Palaeo-environmental reconstruction of pedogenic calcretes in Sathankulam, Southern India: an integrated approach

doi:10.21203/rs.3.rs-2466036/v1

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Palaeo-environmental reconstruction of pedogenic calcretes in Sathankulam, Southern India: an integrated approach

https://doi.org/10.21203/rs.3.rs-2466036/v1

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A widespread and thick calcrete level occurs as an intervening deposit between soil surface and Proterozoic hard metamorphic granite (or) Tertiary calcareous sandstone basement rocks of Sathankulam region, Thoothukudi district of Tamilnadu, India. Field observation reveals the nature of calcrete deposits as gravel, chalky, laminated, massive, and nodular forms. Photomicrographs of calcrete thin sections reveal calcified macrocystis, calcified fungal hyphae, calcified microtubules, peloidal, calloforms with clay clast rimmed by micritic calcite, sesquioxide preservation and micritic calcite preservation in septarian nodules. X-ray diffraction analysis of calcrete profile samples reveals predominance of micritic calcite and limited occurrence of clay minerals of sepiolite, palygorskite, and other grains of quartz, feldspar, hornblende, biotite, and gypsum. Geochemical studies of two calcrete profile samples show the predominance of major elements of CaO, Al₂O₃, MgO, Fe₂O₃, minor/trace elements of Ba, Nb, Zr, Y, Sr, Rb, Ga, Zn, Ni, Cu, and Cr and rare earth elements/chondrite values of La, Ce, Pr, Nd, Sm, Gd, and Dy. Statistical evaluation of all major, minor/trace, and rare earth elements through multiple correlations, principal component analysis, and cluster analysis establish the inter-relationship and affinities between the parameters of the source elements of the two profiles. Stable isotope study of δ¹³C and δ¹⁸O of Hudson diagenitic plot study reveals that the two calcrete profile samples represent the reconstruction of palaeo-diagentic environmental condition as meteoric cement and continental freshwater limestone depositional environment. Further, stable isotope analysis of the area plotted on Julian Andrews and Keith and Weiber standard plot represents the weaker monsoonal climate and meteoric-diagenetic environment respectively.

Geochemistry

Stable isotopes

Statistical evaluation

XRD

Calcrete profile

Carbonates are deposited in a wide range of depositional environments. Important pure carbonate-bearing rocks are shell limestone, carbonatite, and meta-sedimentary crystalline limestone. Depositional environments of carbonates include oceans, estuaries, lakes, rivers, caves, springs, and also within the pedolith and regolith. There is a large group of terrestrial carbonate which precipitates originally as authigenic minerals within the host material, such as soil, saprolite, and sediments. These authigenic carbonates vary widely in composition (calcite dominant to dolomite dominant) from several percent to nearly pure carbonate. Despite several terms are used for calcrete in various countries, most of the authegenic carbonates those deposits are commonly referred as calcrete. It is widespread in many arid and semi arid parts of the world. Calcrete has been described in the 13% of the total land surface of the world (Yaalon, 1981; Chen et al.,, 2002). In Australia, 21% of the land surface is occupied by calcrete occurrence, because of the availability of a large proportion of arid and semi-arid climates (Queen 2006). Since calcrete is an alternate cheap resource material to primary limestone resources, like shell limestone and crystalline limestone for cement production, many cement industries are searching calcrete resources for their cement production. Due to the impotence of the calcrete as an economic resources, numerous researchers have concentrated their research on calcrete, not only in India but also in various parts of the world (Khadikar et al., 2000; Nettleton et al., 2000; Tandon and Andrews, 2001; Hema and Sankar, 2004; Horea Bedlean, 2004; Paul Grevenitz and Allan 2005; Varga Andrea et al., 2005; Queen, 2006; Hirmas et al., 2008; Prudencio et al., 2010; Werner Smykatz-Kloss and Roy, 2010; Udayanapillai et al., 2012, 2014; Ceren küçükuysal and Selim Kapur, 2014; Tukur et al., 2015; Perumal and Udayanapillai, 2015; Armstrong-Altrin (2020); Armstrong-Altrin et al., 2011, 2021; Matthias Alberti et al., 2021; Mattey et al., 2021). Since the study area, Sathankulam and its surrounding villages have boundless deposits of calcrete, not only occurring within the pedolith part, but also occur as exposed eroded surface outcrop up to the extent of the level of seven square km coverage, with more thickness of up to the level of 10ft, above the basement rocks, an attempt has been made in this research paper to concentrate on the geochemistry of calcrete of this region.

1.1. Geological Settings

The study area consists of both sedimentary and metamorphic rocks. Metamorphic terrain of the area consists of Proterozoic basement rocks, such as granite, charnockite, khondalite, calc- granulite, and crystalline limestone. Basement rocks are disposed under Tertiary and Quarternary calcareous sandstone and shell limestone deposit. Recent/Sub-Recent, Teri sand and loamy soil or black soil occurs as surface outcrops rest over the Proterozoic and Tertiary and Quaternary basement rocks. Calcrete occurs within the pedogenic part or as an exposed eroded surface outcrop above the basement rocks (Table 1). Location of the calcrete profile, geological map and schematic stratigraphical successions of the area are given respectively in Fig. 1a & 1b.

Table 1

Startigraphic succession of the study area
Depth range	Lithology	Age
Above the ground level up to 62m	Beach sediment, river alluvium, black soil and teri soil	Recent to Sub-Recent
Below the ground level Upto 14 m	Laterite, Calcrete	Holocene to Pleistocene
From 14m – 60m below ground level	Shell limestone, Calcareous sandstone, Clay, Shell limestone and Sandstone	Quaternary and Tertiary
Below 4m and 60m	Crystalline rocks- Pegmatite, Granite, Charnockite, Hornblende-Biotite gneiss, Calc granulite, Crystalline limestone, Quartzite	Proterozoic

1.2 Material and Method

A total of ten calcrete samples from two representative profiles (Lat N 8^o 28’ 30” and long E 77^o 59’ 50” and lat N 8^o 17’ 47” and long E 77^o 5’ 15”) developed on top of sedimentary and metamorphic granitic rock, were collected from top to bottom (Table 2). While collecting the samples, nature of the calcrete deposit was observed. Hard calcrete samples were used for the preparation of thin sections at Suchitra polishing unit, Ennore, Chennai. Photomicrographs of the micro thin-section were taken for petro-mineralogical observation from the Dept. of Geology, Alagappa University, Karaikudi. Four selected calcrete powdered samples from sedimentary terrain calcrete and metamorphic area were subjected to X-ray diffraction analysis for identifying general mineralogy and clay mineralogy. XRD instrument has been calibrated for 2θ positions from 0 to 30° and 0 to 60° for clay mineralogy and other general mineralogy respectively. Entire mineralogy and clay mineralogy from the same powder samples have been identified through their `d´ spacing values and their respective intensities with the help of the literature (Sachinath Mitra, 1989; Kile and Eberl, 2000; Jimenez-Espinosa and Jimenez-Millan, 2003; Waragai, 2005; Hong et al., 2007; Harris et al., 2008; Moazallahi and Farpoor, 2012; Udayanapillai et al., 2015; Perumal and Udayanapillai et al., 2020). Ten powdered samples from the two calcrete profiles were analyzed for major elements and minor/trace and rare earth elements analysis through the instruments X-ray Fluorescence Spectrometer (XRF) and Inductively Coupled Plasma Multi-Spectrometer (ICPMS) respectively at National Geophysical Research Institute (NGRI), Hyderabad. Total Carbonate (TCO₃) of the ten powdered calcrete samples has been established separately by the titration method (Piper 1947). Loss On Ignition (LOI) in the major element analysis, was calculated by subtracting the total value of ten major oxides from cent percent (100%) values. Geochemical environment of both calcrete profiles of the area were interpreted with advanced statistical methods, such as Pearson multiple correlations, principal component analysis (PCA), and cluster analysis by using the software PAST. Calcrete is formed either by evapotranspiration of alkaline-rich groundwater or by pedogenic leaching of meteoric/surface water (Hill et al., 1999; Queen, 2006; Hema et al., 2010; Udayanapillai et al., 2019; Perumal and Udayanapillai, 2020). Water qualities of the groundwater samples collected from the area were analyzed by APHA (1998) standard procedure. Major elements geochemistry of the source rock and the soil, such as black soil and red teri soil of the area were also analyzed through XRF method at NGRI Hyderabad.

Table 2

clay and general mineralogy of calcrete samples of the Two profiles.
S.No	Minerals	D–Space values in Å	Name of the Mineral	Chemical composition
1	Common Mineral	2.58	Hypersthene	(Mg, Fe) SiO₃
2		1.57	Biotite	K₂(Mg, Fe^+ 2)₆₋₄ (Fe^+ 3, Al, Ti)₀₋₂ (Si_6 − 5 Al_2 − 3 O₂₀) (OH, F)₄
3		8.59	Hornblende	[Na, K]₀₋₁ Ca₂ (Mg, Fe^+ 2, Fe^+ 3, Al)₅ [(Si_6 − 7) Al_2 − 1 O₂₂] (OH, F)₂
4		2.76	Gypsum	CaSO₄ 2H₂O
5		2.03	Feldspar	CaAl_2,Si₂O₈
6		2.09	Calcite	CaCO₃
7		3.33	Quartz	SiO₂
8		2.53	Magnetite	(Fe³⁺) [Fe₂ + Fe₃+]O₄
9	Clay Mineral	11.34	Palygorskite	Mg₃ H₂ Si₈ O₂₂ (H₂O) .2H₂O
10		9.63	Montmorillonite	(Na,Ca)0,3(Al,Mg)₂Si₄O₁₀(OH)₂•n(H₂O)
11		4.42	Illite	(K,H₂O)Al₂[(Al,Si)Si₃O₁₀](OH)₂
12		7.27	Kaoline	Al₄ (Si₄O₁₀) (OH)₃
13		8.14	Sepiolite	Mg₈ H₆ Si₂ O₃₀ (OH)₁₀.6H₂O
14		17.37	Smectite	(1/2 Ca, Na)₀₋₇ (Al, Mg, Fe)₄

Selected powdered calcrete profile samples has been analyzed for δ¹³C and δ¹⁸O isotopes by the instrument triple collecter SIRA mass spectrometer at NEG; LABISE in department de Geologia, Universidat, Federal de per nambugo, Brazil.

For δ¹³C and δ¹⁸O isotopic determination from calcrete samples, CO₂ was extracted from powdered calcrete in a high vacuum line, after reaction with H₂SO₄ at 100% concentration and at 25µc and cryogenically cleared according to the method described by Craig (1957). CO₂ gas released by this method was analyzed for δ¹³C and δ¹⁸O isotopes in a double inlet, triple collecter SIRAII mass-spectrometer using the reference gas BSC (Borboroma Skarn Calcite) calibrated against NBS-18, NBS-19 and NBS-200 have a value of 11.28% POB for δ¹⁸O − 8.58% PDB for δ¹³C. The results are reported as per ml (%0) δ¹³C and δ¹⁸O values relative to Pee Dee Belemnite (PDB international standard of Vienna). Conversion of SMOW value to PDB standard has been attempted by using the formula δ¹⁸O calculate (SMOW) = 1.03086 (Fried man and Neil, 1977; Sankar et al., 2006; Nagendra et al., 2011). Uncertainties of isotopes measurement were estimated at 0.1%0 for C and 0.2%0 for O, based on multiple analyses of an interval of laboratory standard (BSC).

Field observation, mineralogy and clay mineralogy, geochemistry of major, minor/trace, and rare earth elements and stable isotope analysis of the calcrete profiles are discussed as follows.

2.1. Field Observation

Calcrete occurs as gravel or granular layer at the upper part of the profile below the black soil and red teri soil. In the lower part of the profile shows an alternative layer of hard, compact, and chalky layer. Calcrete profile has a maximum thickness of 10 feet between black soil outcrop and weathered granite basement rocks in the metamorphic terrain and red soil and shell limestone basement rocks in the sedimentary terrain. Such similar observation has already been reported in Coimbatore region (Hema and Sankar, 2004) and Pandalgudi region (Udayanapillai et al., 2014, 2015). Calcrete profile in the sedimentary and metamorphic terrain shows the undulating profile below the red teri soil and black soil. Undulation in the calcrete profile below the teri soil and black may be due to the differential evapotranspiration of alkaline-rich groundwater. Soil consists of sand and clay content (Udayanapillai and Perumal, 2010). Elevated beak of the calcrete zone may be happened, due to the more porosity and permeability of sand grain. Calcrete profile is controlled by clay mineral content which will not be permeable to groundwater fluctuation, during the evapotranspiration process. Calcrete profile shows varied forms of massive, chalky, laminated calcrete, nodular, oolitic, and gravel calcrete forms (Fig. 2a-d). Micro-morphological feature of calcrete depends on the degree of carbonate availability from pedogenic or groundwater resources (Perumal and Udayanapillai, 2015, 2019). C3 and C4 plants represent arid and semi-arid climate conditions (Hema and Navin, 2004; Perumal and Udaiyanapillai, 2020). Rhizome concretions of calcrete were also observed in the roots of the plants Prosopis juliflora (C3) Arecaceae (C4), Acacia (C4) in both sedimentary and metamorphic areas. This indicates the causes for more evapotranspiration activities in the study area. Stylolite (CaCO₃) banding of calcrete was also observed in the bottom of the compact teri sandstone beds. Alkaline rich groundwater has been derived from the sources of calc-alkaline and per-alkaline compositional basement rocks, such as from hornblende -biotite gneiss, crystalline limestone, calc-granulite, charnockite and granite, shell limestone, and calcareous sandstone rocks which causes for more calcrete development within the pedolith part of this study area.

2.2. Petro Mineralogy

Petro-mineralogical characters are shown in the photomicrographs (Fig. 3a-f). Petro-mineralogical study establishes petrography and textural characters. Horea Bedlean (2004) has been classified into alpha and beta calcrete. Alpha calcrete represents micro-nodules, circum-granular cracks, whereas beta calcrete represents microbial coating, needle fibre calcite, calcified microtubules, septal fabric, microcodium, and calcified pellets (Wright and Tucker, 1991; Horea Bedlean, 2004). But, it is not a hard and fast rule in possessing above micro-morphological characters (Udayanapillai et al., 2015). Petro-mineralogical characters of the area shows micritic calcite or microsparitic calcite rimming around quartz grain, lensoidal precipitation of micritic calcite, displacement of biotite flakes by micritic calcite and deep brown dendritic impregnation of sesquioxide (Al₂O₃Fe₂O₃) preservation. Sesquioxide preservation indicates arid and semi-arid climate. Such observations have already been reported in the calcrete of the Pandalgudi region (Udayanapillai et al., 2015) and calcrete of the Coimbatore region (Hema et al., 2010). Some calcrete section show calcified tubules, calcified microcystis, clay clast surrounded by a calloform structure of micritic calcite rimming. Micritic calcite precipitation in the pedogenic part of the soil may be due to the alkaline-rich groundwater fluctuation or from pedogenic leaching of meteoritic or surface water. Such similar observation have already been reported from various areas (Udayanapillai and Thirugnanasambandam 2006; Perumal and Udayanapillai, 2019, 2020).

2.3. XRD Analysis

Clay mineralogy of calcrete through XRD analysis is tabulated in (Table 2). Based on `d´ spacing values and their intensity, silicate minerals quartz, orthoclase, plagioclase, hornblende, biotite, hypersthene, gypsum, and little gypsum were identified. Clay minerals kaoline, palygorskite, sepiolite, beidellite, smectite, illite and montmorillonite were also identified from calcrete (Fig. 4a-d). Such similar observations of mineralogy and clay mineralogy in calcrete have already been reported in various areas (Hema and Navin, 2004; Udayanapillai and Thirugnanasambandam, 2012; Perumal and Udayanapillai, 2019; 2020).

2.4. Geochemical Observation

2.4.1. Major Element Geochemistry

Results of the major oxides of two calcrete profiles are tabulated in (Table 3). The two profile samples show the predominant elemental composition of CaO, Al₂O₃, MgO, Fe₂O₃ whereas the other oxides MnO, Na₂O, K₂O, TiO₂, and P₂O₅ show less concentrations (Fig. 5). The chemistry of calcrete is controlled by the groundwater chemistry, lithogenic and pedogenic material under arid and semi-arid climatic conditions. Alkaline-rich groundwater (Table 4) is derived from the source rock aquifer of calc-alkaline and per-alkaline compositional source rocks (Table 5). They are brought to the bottom of the pedogenic part by evaporation and evapotranspiration process and replace the soil part under arid and semi-arid climatic conditions. Rhizome of C3 plants, like prosopis juliflora, C4 plants like Arecaceae in the study area causes for the evapotranspiration of groundwater. Soil, outcrop of teri soil, black soil, and loamy soil derived from the above source rocks are also subjected to pedogenic leaching by meteoric or surface water, under arid and semi-arid climatic conditions. This leaching process is also caused for calcrete development in the pedogenic part. Hill et al (1999) established that calcrete is formed either by evapotranspiration of groundwater or by pedogenic leaching of meteoric water under arid and semi-arid climatic conditions. Such similar reports have also been established in various areas (Hema and Navin, 2004; Queen 2006; Udayanapillai et al., 2015; Perumal Velmayil 2017).

Table 3

The major element geochemistry of two pedolith calcrete profile samples from top to bottom section (values in %)
S.No	Sample Name	SiO₂	Al₂O₃	Fe₂O₃	MnO	MgO	CaO	Na₂O	K₂O	TiO₂	P₂O₅	TCO₃	LOI
1	P1.1 (Top)	44.54	19.71	15.4	0.16	2.07	10.38	2.62	1.37	2.1	0.03	43.5	1.62
2	P1.2	25.31	9.63	4.04	0.36	2.18	35.61	1.79	0.8	0.58	0.06	68.3	19.64
3	P1.3	21.72	8.21	3.64	0.73	2.44	38.13	1.36	0.66	0.27	0.08	73.4	22.76
4	P1.4	27.75	10.09	3.6	0.16	2.92	34.7	2.64	1.00	0.4	0.04	70.2	16.7
5	P1.5 (Bottom)	43.47	13.26	5.22	0.24	3.94	18.78	8.8	1.37	0.63	0.05	48.7	4.24
6	P1.Avg.	32.558	12.18	6.38	0.33	2.71	27.52	3.44	1.04	0.80	0.05	60.82	12.99
7	P2.1 (Top)	7.21	3.13	1.02	0.07	0.62	54.37	0.4	0.37	0.18	0.05	84.6	32.58
8	P2.2	4.4	1.57	0.62	0.06	0.44	58.15	0.36	0.29	0.13	0.03	88.4	33.95
9	P2.3	25.02	5.51	2.45	0.1	1.23	41.23	1.22	0.62	0.32	0.11	75.4	22.19
10	P2.4	10.25	3.85	1.71	0.08	0.74	51.14	0.87	0.68	0.2	0.09	86.3	30.39
11	P2.5 (Bottom)	8.96	2.63	0.92	0.06	0.76	53.61	0.51	0.33	0.12	0.2	88.7	31.9
12	P2.Avg.	11.17	3.34	1.34	0.07	0.76	51.70	0.67	0.46	0.19	0.10	84.68	30.20

Table 4

Water Quality data of the study area.
Sample Number	Ca²⁺mg/L	Mg²⁺mg/L	Na⁺ mg/L	K⁺mg/L	Total Alkaline	Cl⁻mg/L	SO^2 − ₄ mg/L	NO₃⁻mg/L	F⁻mg/L
1	49.03	22.69	90.08	2.64	122.14	186.05	45.05	1.42	0.73
2	50.8	38.72	110.86	3.3	163.37	203.34	106.55	2.64	1.57
3	40.43	31.01	89.8	8.28	133.05	187.73	56.76	1.96	1.29
4	38.63	20.58	59.77	3.47	79.6	152.66	44.11	1.14	0.85
5	46.12	24	99.52	3.53	115.25	194.86	62.94	3.02	1.79
6	39.18	22.72	78.66	2.81	113.71	165.84	48.12	1.56	0.99

Table 5

Source rock geochemical analysis of the study area.
S.No	Source rocks	SiO₂	Al₂O₃	Fe₂O₃	MnO	MgO	CaO	Na₂O	K₂O	TiO₂	P₂O₅
1	Charnockite	61.60	5.70	2.95	0.41	1.64	10.44	2.81	0.96	0.28	0.15
2	Pink Granite	71.11	9.31	3.22	0.07	0.44	5.43	0.33	5.11	0.02	0.72
3	Calc – Granulite	13.87	3.99	3.03	0.42	1.59	41.76	0.60	1.14	0.58	0.54
4	Shell Limestone	2.95	0.14	0.14	0.17	3.25	52.28	0.81	0.18	2.24	0.19
5	Marble	13.09	3.72	4.69	0.40	1.67	41.25	0.61	0.91	0.68	0.49
6	Pink Crystalline limestone	14.70	2.81	1.84	0.59	2.03	42.38	0.47	0.84	0.84	0.44
7	Hb – Biotite Gneiss	55.44	13.47	4.27	0.07	1.16	11.51	3.10	6.26	0.12	0.09
8	White crystalline limestone	10.58	2.64	1.63	0.36	1.37	42.25	0.32	0.75	0.44	0.27

2.4.2. Trace Elements

There are nineteen minor/trace elements analyzed through ICPMS from the two calcrete profiles normalized against with PAAS value (Taylor and Mc Lennan, 1985) are given in (Table 6). Minor/trace element concentration in calcrete profiles of the study area show uniformity in the distribution trend pattern (Fig. 6) with slight changes in elements. Ba, Nb, Zr, Y, Sr, Rb, Ga, Zn, Ni, Co and Cr are more in the calcrete samples of the study area.. These changes may be due to the incorporation of lithogenic and pedogenic constituents added with alkaline-rich groundwater/surface water constituents during calcretization processes. Increasing trace element concentration from lithogenic and pedogenic parts along with groundwater/meteoric water constituents in calcrete have been established by the various researchers from various areas (Eren et al., 2002; Sinha et al., 2006; Erzelgoz et al., 2014; Perumal Velmayil 2017; Eren et al., 2010).

Table 6

Distribution of minor/trace element geochemistry of calcrete profiles sample with average trace/minor elements and PAAS (values in ppm
S.No	Sample Name	Sc	V	Cr	Co	Ni	Cu	Zn	Ga	Rb	Sr	Y	Zr	Nb	Cs	Ba	Hf	Pb	Th	U
1	P1.1 (Top)	1.23	14.30	13.35	1.76	6.61	2.68	30.54	7.83	370.80	48.49	29.24	115.89	33.52	1.29	114.95	1.64	2.77	1.41	1.84
2	P1.2	0.72	10.08	9.27	2.99	5.92	2.43	33.09	4.65	224.50	120.78	32.53	87.00	31.53	0.66	221.36	1.21	2.62	1.17	1.47
3	P1.3	0.43	7.63	15.96	6.17	6.67	14.84	30.72	2.39	106.36	311.66	46.22	29.45	6.92	0.29	995.93	0.42	2.95	0.34	0.81
4	P1.4	0.56	5.01	8.10	1.38	5.68	19.05	32.00	3.08	205.20	206.57	19.37	43.70	7.32	0.42	107.15	0.59	2.84	0.34	1.05
5	P1.5 (Bottom)	0.71	7.38	8.86	1.87	5.74	2.68	39.36	4.51	356.38	110.20	21.17	51.17	13.88	0.62	167.49	0.69	2.56	0.54	1.69
6	P1. Sample Avg	0.73	8.88	11.11	2.83	6.12	8.34	33.14	4.49	252.65	159.54	29.71	65.44	18.64	0.65	321.37	0.91	2.75	0.76	1.37
7	PAAS	16.00	150.00	110.00	23.00	55.00	50.00	85.00	0	160.00	200.00	0	210	2.00	0	650	5.00	20.00	15.00	3.00
8	P1. Sample avg/PAAS	0.05	0.06	0.10	0.12	0.11	0.17	0.39	0.00	1.58	0.80	0.00	0.31	9.32	0.00	0.49	0.18	0.14	0.05	0.46
9	P2.1 (Top)	0.34	2.83	7.34	0.56	4.12	1.75	32.02	0.73	32.80	79.00	5.18	19.28	7.32	0.09	23.14	0.26	1.40	0.19	0.48
10	P2.2	0.31	2.58	7.03	0.67	4.15	1.89	11.94	0.83	35.01	68.05	8.47	23.84	8.55	0.09	26.87	0.31	1.44	0.31	0.38
11	P2.3	0.44	5.68	7.94	0.86	4.22	9.27	33.62	2.88	117.17	261.73	14.88	83.03	26.56	0.08	166.97	1.05	2.37	1.94	2.45
12	P2.4	0.40	5.19	7.71	0.80	4.25	1.96	14.47	2.17	70.74	136.93	18.22	73.43	17.70	0.09	54.15	0.94	1.92	2.03	1.36
13	P2.5 (Bottom)	0.27	1.99	8.36	0.50	5.58	514.42	143.95	1.02	38.57	115.75	8.03	27.68	4.56	0.06	62.47	0.38	59.53	0.39	0.63
14	P2. Sample Avg	0.35	3.65	7.67	0.68	4.46	105.86	47.20	1.52	58.86	132.29	10.96	45.45	12.94	0.08	66.72	0.59	13.33	0.97	1.06
15	PAAS	16.00	150.00	110.00	23.00	55.00	50.00	85.00	0	160.00	200.00	0	210	2.00	0	650	5.00	20.00	15.00	3.00
16	P2. Sample avg/PAAS	0.02	0.02	0.07	0.03	0.08	2.12	0.56	0.00	0.37	0.66	0.00	0.22	6.47	0.00	0.10	0.12	0.67	0.06	0.35

2.4.3. Rare Earth Elements

Rare earth elements concentration from two calcrete profiles have been given in (Table 7) and their average distribution trend normalized against the chondrite values (Taylor Mc Lennan 1985) is also given in (Fig. 7). All the samples show similarities in the distribution trend. Rare earth elements fractionation and mobilization in the pedogenic calcrete profile takes place during the pedogenesis and calcretization process (Ramakrishnan and Tiwari 1997). Further fractionation and mobilization may be due to mineral weathering, neoformation of clay, clay illuviation, formation of sesquioxide, and their movement within the profile. Many researchers have already been discussed the mobilization of rare earth elements in calcrete (Haskin et al.,1968; Varshal et al., 1973); Ramakrishnan and Riwari 1977; Hema et al., 2006; Perumal Velmayil 2017) Element Eu and Ce show negative and positive anomalies respectively in the profile. These anomalies represent that continental source rocks may contribute the rare earth elemental origin to the calcrete profile.

Table 7

Distribution of REE geochemistry of profile samples with average REE and Rock/Chondrite average value (Tayler and Mc Lennan, 1985) (values in ppm).
S. No	Sample Name	La	Ce	Pr	Nd	Sm	Eu	Gd	Tb	Dy	Ho	Er	Tm	Yb	Lu	LREE	HREE	Total REE
1	P1.1 (Top)	51.13	85.18	10.63	57.59	8.66	1.32	14.81	1.85	6.72	1.17	2.68	0.36	2.46	0.36	229.98	15.62	245.60
2	P1.2	52.64	84.57	10.59	58.62	8.60	1.27	15.40	1.89	6.55	1.16	2.60	0.33	2.15	0.31	231.75	14.99	246.73
3	P1.3	48.91	64.29	8.18	47.11	7.24	1.83	15.82	2.03	7.85	1.45	3.12	0.37	2.28	0.30	193.73	17.39	211.12
4	P1.4	21.42	30.32	3.80	20.94	3.35	0.66	6.71	0.87	3.47	0.64	1.43	0.18	1.20	0.17	87.19	7.97	95.16
5	P1.5 (Bottom)	29.53	50.66	6.00	33.49	5.46	0.91	10.07	1.27	4.67	0.82	1.83	0.24	1.56	0.22	136.12	10.60	146.73
6	P1. Sample Avg	40.72	63.00	7.84	43.55	6.66	1.20	12.56	1.58	5.85	1.05	2.33	0.30	1.93	0.27	176.27	43.02	219.29
7	T&M 1985	0.37	0.96	0.14	0.71	0.23	0.09	0.31	0.06	0.38	0.09	0.25	0.04	0.25	0.04	5.58	2.95	8.53
8	S. Avg/Chondrite	130.52	81.38	66.92	70.03	31.45	14.94	43.78	28.72	15.66	12.58	9.72	8.74	8.32	7.78	441.64	92.99	534.62
9	P2.1 (Top)	8.55	13.74	1.74	9.70	1.51	0.25	2.76	0.34	1.11	0.20	0.44	0.06	0.41	0.06	41.19	3.42	44.61
10	P2.2	14.49	20.58	2.77	15.24	2.28	0.37	4.16	0.50	1.65	0.29	0.67	0.09	0.57	0.08	62.73	4.89	67.61
11	P2.3	69.50	124.08	14.84	79.34	9.97	0.79	15.47	1.68	3.64	0.59	1.37	0.16	1.06	0.15	316.54	10.35	326.89
12	P2.4	69.62	113.93	14.46	78.66	10.19	0.74	16.08	1.76	3.93	0.65	1.51	0.18	1.19	0.17	306.43	10.76	317.18
13	P2.5 (Bottom)	15.78	25.67	2.91	15.56	2.23	0.50	4.18	0.51	1.76	0.31	0.70	0.09	0.59	0.09	86.83	7.05	93.88
14	P2. Sample Avg	35.59	59.60	7.34	39.70	5.24	0.53	8.53	0.96	2.42	0.41	0.94	0.12	0.76	0.11	156.66	6.16	162.83
15	T&M 1985	0.37	0.96	0.14	0.71	0.23	0.09	0.31	0.06	0.38	0.09	0.25	0.04	0.25	0.04	4.21	1.59	5.80
16	S. Avg/Chondrite	96.97	62.28	53.6	55.84	22.66	6.1	27.87	16.53	6.35	4.79	3.76	3.24	3.07	2.87	326.76	40.99	367.76

2.5. Statistical Evaluation

Results of major element oxides, minor/trace elements, and rare earth elements of calcrete are interpreted with advanced geostatistical techniques, such as, multiple correlations, principal component analysis (PCA), and cluster analysis.

2.5.1. Multiple Correlations

Multiple correlations of all elements are presented in (Table 8). It is observed from the matrix that CaO shows high negative correlation relation with SiO₂, Al₂O₃, Fe₂O₃,MgO,, Na₂O, K₂O, TiO₂, trace elements Sc, V, Cr, Ni, Y, Zr, Nb, Cs, Hf. U and rare earth elements Eu, Tb, Dy, Ho, Er, Tm, Yb, and Lu. CaO is mainly obtained from groundwater and lithogenic and pedogenic associations are as added sources in the calcrete. CaO shows positive relation with Cu, Zn, Sr, Pb which indicates that they have derived from the same source of groundwater or surface water. High MgO content in calcrete may be due to Ph variation, PCO₃ and landscape setting (Queen 2006). Contact of groundwater movement and soil boundary reflects high Mg content in the bottom samples (Queen 2006, Udayanapillai et.al. 2019). In the study area, there is uniformity in the concentration of CaO and MgO content in the first profile and second profile. But in the second profile, CaO content is more than MgO content which shows less value of MgO content than in the first profile. Alkaline rich water derived from the sedimentary basement aquifer, especially calcareous sandstone/shell limestone causes for higher concentration of CaO content and low MgO content than the first profile, which originated from the aquifer water of metamorphic basement rocks of weathered granite zones.

Distribution of Al₂O₃ vs K₂O shows a high degree of positive correlation which reflects the clay mineral impurities in the calcrete. Al₂O₃ shows a high negative correlation with CaO, TCO₃ and a low degree of negative relation with P₂O₅ and a low degree of positive relationships with all remaining elements. The clay minerals from the pedogenic and lithogenic sources, such as montmorillonite, illite, kaoline minerals may contribute Na₂O, K₂O, and Al₂O_3, during the calcretization process. Such relations of Al₂O₃ vs K₂O in calcrete have been explained in various areas of calcrete deposits (Queen 2006, Hema et al., 2010; Udayanapillai and Thirugnanasambandam, 2012; Perumal and Udayanapillai 2020).

Fe₂O₃ vs CaO and TiO₂ show a high degree of negative correlations and low degree of a negative relationship with the elements P₂O₅, Cu, Zn, Sr, Pb and a positive relationship with all other elements, as they are derived from different sources like, alkaline water and lithogenic/pedogenic association.

Fe₂O₃ vs Al₂O₃ show a high degree of positive correlation which may be due to the formation of sesquioxide preservation, during calcretization processes. A low degree of negative correlation exists with alkaline water resources elements, like CaO, P₂O₅, Cu, Zn, Sr, Pb and low positive relations with all remaining elements. Sesquioxide preservation in calcrete under tropical climates has already been reported in the Coimbatore calcrete (Hema et al., 2010) and Pandalgudi region (Udayanapillai et al., 2015). Presence of dendritic sesquioxide preservation in the thin section analysis supports the evidence of the calcrete formed under an arid and semi-arid climate.

SiO₂ concentration might have contributed to calcrete from unaltered detrital quartz and feldspar from lithogenic/pedogenic sources during calcretization. SiO₂ shows a negative correlation with alkaline water resources elements of CaO, P₂O₅, Cu, Zn, Pb and positive relations with all pedogenic/lithogenic elements. Other oxides Na₂O, MnO, TiO₂, and P₂O₅ are in less concentration in calcrete which mainly contributed from lithogenic/pedogenic sources, during the calcretization process.

Multiple correlations of many minor/trace elements, except Cu, Zn, Pb, and Tn, show a negative correlation with CaO. This result indicates that these exceptional elements are added to the alkaline water along with the carbonate phase, during the calcretization process. Other elements are obtained from the lithogenic/pedogenic sources, during the cacretization processes.

2.5.2. PCA Analysis

Many researchers have applied PCA in various geological studies (Srinivasa et al., 2013; Sridhar et al., 2014; Udayanapillai and Kaliammal 2016; Kuttalingam et al., 2018). PCA analysis reveals the data, eigen value, percentage of variance and cumulative variance, and component loading score of the PCA. The result of the five PCA components accounts for 97.07% of cumulative variance. PCA factor has been considered above the eigen value of 1(one). PCA components are associated with certain major oxides, minor/trace elements, and rare earth elements. They are given as follows in Table 8.

First component includes the greatest amount of variation in the sample. Fifth component has lesser significance. PCA components are systematically decreased from the first component to fifth component. Thus output of the PCA elements data can be used to highlight both the similarities and differences within a dataset.

2.5.3. Cluster Analysis

Cluster analysis mentions a direct relation between the parameters. It is performed on the basis of correlation materials (elements) and the arithmetic average of the correlation coefficient (Davis 1973; Harper 1999). Numerous researchers have applied cluster analysis in various geological studies. (Praus 2007; Srivastava et al., 2015; Udayanapillai and Kliammal 2016; Kuttalingam et al., 2018). In this study, cluster analysis is applied for observing 1). Ionic similarity of major elements, minor/trace elements, and rare earth elements. 2). Identifying similarity of the aerial grouping of calcrete profile samples composition. Ionic similarity of two calcrete profile samples and aerial grouping of similar two profile samples are interpreted by a paired group of dendrogram analysis and Euclidean distance method or Wards method group of dendrogram respectively. There are 3 paired groups of ionic clusters of major, minor/trace and rare earth elements established with the average relative similarity values of 175 (Table 9). Aerial grouping cluster of calcrete profile samples through wards group has established the two profile similarities of the chemical distribution as follows (Fig. 8a&b).

Profile – 3P1 + 2P1 – IP1 –relative distance – 280

Profile – IP2 + 4P2–2P2 + 5P2 + 3P2 – relative distance – 240

The above two aerial grouping clusters represent the average relative distance of 1120.

Thus, interrelationship and relative affinities of each parameter have been interpreted through these geostatistical techniques.

Table 8

Principal Components, Eigen values, Percentage Variances, Cumulative variances and PCA Components.
PC	Eigenvalue	% variance	Cumulative	loading score
1	24.73	54.96	54.96	1. SiO₂ + Al₂O₃ + Fe₂O₃ + MgO + Na₂O + K₂O + TiO₂ + Sc + V + Ga + Rb + Cs + Lu + Yb + Zr + Lu + Hf + Nb = 47.12%
2	7.04	15.64	70.60	2. MnO + Cr + Co + Ba + Eu + Y + Dy + Ho + Er + Tm + Tb + Sr = 22.05%
3	6.70	14.89	85.48	3. Th + U + La + Ce + Pr + Sm + Gd + Nd = 14.43%
4	3.41	7.58	93.06	4. P₂O₅ + TCO₃ + LOI + CaO = 9.38%
5	2.05	4.55	97.61	5. Cu + Zn + Pb = 4.87%
6	0.53	1.19	98.79
7	0.31	0.68	99.48
8	0.21	0.47	99.95
9	0.02	0.05	100.00

2.6. Isotope Geochemistry

Results of stable isotope geochemistry of δ¹³C and δ¹⁸O, CaO, MgO, CaO/MgO, and Z values of two calcrete profiles are given in (Table 10, Fig. 9a&b). Palaeo-environment of carbonate deposits is determined through stable isotopes of carbon and oxygen (Eren et al, 2008; Chen et al., 2002). Concentration of carbon isotopes depends on the availability of plant species (Hema et al., 2010). Oxygen isotopes are widely used in palaeo-climate interpretation (Bradley, 1985; Chen et al., 2002). In general, stable isotopes of δ¹³C and δ¹⁸O values in carbonate reflect the genesis of the environment.

Table 9

Three paired group of ionic clusters of major, minor/trace and rare earth elements geochemistry.
Sl. No	Cluster components	Similarity distance or Correlation coefficients
1	SiO₂ + Al₂O₃-Fe₂O₃ + MnO + CaO + Na₂O + K₂O + TiO₂ + P₂O₅ + TCO₃ + Sc + LOI + Sc + V-Cr + Co-Ni + Cu + Zn-Ga	460
2	Rb + Sr + Y-Zr + Nb-Cs + Ba	480
3	Hf-Pb + Th-U + La-Ce + Pr-Nd + Sm-Eu + Gd + Tb-Dy + HO + Er + Tm + Yb + Lu	180

Table 10

Stable isotopes of carbon (δ¹³C) and Oxygen (δ¹⁸O), CaO, MgO, CaO/MgO ratio and Z values in calcrete profile section 1&2.
S. No	Samples	δ¹³C ‰	δ¹⁸O ‰	CaO %	MgO %	CaO/MgO %	Z
1	P1- 1 (Top)	-2.5	-4.02	10.38	2.07	5.01	118.62
2	P1-2	-3.28	-5.67	35.61	2.18	16.33	117.75
3	P1-3	-3.13	-6.07	38.13	2.44	15.63	118.16
4	P1-4	-4.33	-5.53	34.7	2.92	11.88	115.67
5	P1-5 (Bottom)	-2.93	-2.99	18.78	3.94	4.77	119.8
6	P2-1 (Top)	-7.87	-8.66	54.37	0.62	87.69	106.86
7	P2-2	-5.02	-5.85	58.15	0.44	132.16	114.09
8	P2-3	-4.47	-8.27	41.23	1.23	33.52	114.02
9	P2-4	-6.8	-8.77	51.14	0.74	69.11	109
10	P2-5 (Bottom)	-8.5	-6.42	53.61	0.76	70.54	106.69

Numerous scientists have analyzed the environmental significance of carbonate deposits through stable isotope signatures (Keith Weiber, 1964; Kumar et al., 1992, Ramkumar, 2008; Cerling and Quade, 1993, Paul knaults et al., 2000; Andrew and Hairuo 2004; Sinha et al., 2006, Armstrong Altrin et al., 2009; Hema et al., 2010; Nagarajan et al., 2013, Ersel Goz et al., 2014, Gazquez et al., 2017; Perumal 2017; Deiron et al., 2019; Hansen et al., 2019; Aeberty et al., 2010, Jackson et al., 2021). Hema et al., (2010) explained the stable isotope of oxygen and carbon in the regolith calcrete of Coimbatore region and C4 and C3 Plants causes for the diagenetic environment of δ¹³C and δ¹⁸O isotopes development in the calcrete deposits.

Singh et al., (2011) discussed the pedogenic carbonate from the Siwalik section in the Ramnagar basin to reconstruct the paleo-vegetation history over the past 12Ma. Carbon isotope records of the younger part (> 7 Ma). C3 and C4 plants such as Prosopis juliflora (C3), Arenacea (palm tree, C4) Acacia (C3) cause for the reconstruction of the diagenetic environment of stable isotopes of δ¹³C and δ¹⁸O values in pedogenic calcrete of the study area.

Stable isotope values of two calcrete profiles of the Sathankulam region are plotted on a bivariate climate plot (Fig. 10) (Julian Andrews et al., 1998) indicates an environment of weaker monsoonal climate or an arid environment. Singh et al., (2012) established the palaeo-precipitation record using oxygen isotopes in foreland basin sediments, NW India. Oxygen isotopes varied from − 12% to -5.89%. They observed progressive increasing oxygen isotope value in aridity period and low level range of oxygen isotope, during monsoonal precipitation.

The diagenetic environment of a stable isotope of δ¹³C and δ¹⁸O of calcrete profiles plotted on the diagram (After Keith and Weiber, 1964; Kumar et al., 1992, Ramkumar 2008, Gazquez, 2017) of the study area represents the meteoric diagenetic environment field or fresh continental water origin. (Fig. 11).

Hudson (1977) proposed a discriminatory diagenetic environment plot of δ¹³C and δ¹⁸O isotopes diagram (Fig. 12). He classified 17 environmental field regions in this diagram. Later many scientists applied this diagram to identify the carbonate environment (Nagarajan et al., 2008; Armstrong-Altrin et al., 2009; 2011).

Stable isotope value of carbon and oxygen of the two calcrete profile of the area plotted on Hudson Plot (1977) diagram falls on the field 12 and 13 which represents meteoric cement and freshwater limestone environmental field. CO2 degassing from alkaline water, evaporation, and evapo-transpiration, rainfall, temperature and mode of formation are the important factors that are attributed to the formation of calcrete. Discrimination of environment of marine and freshwater limestone has been established by Z values of stable isotope signature. (Keith and Weiber 1964; Stela Cuna et al., 2001, Armstrng-Alrin et al., 2003). Z value of stable isotopes are calculated in the following formula

Z = a (δ¹³C+50) + b (δ¹⁸O+50)

Where a & b are constants that have the values of 2.048 and 0.498 respectively.

Carbonate with Z values above 120 has been a marine environment. Those having a Z value below 120 have been considered as freshwater-type environments. Z value as 120 is treated as the intermediate environment of both marine and freshwater. Z value of two calcrete profiles of the area falls within the values of below 120 which indicate freshwater type origin of environment.

Calcrete occurs as a boundless deposit, not only as an exposed surface outcrop, but also occur as a pedolith deposit within the black soils and red teri soil of surface outcrop. Proterozoic metamorphic rocks and Tertiary sedimentary rocks are the basement rocks which occur below the calcrete profiles. Calcrete occurs as gravel, chalky, laminated, massive, and nodular forms. Petro-mineralogical studies from thin section analysis reveal calcified microcystis, calcified microtubules, calloform structure, and dendritic sesquioxide preservation with micritic and microsparitic calcite matrix around the mineral grains. Calcrete possesses the sap rocks grains of quartz, feldspar, hornblende, biotite, and gypsum. XRD analysis of calcrete reveals the pedolith minerals of quartz, feldspar, calcite, gypsum and clay minerals smectite, palygorskite, sepiolite, kaolinie and illite. Geochemical analysis of calcrete profile samples reveals the predominance of major elements of CaO, SiO₂, Al₂O₃, MgO, Fe₂O₃, minor/trace elements of Ni, Cu, Cr, and rare earth elements La, Ce, Pr, Nd, Sm, Gd, and Dy. Statistical evaluation of multiple correlations, PCA, and cluster analysis of all elements of calcrete reveals the interrelationship and affinities between the elements and also represents whether the elements derived from the same sources or different sources. Stable isotopes geochemical study of calcrete profile reveals that it is formed under meteoric cementing process and the continental freshwater environment under arid and semi-arid climate.

Competing interests

The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.

Authors' contributions

Corresponding author - Perumal Velmayil– Manuscript writing

Co-author - Udayanapillai Alagaiah Venu – Overall evaluation of the manuscript

Funding

Not applicable

Availability of data

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Ethics Approval

The manuscript has not been submitted to more than one journal for simultaneous consideration.

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No competing interests reported.

supplementarymaterials.xlsx
Table S1. Correlation matrix of Major, Trace and rare earth elements Geochemistry of two calcrete profiles samples.

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Palaeo-environmental reconstruction of pedogenic calcretes in Sathankulam, Southern India: an integrated approach

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Abstract

Figures

1. Introduction

1.1. Geological Settings

1.2 Material and Method

2. Results And Discussion

2.1. Field Observation

2.2. Petro Mineralogy

2.3. XRD Analysis

2.4. Geochemical Observation

2.4.1. Major Element Geochemistry

2.4.2. Trace Elements

2.4.3. Rare Earth Elements

2.5. Statistical Evaluation

2.5.1. Multiple Correlations

2.5.2. PCA Analysis

2.5.3. Cluster Analysis

2.6. Isotope Geochemistry

3. Conclusion

Declarations

References

Additional Declarations

Supplementary Files

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