NOVYI MIR Research Journal ISSN NO: 0130-7673

IDENTIFICATION OF MINERALS AND PHOTONIC CHARACTERIZATION OF COASTAL SOIL SAMPLES OF

THENGAPATTANAM BEACH

S.S.Sajitha1*, G.Aldous Jenin2, M.Michael Babu3

1. Assistant Professor, Department of Chemistry, Annai Velankanni College, Tholayavattam.

2. Assistant Professor, Department of Bio-Chemistry, Lekshmipuram College of Arts and Science, Neyyoor.

3. Coordinator-UGC Innovative Programme & Assosiate Professor, Centre for Marine Science and Technology, Manonmanium Sundranar University, Rajakkamangalam.

Email: [email protected]. [email protected] [email protected]

ABSTRACT:

Coastal soil samples contain the most economically important mineral accumulations. This present study is aimed to identify the minerals, particle size, zeta potential and poly dispersive index values of coastal soil samples collected from ten different places near sea shore regions of Thengapattanam beach. The FTIR and diffuse reflectance UV spectroscopy studies were confirmed the enrichment of minerals like quartz, calcite, aragonite, alumina, gypsum, feldspar, almandine and dolomite. In XRD the mineral identification was confirmed by powder X-Ray diffraction patterns in association with JCPDS data. The Photon correlation spectroscopy clearly represented the z average values, pdi value, intercept, size, percentage of intensity and width (d.nm) values of coastal soil samples of Thengapattanam beach.

Keywords: Dynamic Light Scattering, Photon Correlation Spectroscopy and Poly dispersive index(pdi).

1. Introduction:

The total land mass of the earth we can live is only 30% of our planet. Above 20% of the population of lives in coastal area. Humans have dumped so much non-biodegradable wastes in the coastal region, its being ingested by marine wild life. Our survival is threatened because of the prediction of the scientists that the sea level will rise due to global warming. The formation and concentration of heavy minerals differ from place to place and location to locations based on various factors such as geodynamic, sea wave directions, geo interstitial separation, sea wave height and tidal variations[1]. Soil materials are strong candidates as adsorbents[2]. Soil is a component of the terrestrial ecosystem fulfills many functions[3]. Thengapattanam (also referred to as "Thengapattinam", thennaipattinam" and "thenpattinam" ), named after dense grooves, is a major trade and tourism centre in the painkulam panchayath along the coastal plains of . Thengapattanam, once part

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of and later , was bequeathed upon to on 1 November 1956 along with some parts of today's Kanniyakumari District.

Thengapattanam is located in the South western coast of India bordering the Arabian sea to the west, western ghats to the north, and vast fertile plains with intermittent Rocky hills to the east. The town is 11 km into the Tamil Nadu border from Kerala. The Kerala state capital is 45 km away from here, whereas is 35 km away. It shares borders with Erayumanthurai, and Amsi villages on either side. The mean elevation of the town is 9 ft (2.7 m) with the highest point Chentapalli Rock being 50 ft (15 m) high above sea level. The wraps around most parts of the and becomes Kuzhithurai River before reaching Thengapattanam Estuary.

The AVM Canal (Anantha Victoria Canal) commissioned by Marthanda Varma Maharaja in the 1860s to facilitate smooth trade, and navigation, passes through this town, the waterway lost its signiface and consequently had to cess operation in the 1980s following the establishment of roadways, unmitigated moderation, and unlawful encroachments adjoining the canal. The Canal, while it functioned, merged with Thamirabarani River River at Thengapattanam, and formed a basin known as Valiyar. The development project mooted to revive AVM Canal Waterways would link Thengapattanam with Kanyakumari in the east and Kasargode in the north-west in Kerala, when it becomes operational.

FT-IR spectroscopy was used to identify primary (quartz, feldspars) and secondary (silicates, clays and aluminosilicates) soil minerals [4],[5],[6],[7]. Mid-Infrared (M-IR) spectroscopy has frequently been applied to investigate soil properties and soil organic matter (SOM) characteristics [8],[9][10],[11],[12]. Currently, the combination of multivariate statistical methods used for the FT-IR spectra analysis has provided a powerful method for the discrimination and identification and/or quantification of single components in soils [13],[14][15],[16],[17][18],[19],[20]. Powder X-ray diffraction pattern gives more information about minerals present in soil or sedimentary samples[21],[22]. Diffuse reflectance spectroscopy (DRS) is used as a reliable, efficient and inexpensive means of characterizing soils [23],[24],[25]. Soil chemical and physical properties have been predicted by reflectance spectroscopy successfully in the past [26]. 2. MATERIALS AND METHODS

2.1. Study Area

The study area chosen for the present work is Thengapattanam beach. Thengapattanam beach is located at about 14 Kms from Colachel, 21 Kms from Thuckalay, 12 kms from Pariakal beacg, 14 Kms from marthandam.Numerous industries, chemical factories and aquaculture farms are also developing along these coastal areas and it makes much attention for present and future research. The coastal soil samples were collected from ten different near sea shore of coastal regions of ThengaPattanam beach (site numbers T1-T10 )

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Figure.1. Study Area Profile

Figure: 2.Sample Collection sites in Thengapattanam beach 2.2. MINERALOGICAL ANALYSIS

The mineralogical analysis was performed using different methods like FTIR, DRS-UV and XRD methods.

2.2.1. FOURIER TRANSFORM INFRA RED SPECTROSCOPY (FT-IR) ANALYSIS:

The FT-IR spectrum was used to determine the nature of functional groups which could possibly influence the adsorption of the soil. The infrared spectra were recorded in the mid IR region 400-4000 cm- 1 using Nicolet iS5 Fourier Transform Infrared Spectrometer (IR-Affinity-1).

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2.2.2. X-RAY DIFFRACTION ANALYSIS (XRD)

The coastal sediment samples were analyzed by XRD technique to yield more information about minerals. The full width at half maximum (FWHM) of XRD profiles were used to characterize different mineral properties and surface integrity of coastal soil samples. In each peak in a diffraction results from corresponding d-spacing values and the 2Ɵ values are the angle between the transmitted and reflected X- ray beam. To identify the mineral phases in the samples, X-ray diffractograms were recorded using Schimadzu XRD 6000 (25oC of λ = 1.5405 Ao). 2.3. DYNAMIC LIGHT SCATTERING STUDIES 2.3.1.Particle Size and Zeta potential Analysis:

The soil samples were processed by Ball Milling process for particle size analysis. Dynamic Light Scattering Particle Size Analyzer was used to find out the particle size distribution of soil samples. The processed soil samples were dispersed in HPLC water. Then experiment was carried out in computer controlled particle size analyzer to find out the particles size distribution. Zeta potentials values of soil samples were determined by Zeta Sizer Nano ZS90 made in England. 3. Results and Discussion 3.1. MINERALOGICAL ANALYSIS

3.1.1.FT-IR spectroscopy studies of coastal soil samples of Thengapattanam beach.

In this present study the mineralogy, absorption frequency and functional groups were analyzed through FTIR. FTIR absorbance frequency values can easily identify the primary (quartz, feldspar) and secondary (silicates, clays, alumino silicates) soil minerals.

The IR absorption band at 695-700cm-1 , 795-810cm-1 , 1050-1150cm-1 , 1600-1800cm-1 indicates the presence of quartz in all samples. The presence of microcline was indicated in the absorption frequencies at 1050-1055cm-1 , 740-745cm-1 , 640-645cm-1 , 585-590cm-1 , 535-540cm-1 , 460-465cm-1 and 425- 430cm-1. The presence of orthoclase was indicated in the absorption frequencies at 1040-1045cm-1,765- 770cm-1 645-650cm-1 , 580-585cm-1 , 465-470 cm-1 and 431-435cm-1. The presence of albite was indicated in the absorption frequencies at 990-995cm-1, 785-790cm-1 , 720-725cm-1 , 420-425, cm-1 and 405- -1 410cm .The enrichment of potassium and aluminium represented the presence of Orthoclase (KAlSi3O8) and Albite (NaAlSi3O8). Feldspar mineras availability depends on the enrichment of sodium and aluminium.

Figure:3. FTIR spectrum of Thengapattanam beach.

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The observed frequencies ranges from 905 – 910 cm-1 , 950 – 955 cm-1 , 1010 – 1015 cm-1 ,1030 – 1035 cm-1 , 1115 – 1120 cm-1 and 1150 – 1155 cm-1 indicated the presence of kaolinite. The observed band values at 1640-1645cm-1 and 3440-3445 cm-1 showed the presence of montmorillonite clay. The IR absorption peaks at 3699.5 cm-1,3425 cm-1, 2360 cm-1 , 2361 cm-1, 033.8 cm-1, 779.2 cm-1, 694.4 cm-1, and 447.5 cm-1 indicated the presence of illite. The IR absorption bands at 875 -880cm-1 , 1420 - 1425 cm-1 and 1795 -1800 cm-1 indicated the presence of calcite.

Table 1.Band Assignments of different inorganic components of Thengapattanam beach

Integration limits Peak Band assignments Sample site number (cm-1) 3698 3719-3685 Si-O-H vibration of clays, T4,T6,T7,T10, Kaolinite and Fe oxides. 3622 3682-3577 Si-O-H vibration of clays, T4,T6,T9 Kaolinite, gibbsite and Fe oxides.

~3460 3525-3460 O-H stretching of Gibbsite. T4, T7, T8 ~3430 3420-3450 O-H stretching of H-bonded water. T1-3 and T7 O-H stretching of absorbed water 3440 molecule. T7 ~2520 2562-2480 Carbonate (calcite and aragonite) (overtone and combination band) T1-4 Si-O vibration of quartz mineral 1463 1479-1408 carbonates T1-5 520 515-525 Si-O-Al bending T3,T4 ( octahedral Al) 535 530-535 Si-O assymmetrical bending vibrationAl-O-CO. 470 Si-O-Si bending 470-420 Kaolinite, illite, smectite T1-6 and T10 459 Si-O assymmetrical bending vibration. 935 930-935 OH deformation T2,T7and T8 875 875-879 Fe3+ (Al-OH) T1,T6

The band assignment values of 1403-1354 cm-1 showed the C-O of phenolic OH, COO- and O- H, CH3 bend, COCH3.

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Table 2.Band Assignments of different organic components of Thengapattanam beach

Integration limits Peak Band assignments Sample site number (cm-1) O-H and N-H stretching, H- 3440-3320 bonded OH T3,T5,T10 Aryl-H,R2C=CH2, R2C=CHR 3107-3042

2930 3010-2800 Aliphatic C-H stretching T7,T8, C=O stretching of amides, H- 1775-1711 bonded conjucated ketones, 1730-1700 T3,T10 Carboxyls and quinones, C=N stretching C-O of phenolic OH, COO- 1380 1403-1354 T2,T9,T10 and O-H, CH3 bend, COCH3. C-O stretching and OH ~1230 1256-1198 T5 deformation of COOH

R2C=CHR, phenyls with 835 820-752 three H adjacent long chain T3,T7 535 530-535 alkanes (CH2 wag)

3.1.2. Diffuse reflectance UV-Visible spectroscopy analysis of coastal soil samples The variations of absorbance and wave length clearly showed the presence of elements and minerals in the coastal soil samples. The UV spectral images clearly indicated the absorbance variations of coastal soil samples 1.3 305 nm

1

Abs

0.5

0.2 200400 600 800 900 Wavelength [nm]

Figure.4. UV spectrum of Thengapattanam beach.

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Table 3. UV spectral data on Thengapattanam beach

Sample Wave Absorbance no length(nm) T1 309 1.39966 T2 307 1.37588 T3 303 1.25485 T4 308 1.37191

T5 307 1.35889 T6 308 1.35932

T7 311 1.36153 T8 309 1.35725 T9 305 1.29412 T10 306 1.37204

The absorbance values ranged from 1.25485 to 1.39966 indicated the increases in concentration of various metals. Lambda value corresponds to specific electronic transitions of metals and metal compounds.

3.1.3. X-ray diffraction analysis of coastal soil samples of Thengapattanam beach

In qualitative mineralogy, the coastal soil samples were determined with the standard interpretation procedures of XRD. The d-values of XRD pattern of soil samples were identified and compared with standard values of clay minerals, the d-spacing values obtained from X-ray diffractograms with the standard d-spacing values were given by Joint Committee on Powder Diffraction Standard (JCPDS).

X-ray Diffraction (XRD) method was used to confirm the presence of coastal soil minerals. In this study, the mineral identification was confirmed by powder X-Ray diffraction patterns in association with JCPDS data. The observed XRD patterns indicated quartz, feldspar, calcite, hematite, kaolinite as the major constituents and other minerals as the minor constituents in coastal soil samples of Pattanam beach. In this study, the mineral identification was confirmed by powder X-Ray diffraction patterns in association with JCPDS data.

Figure.5. XRD spectrum of coastal soil samples of Thengapattanam beach

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The full width at half maximum (FWHM) of XRD profiles were used to characterize different mineral properties and surface integrity of coastal soil samples. In each peak in a diffraction results from corresponding d-spacing values and the 2Ɵ values are the angle between the transmitted and reflected X- ray beam. The observed XRD patterns indicated quartz, feldspar, calcite, hematite, kaolinite as the major constituents and other minerals as the minor constituents in coastal soil samples of Kanyakumari District. The XRD results indicated high concentration of SiO2 corresponded to the dominant of quartz. The X-ray diffraction patterns of other minerals like dolomite, bischofite, anhydrite, gypsum, calcite, bassanite and kaoline.

3.2. DLS ANALYSIS OF THENGAPATTANAM BEACH 3.2.1. Particle size analysis of coastal soil samples of Thengapattanam beach

Photon correlation spectroscopy clearly represented the size distribution, Z average (grand average) values, size and percentage of intensity of the samples. The size verse percentage of intensity spectrum showed that the sample site one was of high distribution of particle when compared to other samples. This is mainly due to the presence of more number of particles like elements and enrichment of minerals that site.

Figure.6. Size distribution spectrum of soil

Poly dispersity index (pdi) values were dimension less and scaled values. The mono disperse standards the pdi values were smaller than 0.05 and the pdi values were greater than 0.7 indicated that the sample has a very broad size distribution. The pdi values were greater than 0.7 in the sample sites are T3, T6 and T7. Particle distribution was high due to the presence of more number of particles. But more aggregation of particles leads to less zeta potential values of samples.

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3.2.2. Zeta potential analysis of coastal soil samples

The conductivity values were higher on sample sites T1-T5 when compared to the T6-T10 samplesites. The higher conductivity values indicated that the soil samples contain flocculation nature of clay minerals. The clay minerals were flocculated in the soil developed small clods of a cramby nature and allowed free movement of air and water.

Fig.7.Zeta potential distribution of soil samples

The results revealed that the zeta potential value was approximately -12 mv and it has clearly represented the stability behaviour of soil samples are incipient stability. Low zeta potential indicated less stability and also the aggregation of the particles. Higher zeta potential values either positive or negative were necessary to ensure stability and avoid aggregation of particles.

4. Conclusion

Thengapattanam beach is one of the natural beauty and very peaceful beach. Also this beach is very famous for fresh fishes. Now a day’s people dumped non biodegradable wastes near this beach soils. Beach soil fertility destroyed. The least amount of organic carbons leads to soil erosion in many beach region of Thengapattanam. Stress on coastal zone developed by the increasing population combined with other factors often leads to erosion of coastal areas. Problems like pollution, siltation, erosion, flooding, salt water intrusion, storm surges and ever expanding human settlement threats highly disturb the coastal ecosystem. The mineralogical, imaging, photonic nature, ultra structure and micro morphological variations of coastal soil samples were based on factors such as geo dynamic sea wave direction, geo interstitial separation, pollution, sea wave height, tidal current and wave spread nature.

The FTIR, DRS-UV and XRD results confirmed the enriched minerals in Pattanam beach. are Quartz (Rock Crystal), Feldspar- Group of silicate minerals ,Clay minerals such as Kaolinite, montmorillonite and Illite. Carbonate minerals like Calcite and Aragonite. The various physical parameters such as added ionic concentration, centrifugation rate, temperature and PH affect the zeta potential values. Zeta potential values depend on the interaction between charged particles this was due to the very high surface electrical conductivity, which is inversely proportional to the size of the particles. Everyone should responsible to protect the coastal area.

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5. ACKNOWLEDGEMENTS We would like to thank Dr .Rajesh Kannan, Scientist , Sathyabhama Univesity for his kind help in the mineralogical studies.

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