE in the Surface Sediments
The inner shelf sediments along the
southern coast of Kerala has high
concentration of heavy minerals which include
monazite, zircon, garnet and sphene23, 25-27, 36-37.
These minerals, due to their high distribution
coefficient,
incorporate
REE
during
crystallization,
depending
upon
the
temperature, pressure, composition of the
mineral and melt35. Study by Siby Kurian et al
(2013)38 suggested high ΣREE in the
sediments off Kollam and Kochi which was
related to monazite bearing placers. Anil
Kumar et al (2016) considered REE in the
heavy mineral rich sediments along Kerala
coast as the contribution by monazite39. REE
are concentrated by clay fraction in fine
grained sediments 2 and also by fractionation
by authigenic minerals during diagenesis40.
Prudencio et al (1989)41 suggested kaolinite as
the principal carrier of REE in the clay
fraction. Seafloor of the inner shelf of
northern Kerala is covered by silty clay and
clayey silt containing negligible amount of
heavy minerals42-45. Very low ΣREE in this
sector could be the resultant of insignificant
heavy minerals content in them.
The LREE in inner shelf sediments along
southern sector is high and is moderate to low
in northern sector. High heavy mineral content
in the inner shelf sediments along the southern
sector is reported by Geological Survey of
India (GSI). Ilmenite and sillimanite are
dominant in this sector while rutile, zircon,
monazite, magnetite, garnet, pyroxenes, biotite
and iron oxides occur in subordinate
quantities36-37.
Heavy minerals are
concentrated more in the finer fractions25, 36-37.
The northern sector between Ponnani and
Kasaragod has extremely low heavy mineral
content45. Monazite is a known source of
LREE and might have contributed most of the
LREE along Kerala coast. Minerals such as
apatite and sphene also contain LREE and
could be the source of these metals.
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INDIAN J. MAR. SCI., VOL. 45, NO. 12, DECEMBER 2016
HREE is very low in shelf sediments off
Kerala coast. Mineralogical and chemical data
of shale samples indicate that distribution of
HREE in the fine fraction is mainly controlled
by zircon46. Small percentage of other heavy
minerals such as garnet, amphibole and
pyroxene also could be a source of HREE35,46.
Considering the high concentration of minerals
such as garnet, sillimanite, rutile, zircon, mica,
hornblende and in the coarse fractions from
southern inner shelf and insignificant quantity
from northern inner shelf42-45, and congruent
variation in HREE with heavy minerals, HREE
is suggested to be contributed by the heavy
minerals.
The pattern of distribution of heavy
minerals and REE are mutually complimenting
all along Kerala coast. Along southern Kerala,
both heavy minerals and REE are high in inner
shelf sediments whereas along the northern
sector both are present in insignificant
quantities. Sediments devoid of heavy
minerals are not showing appreciable REE
enrichment. Based on this, it is possible to
correlate REE in the inner shelf sediments to
their heavy mineral content. The study
suggests minerals such as monazite, garnet,
sphene, apatite, zircon, amphibole and
pyroxene as the principle contributors of REE
in the inner shelf sediments. Kaolin is present
in good amounts in the inner shelf off
Kasargod42 which also got the ability to enrich
REE41. Considering the dominance of clayey
sediments along the northern inner shelf and
its ability to enrich REE, a part of REE in this
sector also might have contributed by clay
which adsorb these trace metals on their
surfaces while interacting with seawater.
The sediments from southern and central
sector show enrichment in ΣLREE whereas a
depletion in La, Ce and Pr was observed in the
northern sector from Kasaragod than PAAS.
HREE is enriched in the central and northern
sectors and depleted in the southern sector.
Southern inner shelf have higher concentration
of heavy minerals compared to that of northern
inner shelf. Southern shelf sediments hold
considerable concentration of heavy minerals
such as monazite, garnet, sphene, apatite,
zircon, amphibole and pyroxene which contain
fairly high REE. ΣREE vary from 9.15 mg.
kg-1 to 319.66 mg. kg-1 , ΣLREE between 5.61
mg. kg-1 and 306.31 mg. kg-1 and ΣHREE
between 2.91 mg. kg-1 and 36.8 mg. kg-1 .
REE content is high along southern inner shelf
than the northern shelf. The southern shelf also
has high content of LREE. Heavy minerals
such as monazite and sphene contribute most
of the LREE present in sediments. High heavy
mineral content along the southern sector
appears to have caused high LREE content in
the shelf sediments. In the norther inner shelf,
heavy minerals are found in negligibly low
amounts, which is also reflected in the
distribution pattern of LREE.
HREE in
general is very low in the shelf sediments of
Kerala coast. Heavy minerals such as zircon,
garnet, amphibole and pyroxene are the
principle sources of HREE and their content is
also low in the shelf sediments, particularly
along the norther sector. These heavy minerals
would have contributed the HREE present in
sediments.
REE in sediments are also enriched in the
clay fractions. In the surface sediments off
Kasaragod, kaolin is a major constituent.
Considering the dominance of clay sediments
along the northern inner shelf and its ability to
enrich REE, a part of REE also might have
contributed by clay which adsorb these metals
on their surfaces. The sediments from southern
sector and central sector show enrichment in
ΣLREE compared to PAAS. There is a
depletion in La, Ce and Pr in the shelf
sediments from the northern sector and
remaining LREE in this sector show
enrichment. HREE is enriched in the central
and northern sectors and depleted in the
southern sector compared to PAAS.
Conclusion
Acknowledgement
Shallow part of the seafloor adjoining the
coast of Kerala is mostly covered by silty clay
and clayey silt, from north of Quilon to
Kasaragod.
Sand dominate the shallow
seafloor south of Quilon as well as the deeper
part of inner shelf from Vizhinjam to Ponnani.
Authors are highly thankful to Sri. V. Devdas,
Deputy Director General & HOD, M&CSD,
GSI, Mangalore, for the logistic and technical
support extended during this work.
JAYAPRAKASH et al.: RARE EARTH ELEMENTS IN THE INNER SHELF SEDIMENTS
1629
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References
1. Rudnick, R. L., Heinrich, D. H., and Karl, K. T.,
Composition of the Continental Crust, Treatise on
Geochemistry, Oxford, Pergamon (2005) 1-64.
2. Taylor, S. R and Mclennan, S.M., The continental crust:
Its composition and evolution, Blackwell Scientific
Publication (1985) 275–282
3. Dubinin, A.V., Geochemistry of rare earth elements in
the ocean, Lithol. Miner. Resour., 39 (2004) 289–307.
4. British Geological Survey Natural Environment Research
Council, Centre for sustainable mineral development,
Rare Earth Elements, www. MineralsUK.com (2011) 111.
5. David, Z. Piper., Michael Bau., Normalized Rare Earth
Elements in Water, Sediments, and Wine: Identifying
Sources and Environmental Redox Conditions, American
Journal of Analytical Chemistry,4 (2013) 69-83.
6. Henderson, P., General geochemical properties and
abundances of the rare-earth elements, In: Henderson, P.
(Ed.), Rare Earth Elements Geochemistry, Elsevier, New
York (1984) 1–32.
7. Piper, D.Z., Rare earth elements in the sedimentary
cycle: a summary, Chem. Geol., 14 (1974) 285–304.
8. Sholkovitz, E. R., Artefacts associated with the chemical
leaching of sediments for the rare earth elements. Chem.
GeoIogy, 77 (1989)47-51.
9. Toyoda, K., Nakamura, Y., Masuda, A., Rare earth
elements of Pacific pelagic sediments, Geochim.
Cosmochim. Acta, 54 (1990) 1093–1103.
10. Murray, R.W., Buchholtzten Brink, M.R., Gerlach, D.C.,
Russ, G.P., Jones, D.L., Rare earth, major, and trace
elements in chert from the Franciscan Complex and
Monterey Group, California: assessing ΣREE source to
fine-grained marine sediments, Geochim. Cosmochim.
Acta, 55 (1991) 1875–1895.
11. Piper, D.Z., Perkins, R.B., Rowe, H.D., Rare-earth
elements in the Permian phosphoria formation: Paleo
proxies of ocean geochemistry. Deep-Sea Res., 54 (Pt. II)
(2007) 1396–1413.
12. Censi, P., Incarbona, A., Oliveri, E., Bonomo, S.,
Tranchida, G., Yttrium and ΣREE signature recognized
in Central Mediterranean Sea (ODP Site 963) during the
MIS 6–MIS 5 transition, Palaeogeogr. Palaeoclimatol.
Palaeoecol., 292 (2010) 201-210.
13. Sholkovitz, E. R., Landing, W. M., and Lewis, B. L.,
Ocean particle chemistry: The fractionation of rare earth
elements between suspended particles and seawater.
Geochim. Cosmochim. Acta 58 (1994)1567– 1579.
14. Elderfield, H., Greaves, M.J., The rare earth elements in
seawater, Nature 296 (1982) 214–219.
15. Whitfield, M., Turner, D.R., The role of particle in
regulating the composition of seawater, In: Stumm, W.
(Ed.), Aquatic Surface Chemistry, Wiley, New York
(1987) 457–493.
16. Elderfield, H., The oceanic chemistry of the rare earth
elements, Philos. Trans. Roy. Soc. Lond. Ser. A 325
(1988) 105–126.
17. Haley, B.A., Klinkhammer, G.P., McManus, J., Rare
earth elements in pore waters of marine sediments,
Geochim. Cosmochim. Acta, 68 (2004) 1265–1279.
18. Liu, Y.G., Miah, M.R.U., Schmitt, R.A., Ce: A chemical
tracer for paleo-oceanic redox conditions, Geochim.
Cosmochim. Acta, 52 (1998) 1361–1371.
19. Chaudhuri, S., Cullers, R.L., The distribution of rare
earth elements in deeply buried gulf coast sediments,
Chem. Geol., 24 (1979) 327–338.
20. Taylor, S.R., McLennan, S.M., The Continental Crust, Its
Composition and Evolution, Blackwell Scientific
Publications, Oxford, 1985.
21. Olmez, I., Sholkovitz, E.R., Hermann, D., Eganhouse,
R.P., Rare earth elements in sediments off southern
California: a new anthropogenic indicator, Environ. Sci.
Technol., 25 (1991) 310–316.
22. Folk, R.L., Petrology of sedimentary rocks. Hemphill
Publishing Co. Texas (1974).
23. Senthiappan, M., Adiga, K.S., Durairaj, U., Sreepada
Rao, N., Abdulla, N.M., Sankar, J., Kumaran,K., and
Ramachandran, K.V., Seabed survey and sampling
within territorial waters off Attipara-Anjengo and
preliminary investigation for heavy mineral sands off
Quilon, Chavara and Varkala, Kerala, Cruise Report
SSAU 34 & 35, Geological Survey of India, M&CSD,
Mangalore (1989) 8.
24. Senthiappan, M., Raghavan Nambiar, A., Michael, G.P.,
Durairaj, U., Abdulla, N.M., Sankar, J., Kumaran, K.,
Unnikrishnan, E., and Mukhopadhyay, T.K., Report on
exploration for heavy mineral sands off Paravur and
Varkala, Kerala, Cruise Report SS-46 & 47, Geological
Survey of India, M&CSD, Mangalore, (1989) 18-22.
25. Nambiar, A.R., Venkataramana,P., Kannan, S.,
Rao,M.K., Gangadharan,A.V., Pai,P.R., Rahothaman,
V.K., Das, A., Prakash Kumar, R., Davis, K.J., Report
on geological sampling in territorial waters of India in
Arabian Sea off Cochin and off Valapatanam river,
Kerala coast, Cruise Report SS.112, Geological Survey
of India, M&CSD, Mangalore, (1995) 1-96.
26. Senthiappan, M., Michael, G.P., Kannan, S.,
UnniKrishnan, E., Hegde, S.V., Gangadharan, A.V.,
Chaki, S.,Patra,S., Nandi,B.K., Exploration of heavy
mineral sands off Vettutura – Trivandrum and shallow
seismic survey off Chavara - Trivandrum, Kerala, Cruise
Report SS-123, Geological Survey of India, M&CSD,
Mangalore (1999) 19.
27. Lakshmana, B.K., Kumaran, K., Maran, N., Dinesh,
A.C., Shareef, N.M., Dutta, G.K., Ramesh Singh, Borkar,
B.N., and Veerabhadraiah, D., Parametric studies within
Territorial Waters off Kerala coast between
Ambalapuzha and Anjengo (Karunagapalli-Anjengo
sector), Cruise Report SD-217, Geological Survey of
India, M&CSD, Mangalore (2010) 14.
28. Sukumaran, P.V., Unnikrishnan, E., Gangadharan, A.V.,
Zaheer, B., Abdulla, N.M., Kumaran, K., Ramachandran,
K.V., Hegde, S.V., Maran, N., Bhatt, K.K., Rao, M.K.,
Dinesh, A.C., Jayaprakash, C., Praveen Kumar, P.,
Shareef, N.M., and Gopalan, C.V.,
Marine sand
resources in the south-west continental shelf of India,
Indian Jour. Of Geo. Mar. Sci ., 34(4) (2010) 572-578.
29. McLennan, S. M., Rare earth elements in sedimentary
rocks: influence of provenance and sedimentary
processes. In: Lipin B. R., McKay G. A. (Eds):
Geochemistry and Mineralogy of Rare Earth Elements.
Reviews in Mineralogy. Mineral Soc Am, 21 (1989)169–
200.
30. Tranchida, G., Oliveri, E., Angelone, M., Bellanca, A.,
Censi, P., D'Elia, M., Neri, R., Placenti, F., Sprovieri, M.,
1630
1626
31.
32.
33.
34.
35.
36.
37.
38.
39.
INDIAN J. MAR. SCI., VOL. 45, NO. 12, DECEMBER 2016
Mazzola S., Distribution of rare earth elements in marine
sediments from the Strait of Sicily (western
Mediterranean Sea): Evidence of phosphogypsum waste
contamination, Marine Pollution Bulletin, 62 (2011)
182–191.
Bea, F., Pereira, M.D., Stroh, A., Mineral/leucosome
trace-element partitioning in a per-aluminous migmatite
(a laser ablation-ICP-MS study), Chem. Geol, 117,
(1994) 291 – 312.
Jung, H. S., Lim, D. I., Yang, S. Y., and Yoo, H. S.,
Constraints of ΣREE distribution patterns in core
sediments and their provenance, Northern East China
Sea, Economic and Environmental Geology, 39
(2006)39–51.
Jung, H.S., Lim, D.J., Choi, Y., Yoo, H. S., Rho, K. C.,
and Lee, H.B., Rare earth element compositions of core
sediments from the shelf of the South Sea, Korea: Their
controls and origins, Continental Shelf Research, 48,
(2012)75–86.
Gonzalez Lopez, M., Bauluz, B., Fernandez-Nieto, C.,
and Oliete, A. Y., Factors controlling the trace-element
distribution in fine-grained rocks: the Albian kaoliniterich deposits of the Oliete Basin (NE Spain),Chemical
Geology, 214, no. 1-2, (2005)1–19.
Gilbert N Hanson., Rare Earth Elements in Petrogenetic
Studies of gneous Systems, Ann. Rev. Earth Planet
Sci.8, (1980) 371-406.
Charlu, T.K., Jayakumar,R., Abdulla, N.M., Kumaran,
K., and Unnikrishnan, E., Exploration for placer sands in
the near shore shelf area off Quilon — Varkala, Kerala,
Cruise Report SS-100, Geological Survey of India,
M&CSD, Mangalore, (1993) 12-14.
Senthiappan, M., Michael, G. P., Charlu, T. K.,
Jayakumar, R., Abdulla, N. M., Kumaran, K., and
Unnikrishnan, E., Exploration for placer sands off
Varkala - Anjengo, Kerala, Cruise Report SS-III,
Geological Survey of India, M&CSD, Mangalore,(1995)
11-13.
Siby Kurian, B. Nagendaer Nath, N. Chandramohana
Kumar, and Nair, K.K.C., Geochemical and Isotopic
Signatures of Surficial Sediments from the Western
Continental Shelf of India: Inferring Provenance,
Weathering and the Nature of Organic Matter, Jour.
Sediment. Res, 83(6), (2013) 427-442.
Anil Kumar, A., Renjith, M.L., Anju, P.V., and
Premakumar, P., Preliminary evaluation of REE in the
40.
41.
42.
43.
44.
45.
46.
marine sediments from west coast of India, FSP 2014-15,
Report, Geological Survey of India, M&CSD,
Mangalore,(2016) 80-99.
Honty, M., Clauer, N., and Sucha, V., Rare-earth
elemental systematics of mixed-layered illite-smectite
from sedimentary and hydrothermal environments of the
Western Carpathians (Slovakia), Chemical Geology, 249,
no. 1-2, (2008) 167–190.
Prudencio, M. I., Figueiredo, M. O., and Cabral, J. M. P.,
Rare earth distribution and its correlation with clay
mineralogy in the clay-sized fraction of Cretaceous and
Pliocene sediments (central Portugal), Clay Minerals, 24,
no. 1, (1989) 67–74.
Sukumaran, P.V., Kumaran, K., Rao, Ch. V.,
Jayaprakash,C., Dinesh, A.C., Sastry, G.M.N., Rao,
J.A.N., Sathyanarayana,G.V., Joseph, P.J., Report on the
seabed survey in the territorial waters off SuratkalKasaragod, Geological Survey of India, M&CSD,
Mangalore, Cruise Report SD-154, (2002) 16-17.
Jayakumar, R., Unnikrishnan, E., Bhat, K.K., Padmaiah,
N., Maran N., and Jayaprakash, C., Progress report on
parametric studies within territorial waters of India off
Kerala coast between Kannur and Kadalur point, (Part of
Kannur - Azhikode Project), Geological Survey of India,
M&CSD, Mangalore, Cruise Report SD-182,(2006) 141.
Jayakumar, R., Unnikrishnan, E., Bhat, K.K., Padmaiah,
N., Dinesh, A.C., Mukherjee, G.S., Mukherjee, K.K.,
Naskar, B.N., and Premakumar, P., Progress report on
parametric studies within Territorial Waters of India off
Kerala coast between Kadalur point and Beypore (Part of
Kannur-Azhikode project), Cruise Report SD.188,
Geological Survey of India, M&CSD, Mangalore,
(2007)1-35.
Kannan, S., Ramachandran, K.V., Maran, N., Rao, M.K.,
Rao, J.A.N., Vijayarajulu, H., Singh, U.V., and Sengupta,
B.J., Report on parametric studies within the territorial
waters of Kasargod-Mt Dilli, Kerala coast and surveys
for IGCP Project 464, Cruise Report SD-193, Geological
Survey of India, M&CSD, Mangalore, 2010.
Francesco Cavalcante., Claudia Belviso., Giuseppe
Piccarreta., and Saverio Fiore., Grain-Size Control on the
Rare Earth Elements Distribution in the Late Diagenesis
of Cretaceous Shales from the Southern Apennines
(Italy). Journal of Chemistry, Article ID 841747, (2014)
11.