JOURNAL GEOLOGICAL SOCIETY OF INDIA Vol.77, May 2011, pp.

459-477

Chemical Weathering of the Indo-Gangetic Alluvium with Special Reference to Release of Fluoride in the Groundwater, Unnao District, Uttar Pradesh
S. KUMAR and A. SAXENA+
Centre of Advanced Study in Geology, University of Lucknow, Lucknow - 226 007 + Present Address: SMEC India Pvt. Ltd., Gurgaon - 122 002 Email: surendra100@hotmail.com Abstract: In the central part of Indo-Gangetic alluvium in the Unnao district, Uttar Pradesh there are many pockets where groundwater shows high fluoride content. Drinking of fluorinated ground water has effected a large population and in many villages more than 80% of the population is suffering from fluorosis. The source of this fluoride appears to be the alluvial sediments deposited in the geological past as no hard rock terrain is present in the nearby areas. The area is dominantly made up of mud with pockets of sand. The sand fraction is made up of quartz, plagioclase, microcline, muscovite and biotite along with some accessory minerals like garnet, epidote, chlorite, tourmaline, hornblende, kyanite and a few opaque minerals. Moreover, the fluoride content in the groundwater varies both spatially and with depth indicating a sporadic occurrence. The surface water is devoid of high content of fluoride but is reported in hand pumps and in the dug wells. This paper deals with the geochemical study of the sediments up to a depth of 45m as most of the hand pumps are up to this depth to understand the source of fluoride. 14C dates of calcretes have suggested that the 45 m thick succession must have been formed in about 45000 years. Two different location sites were selected; one showing higher concentration of fluoride (Marksnagar village) while at other site which is about 4 km east of Marksnagar, the fluoride content was minimal (Durgajkhera village). Major elements and 24 trace elements were determined using XRF and it was found that when major elements are normalized with respect to upper continental crust (UCC) there is an enrichment of Si in all the samples. Na shows depletion where as Ti and K show enrichment. Fe and Mn show enrichment probably due to the formation of clay minerals. Si, and K enrichment is due to weathering of feldspar while Mg, Fe and K may have been released by the weathering of biotite. The CIA for the ancient sediments ranges from 54 64 while for the modern sediments of the Ganga River it varies from 50 64 indicating that there is no change in the rate of weathering in both modern and ancient sediments. The rate of weathering at all the sample locations was compared with that of UCC. The CIA values also suggest that there is an incipient weathering and indicate that the weathering of biotite is more progressive than muscovite. There is also a positive correlation between CIA values and the fluoride content in the ground water. Higher percentage of biotite and chlorite (altered biotite) was found at Marksnagar in comparison to Durgajkhera. It appears that the fluoride content in the ground water is due to dissociation/alteration of mica minerals mainly biotite. Keywords: Groundwater, Chemical weathering, Fluoride, Uttar Pradesh.

INTRODUCTION

The Indo-Gangetic alluvial plain covers an area of about 700,000 km2 and separates the Peninsular India (Indian Shield) from the Himalayas (Fig.1). It represents deposits of an active foreland basin formed as a result of continentcontinent collision of the Indian plate with the Asian plate (Singh, 1996). The rivers originating from the Himalaya deposit their load in the alluvial plain constituting the worlds largest alluvial tract (Singh, 1996). The alluvium represents Quaternary and Recent deposits comprising mud, sand and clays and devoid of any hard rocks.

In the Indo-Gangetic alluvium the groundwater is mainly used for drinking purposes. In last one to two decades, some water related problems are encountered in this region. It is noted that in many areas of the Gangetic alluvial tract, a large population is suffering from fluorosis, a deadly incurable disease caused due to high intake of fluoride (Pandey, 2001) from dugwells and hand pumps mainly in rural areas. It is also reported by various government agencies (CGWB, 1999) that this problem is spreading in other areas also. The cause of fluorosis is mainly due to the drinking of

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Fig.1. Geological setting of the study area (depicted by dot) (after Singh, 1992).

fluoride contaminated groundwater. It has been now confirmed that the villagers are drawing water from the dugwells and the shallow hand pumps for their drinking purposes and other domestic uses (Mukherjee et al. 1995). These wells and hand pumps show a very high concentration of fluoride in their water. In the year 1995 Mukherjee et al. (1995) have identified that the Marksnagar village is the most adversely affected area. At that time the value of fluoride concentration in the dugwell measured 6.3 ppm and about 50% of the population were reportedly suffering from the fluorosis which was more pronounced in the children below 20 years of age group (as per BIS 1991 norms the permissible limit for fluoride in drinking water is 1.2 ppm). They further added that the dental fluorosis was prevalent in this area for the last 15-20 years. In a recent survey the Marksnagar village of Unnao district, U.P. shows the maximum of 9 ppm of fluoride in the dugwell (Saxena, 2005). This value shows a monthly fluctuation between 7 to 9 ppm throughout the year and in absence of any other alternative source the villagers are forced to use this water

for the drinking and their domestic purposes. About 90% of the population was found to be adversely affected by the fluorosis in this village. In the absence of any industrial effluents in the nearby areas, the release of fluoride in the groundwater is definitely due to the weathering of sediments. Since Marksnagar has already been identified for the high fluoride contamination in the groundwater, as confirmed by various other agencies (Mukherjee et al. 1995; Rai, 1997; CGWB, 1999), this area was selected for the detailed study of the weathering processes active in the region for finding out any probable source and mechanism for the release of fluoride in groundwater.
GEOLOGICAL AND HYDROLOGICAL SETTING

The area under study forms a part of the Central Ganga plain (Pathak, 1982 in Khanna, 1992). The alluvial sediments of Ganga Basin have been classified as Older Alluvium and Newer Alluvium; the former consists of sediments which
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were formed in distant past and are partly undergoing denudation, while the latter is under its process of formation (Khanna, 1992). The Older Alluvium is made up of massive beds of clay of a pale reddish brown colour, very often yellowish with kanker (calcrete) present in between the clay layers. The Newer Alluvium is light coloured and poor in calcareous matter. The major part of the Central Ganga plain is composed of Older Alluvium (Khanna, 1992). The area in the Unnao district is a flat alluvial tract with soil exhibiting a wide variance; sandy on the elevated locations, clayey in the topographical lows and loamy on the flat surfaces. Figure 2 gives the location map of the study area. The area is mud (silt + clay) dominated and thus leads to water logged conditions which are supposed to be responsible for the sodic soil present in the area. The Ganga and Sai are the main rivers of the area and are responsible for many paleo-channels and ox-bow lakes. The general trend of both the rivers is northwest to southeast. The study area falls in doab of the rivers Ganga and Gomati, intersected by Sai River and many other streamlets. The area shows low regional surface gradient from northeast to southwest, varying from 10 to 30 cm/km (Rai, 1997). The upper layer of alluvium is composed of sandy loam and clayey loam. The main source for irrigation in the area is Sharda canal and shallow tubewells bored in the fields generally at about 45 m depth. The aquifer material is fine to medium grained sand and generally micaceous in nature with calcrete. The chemical analysis of groundwater (Rai, 1997) of Unnao district indicates that both good and moderate/bad quality groundwater found in the sand dominated areas and moderate to bad quality groundwater occurs in clay dominated areas under confined and semi-confined conditions. The bad quality water is mostly found in waterlogged areas and shows an increasing trend of groundwater salinity/alkalinity. The problem of leaching of fluoride in groundwater is more confined to this zone and had effected the local population adversely. The high fluoride content is found in well water which intersects clay dominated sediments and the water table is very shallow due to excess recharge from canals. Rai (1997) suggested that since these soils are sodic the groundwater contaminated with high fluoride is also alkaline with high sodium bicarbonate and sulphates. Thus, the fluoride in groundwater of Unnao district is closely related with soil/ groundwater alkalinity under waterlogged conditions. The climate of the area falls under the warm temperate type with dry winters (Cwg type) or C1 type of climate i.e., dry sub-humid type of climate (Ahmad, 1999). The climate can be broadly divided into summer, monsoon and winter. The average annual rainfall of the district is 837.80
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millimeter (http://cgwblucknow.up.nic.in/hydro/dist36.pdf). Almost 90% of the annual precipitation is received during the period from June to September.
SAMPLING AND ANALYTICAL METHODS

As mentioned earlier, for understanding the weathering process involved in the release of fluoride, two areas were selected; one is Marksnagar village where excess fluoride is reported in the groundwater and another is nearby village Durgajkhera from where no such excess is known. Six piezometers were installed in the study area in order to get a representative water samples at various depths for the water quality analysis as well as to get the vertical sediment samples at uniform depth interval; four piezometers were installed at Marksnagar (at depth intervals of 8, 21, 33 and 45 m) and two at Durgajkhera (at 12 and 33 m of depth). The piezometers were installed with the help of an augur by rotary method and the sediment samples were collected during the installation of the piezometers. In all 26 sediment samples were collected at depth interval of 3 m up to a depth of 45 m below ground level at Marksnagar and up to a depth of 33 m at Durgajkhera. On the basis of grain size analysis of the sediment samples, the strata chart was also prepared representing the vertical variation in the lithology of the selected sites. The vertical variation in the sediments in Marksnagar and Durgajkhera are shown in Fig.3. In addition to the above sediments, the recent sand and mud samples were also collected from the left bank of Ganga River at Bithur and Kanpur (Jajmau Bridge) for the comparative study with older sediments. There is some basic difference in the nature of sediments at Marksnagar and Durgajkhera. The sediments of Marksnagar are generally mud dominated with few regular patches of calcrete while that of Durgajkhera are sand dominated with kanker formation invariably at a depth below 18 m. The basic mineralogy of the sand fraction confirmed the dominant presence of quartz, muscovite, feldspar and biotite as major minerals with hornblende, garnet, tourmaline, kyanite and epidote present in minor amount. Two samples of calcrete collected at a depth of 7 m and 30 m were dated by 14C method in the laboratory of the Birbal Sahani Institute of Paleobotany, Lucknow (pers. commn. Dr. G. Rajgopalan) to have an idea about the approximate age of the calcrete bearing horizons. The radiometric dates of calcretes at the depth of 7 and 30 m are 3060140 years B.P. and 276701490 years B.P. On this basis it can be inferred that ca. 23 m thick succession was deposit in ca. 24000 years. It can be presumed that about 1 m was deposited in ca. 1000 years. Thus, the total profile of 45 m thick succession must

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have been deposited in ca. 45000 years B.P., this is not an absolute age of the sediments but an approximation for the deposition of the sediments of about 45 m thick profile. The chemical analysis of sediments was done by X-ray Fluorescence Spectrometry (XRF) at the laboratory of the Institute of Geology and Mineralogy, University of ErlangenNurenberg, Erlangen, Germany. Philips PW 2400 X-Ray fluorescence spectrophotometer was used for the determination of major and trace elements.
Loss of Ignition (LOI)

The dry weight of the porcelain crucible was noted and 2 gm of the bulk sample was weighed in the crucible and again the weight was noted. These crucibles were kept in the furnace for 24 hours at about 1000oC. After 24 hours these crucibles were cooled in an exsiccator and were weighed again.
Calculation of the LOI

five burners were used starting from the extreme left. The crucibles were left over at each burner for 5 10 minutes. In front of the last one laid the form for the tablets. After 10 - 20 minutes on the last burner the liquefied material was poured in the tablet holder and was kept for cooling. The samples are labeled as required. Then after melting these crucibles were kept in a plasticbox with 25% HCl and was processed in the ultrasonic bath for 10 minutes. Finally douched them with normal water and aqua dest and dried with paper. The precision and accuracy of the preparation and the instrumental performance of the XRF was checked using the international reference samples. With few exceptions, there were no discrepancies between the analytical data obtained and the consensus data in the international reference samples.
RESULTS

LOI = (Empty crucible weight + weight of sample before heating) (weight after heating/ weight of sample before tempering) X 100 [%] Tablet Preparation: About 1.0000.0005 gm of the samples were taken in bigger crucibles and were mixed thoroughly with 4.830 gm of Li3B2O7. This mixture was then kept in the platinum crucible and was melted. All the

The grain size analysis was done for the sediment samples collected during the installation of piezometers. The piezometers were installed for two villages; one is Marksnagar where maximum number of fluorosis patients were recorded and the other is a near by village Durgajkhera, where only about 10% patients were noted. Durgajkhera is about 3 km east of Marksnagar (Fig. 2). Mud is the dominant fraction in both the villages. In Marksnagar mud is about

Fig.2. Location map of the study area, Unnao district, Uttar Pradesh
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kaolinite (kaoline and amesite) groups were found (Saxena, 2005). The geochemical analysis for these sediments was done for all the ten major elements viz. Si, Ti, Al, Fe, Mn, Mg, Ca, Na, K, P were determined and analyzed in their oxide form. 24 trace elements viz. As, Ba, Bi, Ce, Co, Cr, Cu, Ga, Hf, La, Mo, Nb, Ni, Pb, Rb, Sr, Ta, Th, U, V, W, Y, Zn, Zr were also analyzed along with the major elements. Table 1 gives the concentration of the major elements for all the sediment samples and Table 2 gives the concentration of the trace elements. The correlation coefficients between each pair of elements were calculated in order to search for the inter-elemental relationship. The results are further compared with the data of Upper Continental Crust (UCC) sediments for better understanding of the chemical maturity of the sediments. Furthermore, an attempt was also made to study the enrichment and depletion of the elements along with the depth. We also tried to establish the relationship between the CIA values of the sediment samples with the fluoride content in the groundwater at the respective depth of the sediment sample.
Major Elements

Fig.3. Strata charts for the piezometers installed at the selected sites of Nawabganj Block, Unnao District, U.P.

76% while in Durgajkhera it is 57%. Besides mud, the variation in the content of sand and calcretes was also noted up to the maximum depth of 45m below the ground surface. At Durgajkhera more calcrete was found. The sediment samples at Marksnagar generally show moderate sorting while the samples collected at Durgajkhera the sorting lies between moderately well sorted to well sorted. The samples were found to be very coarse skewed for Marksnagar and very coarse skewed to fine skewed for Durgajkhera. Mineralogically, the sand fraction is dominantly composed of quartz, plagioclase, microcline, muscovite and biotite along with some accessory minerals like garnet, epidote, chlorite, tourmaline, hornblende, kyanite and a few opaque minerals. It was noted that the minerals identified at Marksnagar were found in more altered form as compared to Durgajkhera. The minerals dominantly identified in their altered form were plagioclase and biotite. In the silt fraction quartz, albite, microcline, muscovite and biotite were identified where as in the clay fraction the minerals of mica (illite and muscovite), smectite (sauconite and montmorillonite), chlorite (vermiculite and clinochlore) and
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Major element composition of the bulk sediments of Marksnagar and Durgajkhera indicates that these sediments mainly consist of three elements; Si, Al and Ca. Silica is the dominant major component in the sediments of the two sites as well as in the recent sediments of Ganga River. The greater amount of Al2O3 was found at Marksnagar where it was about 12% while CaO was only about 8%. But at Durgajkhera the average percentage of CaO is marginally higher than Al2O3; here CaO is about 11.2% where as Al2O3 is just about 10%. The relatively high percentage of Ca in these bulk sediments is due to the extensive calcrete formation. The average concentration of Al2O3 and CaO in the recent sediments was 11% and 1.5 % respectively. The other dominant major elements are Fe2O3, K2O and Na2O. Not much variation was noted for the average concentration of MgO in these villages and it ranges between 2.6% to 3%. Marginally higher concentration of K2O was found for Marksnagar compared to Durgajkhera, and this difference in the concentration of K2O may be due to the difference in the altered feldspar present in the sediments. The high content of clay was found at Marksnagar which is indicated by the relatively higher percentage of Al2O3, Fe2O3 and K2O.
Relative Mobility of Elements with Respect to Al2O3 Elemental Ratio for Major Elements

The chemical composition of the sediments is expected

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S. KUMAR AND A. SAXENA Table 1. Chemical composition of the major elements SiO2 % Marksnagar M1 M2 M3 M4 M5 M6 M7 M8 M9 M10 M11 M12 M13 M14 M15 59.5 54.6 54 57.3 57.2 51.8 57.2 52.8 58.4 67.4 53.4 63.3 61.3 58.4 58.4 0.63 0.63 0.67 0.71 0.68 0.62 0.68 0.62 0.69 0.56 0.6 0.53 0.64 0.64 0.56 12.39 12.57 13.97 13.62 12.34 11.36 12.79 12.49 12.74 9.84 11.55 10.48 11.29 11.61 10.9 4.76 5 5.7 5.56 5.04 4.59 5.08 4.82 5.03 3.05 4.55 3.39 4.03 4.37 4.02 0.095 0.079 0.092 0.084 0.093 0.093 0.081 0.081 0.082 0.056 0.098 0.074 0.081 0.093 0.124 3.08 3.99 4 3.1 2.94 2.81 3.06 4.64 2.8 2.28 2.79 2.64 2.54 2.58 2.15 6.36 7.36 7.2 6.08 7.7 11.99 7.1 8.26 7 6.01 11.19 7.09 7.15 8.48 9.65 1.47 1.35 1.41 1.32 1.37 1.22 1.38 1.38 1.38 1.73 1.15 1.58 1.54 1.47 1.43 2.75 3.12 3.47 3.14 2.6 2.44 2.84 3.06 2.76 2.08 2.52 2.41 2.52 2.66 2.55 0.158 0.162 0.13 0.133 0.123 0.114 0.131 0.129 0.137 0.152 0.121 0.137 0.144 0.143 0.13 9.26 10.66 9.73 8.69 9.92 12.97 11.29 11.49 9.11 6.67 12.59 8.19 8.38 9.5 9.96 100.4 99.6 100.4 99.7 100.1 100 101.7 99.7 100.1 99.9 100.6 99.8 99.6 99.9 99.8 TiO2 % Al2O3 % Fe2O3 % MnO % MgO % CaO % Na2O % K2O % P2O5 % LOI % SUM %

Durgajkhera D1 D2 D3 D4 D5 D6 D7 D8 D9 D10 D 11 35.9 56.8 74.9 73.5 59.3 50.8 49.8 57.4 53.7 52.4 48.6 0.33 0.47 0.38 0.41 0.52 0.62 0.55 0.54 0.56 0.54 0.56 6.52 8.87 9.16 9.83 10.52 11.99 11.06 10.28 10.52 10.9 10.99 2.61 3.07 2.5 2.86 4 4.93 4.55 3.94 4.07 4.29 4.56 0.139 0.088 0.049 0.046 0.097 0.081 0.137 0.105 0.094 0.084 0.119 2.6 2.43 1.59 1.85 2.81 3.89 3.65 3.1 2.77 3.98 3.67 26.57 12.54 3.59 3.39 8.54 10.9 12.44 9.52 12.08 11.08 12.92 0.8 1.22 1.63 1.6 1.27 1.15 1.18 1.1 1.08 1.1 1 1.6 2.13 2.22 2.45 2.54 2.68 2.54 2.38 2.3 2.45 2.61 0.075 0.107 0.103 0.094 0.1 0.121 0.116 0.104 0.11 0.082 0.109 23.45 12.38 3.94 4.05 10.15 13.26 13.87 11.42 13.12 13.51 11.2 100.6 100.2 100.1 100.1 99.8 100.5 99.9 99.9 100.4 100.4 99.8

Recent sediments (of Ganga at Kanpur and Bithur) Bit1 Bit2 Kan1 Kan2 Kan3 82.1 73 82.9 62.7 63.7 0.3 0.59 0.23 0.74 0.66 8.29 11.14 8.23 15.11 12.84 2.11 3.94 1.69 5.95 5.02 0.04 0.06 0.029 0.097 0.079 0.94 1.94 0.77 2.83 2.49 1.07 1.68 0.8 1.91 1.91 1.64 1.41 1.7 1.11 1.24 1.97 2.5 2.04 3.3 2.94 0.067 0.108 0.052 0.13 0.118 1.37 3.92 1.21 5.57 5.58 99.8 100.3 99.6 99.5 96.5

to demonstrate well established concepts on the mobility of various elements during the weathering (Berner and Berner, 1996). The elemental ratio refers to the relative enrichment or depletion of the element with respect to the least mobile element, Al. It is given by dividing the ratio of the element X and Al2O3 of the sediment sample with the ratio of the same element content in the UCC. i.e. Element Ratio (X) = [X/ Al2O3 (sediment sample)] [ X/ Al2O3 (UCC)]

X > 1 indicates enrichment X < 1 indicates depletion X = 1 indicate no change in relative abundance of the element. Figures 4a and b display the elemental ratios of the major

elements of the sediments of Marksnagar (where M1 to M15 are sampling codes number each representing a sample of 3 m depth; M1 ranges from 0-3 m while M15 increases to depth range of 42-45 m) and Durgajkhera (D1 to D11 are sampling codes number each representing a sample of 3 m depth; D1 ranges from 0-3 m while D11 increases to depth range of 33-36 m). As demonstrated in Figs. 4a and b, the SiO2 content in the sediments of all the sites is found to be enriched. TiO2 is considered relatively immobile and thus remains enriched in all the samples. Whereas Na2O, which is highly mobile (Singh et al. 2004) shows a relative depletion. Though CaO is also very mobile in nature but due to secondary formation of calcrete a relative enrichment is seen for the calcium. Potassium is considered to be less mobile than Na and thus generally shows enrichment. Mg also shows a relative
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Table 2. Concentration of trace elements (in ppm) As Marksnagar M1 M2 M3 M4 M5 M6 M7 M8 M9 M10 M11 M12 M13 M14 M15 8 11 15 11 8 4 9 4 7 4 10 2 7 8 8 501 499 560 530 466 421 499 516 441 377 456 469 534 564 561 0 2 0 0 1 1 0 0 1 3 0 2 1 1 2 93 69 66 99 99 83 96 85 95 107 77 95 116 107 118 17 18 14 17 14 17 19 17 14 8 15 8 11 17 18 80 73 73 86 83 69 80 74 82 56 63 55 65 67 54 16 18 18 21 18 10 16 7 17 12 20 2 12 12 14 17 18 18 19 15 15 18 17 18 12 16 14 15 16 14 4 4 5 5 5 4 5 5 5 3 3 4 5 5 3 36 40 35 40 40 24 32 372 33 27 29 23 31 36 34 1 0 0 2 2 2 0 2 3 2 0 2 2 1 0 11 10 11 11 13 9 13 11 11 12 11 11 13 13 12 34 37 36 40 46 33 40 21 41 21 32 11 23 29 28 29 28 30 28 25 26 27 24 29 22 25 24 27 31 38 135 161 185 168 133 127 149 163 143 102 139 124 127 141 138 321 394 252 182 316 297 241 396 221 162 183 191 165 163 154 3 3 0 3 0 0 0 0 0 1 0 1 1 0 0 16 10 12 16 16 15 14 14 21 22 12 17 23 25 18 8 9 8 6 8 7 7 7 7 8 8 5 5 6 7 86 90 104 103 91 91 94 90 94 61 84 57 78 89 76 2 2 2 4 4 0 4 3 3 2 0 2 4 4 0 29 29 28 34 34 30 32 30 35 37 28 33 36 38 36 76 86 94 86 77 68 81 74 75 60 86 71 70 79 71 232 209 164 215 251 215 225 205 243 301 209 244 278 272 225 Ba Bi Ce Co Cr Cu Ga Hf La Mo Nb Ni Pb Rb Sr Ta Th U V W Y Zn Zr

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Durgajkhera D1 D2 D3 D4 D5 D6 D7 D8 D9 D10 D11 0 3 0 3 6 11 9 5 5 7 6 312 373 359 385 482 463 576 523 458 433 495 2 2 4 3 2 2 2 1 0 0 0 54 115 72 71 72 70 107 97 100 96 93 16 11 5 10 13 13 21 16 14 15 16 23 38 34 37 55 71 58 52 56 49 61 7 5 5 0 9 21 14 7 10 13 10 11 14 11 13 15 18 16 15 15 16 16 0 3 3 3 3 4 2 3 3 3 3 13 23 18 18 30 30 29 28 28 34 29 0 1 2 2 2 0 0 1 2 2 1 8 9 9 9 11 10 10 10 9 8 7 7 11 13 11 25 37 30 21 23 20 28 29 21 26 22 33 23 34 33 31 33 33 93 114 110 126 132 145 142 124 123 135 139 139 150 113 116 228 396 435 307 279 219 282 0 0 0 0 2 0 1 0 0 2 0 11 18 18 13 12 12 15 21 17 17 14 5 8 5 3 6 6 10 8 9 5 8 44 60 45 50 72 93 94 73 78 77 86 0 1 0 1 1 0 3 0 0 2 1 20 34 26 24 30 28 35 36 34 31 31 42 48 40 54 58 77 73 57 68 64 84 118 246 212 193 204 206 204 244 225 202 186

Recent sediments (of Ganga at Kanpur and Bithur) Bit1 Bit2 Kan1 Kan2 Kan3 1 7 1 12 12 311 436 302 610 511 5 3 5 <1 2 63 90 57 102 87 6 10 4 14 12 25 46 21 67 59 <1 16 <1 21 17 10 14 9 20 17 2 4 1 5 4 12 23 10 45 52 1 2 2 3 2 7 12 6 14 13 7 22 3 31 28 21 24 24 29 26 100 132 103 178 157 73 74 75 75 78 8 1 3 1 3 9 16 16 10 15 4 5 4 5 5 33 100 87 31 68 0 1 5 0 0 15 39 34 21 32 27 89 75 30 58 116 204 213 201 244

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Fig.4. Relative abundance of the elements at (a) Marksnagar. (b) Durgajkhera.

enrichment trend because of incipient weathering in the area. Thus, both Mg and K are preferentially adsorbed and tightly incorporated in clay minerals of the sediments (Singh et al. 2005). It can also be seen that there is a remarkable enrichment of both Fe2O3 and MnO. This is probably due to the formation of clay minerals. During the mineral weathering in the area the SiO2, Na and K originate by incongruent dissolution of feldspar while the magnesium, iron and potassium may be released from the biotite and ferromagnesium minerals. Calcium may be derived from the dissolution of calcretes
Inter-Element Relationship Between Major Elements

The inter-element relationships were plotted on the variation diagram considering Al2O3 (Singh et al. 2005) and TiO2 (Sharma and Rajamani, 2000) as relatively stable phases. Figure 5 shows the relationship of Al2O3, Fe2O3 and K2O with TiO2 for the sediments of Marksnagar and Durgajkhera. There is a very good positive correlation between Al2O3, Fe2O3 and K2O with TiO2 with correlation coefficient of 0.9, 0.95 and 0.79 respectively at Durgajkhera whereas at Marksnagar this correlation coefficient value for Al2O3, Fe2O3 and K2O with TiO2 was 0.84, 0.85 and 0.6 respectively (Table 3). The positive trend of Al2O3, Fe2O3 and K2O with TiO2 indicates the enrichment of these elements as the concentration of TiO2 increases. This is due to the formation of secondary clay minerals such as illite, which is the result of the weathering of mica and feldspar (Wilson, 1987). Some

amount of iron may also have been released from heavy minerals. A more positive correlation of these elements is seen at Marksnagar as compared to Durgajkhera. The interrelationship of TiO2 with Na2O, SiO2 and CaO is given in Fig.6. A poor negative trend of Na2O and SiO2 with TiO2 was found with average correlation coefficient of about -0.40 and -0.23, at Marksnagar and Durgajkhera respectively (Table 3). Both Na2O and SiO2 are mobile elements and thus are lost due to their dissolution in the water while TiO2 being the least mobile element remains in the sediments. This negative correlation is better seen for Marksnagar indicating a comparatively higher rate of weathering in the area. According to Middelberg et al. (1988) both Na and Ca (in silicate form) decrease more rapidly than K and thus are depleted more than K. The negative trend of Na2O and CaO and positive trend of K2O with TiO2 result from the greater alteration rate of plagioclase as compared to that of K feldspar. However, CaO does not show a good negative trend due to its secondary precipitation in the form of calcrete in Durgajkhera thus it is not lost due to dissolution in water while remains in the sediments as calcrete. In general the relationship between TiO2 and CaO gives a strong negative trend on weathering and could be seen in Marksnagar. Inter elemental relationship between Al2O3 with MgO, Fe2O3 and K2O is given in Fig.7. There exists a very strong positive correlation between Al2O3 with MgO, Fe2O3 and K2O which is 0.66, 0.97 and 0.91 respectively for the sediments of Marksnagar and 0.62, 0.86 and 0.96 respectively for Durgajkhera. The positive correlation between K2O with Al2O3 is indicative of the feldspar and mica weathering that may lead to the formation of illite, which is the dominant clay mineral in these sediments and controls the concentration of Al and K. The weathering/ alteration of biotite may be responsible for the presence of MgO in the sediments. As compared to Na2O and CaO, K2O and MgO are less mobile and remain in the sediments during the incipient weathering and only become mobile in the solution during the latter stage of weathering. A positive correlation between Al2O3 with Fe2O3 indicates that their source of origin could be the alteration of biotite into aluminosilicates and Fe (III) oxides due to biotite weathering (Appelo and Postma, 1993) as per the following equation: 2K[Mg2Fe][AlSi3]O10(OH)2+10H+.5O2+7H2O Al2Si2O5(OH)4+2K++4Mg2++2Fe(OH)3+4H4SiO4 Figure 8 shows a strong negative correlation of SiO2 with the major elements; MgO, Fe2O3 and Al2O3 with correlation coefficient of -0.6, -0.7 and -0.6 respectively
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CHEMICAL WEATHERING OF THE INDO-GANGETIC ALLUVIUM, U.P. Table 3. Inter elemental relationship between the major elements SiO2 Marksnagar SiO2 TiO2 Al2O3 Fe2O3 MnO MgO CaO Na2O K2O P2O5 (CI) Durgajkhera SiO2 TiO2 Al2O3 Fe2O3 MnO MgO CaO Na2O K2O P2O5 (CI) 1 -0.20 0.147 -0.38 -0.87 -0.64 -0.92 0.963 0.296 0.156 -0.93 1 0.9 0.953 0.163 0.78 -0.18 -0.25 0.789 0.662 -0.08 1 -0.39 -0.59 -0.72 -0.47 -0.61 -0.60 0.89 -0.59 0.52 -0.63 1 0.843 0.851 0.02 0.331 -0.26 -0.41 0.611 -0.13 -0.24 TiO2 Al2O3 Fe2O3 MnO MgO CaO Na2O K2O P2O5

467

1 0.971 0.143 0.659 -0.24 -0.49 0.916 -0.1 0.037

1 0.2695 0.6103 -0.043 -0.651 0.8534 -0.234 0.1361

1 -0.14 0.556 -0.50 0.143 -0.40 0.525

1 -0.119 -0.305 0.793 0.0295 0.2687

1 -0.648 -0.236 -0.65 0.7239

1 -0.37 0.586 -0.49

1 0.0224 0.166

1 -0.62

1 0.858 -0.14 0.615 -0.52 0.135 0.961 0.663 0.44

1 0.3402 0.8985 -0.014 -0.377 0.7497 0.5456 0.0785

1 0.524 0.795 -0.84 -0.23 -0.04 0.812

1 0.2959 -0.619 0.4823 0.2302 0.3688

1 -0.878 -0.636 -0.379 0.9704

1 0.294 0.186 -0.91

1 0.6355 -0.56

1 -0.36

for Marksnagar. This indicates the grain size control on the geochemistry of the sediments; with higher grain size higher is the silica content. This silica dilution effect lowers the concentration of other major and trace element. At Marksnagar the negative correlation between SiO2 is better seen with MgO, Fe2O3 and Al2O3.
Chemical Maturity of the Sediments A-CN-K Diagram and Chemical Index of Alteration

To ascertain the chemical maturity of the sediments the CIA value scheme has been selected. Nasbitt and Young (1982) proposed the quantification of chemical weathering intensity as the Chemical Index of Alteration (CIA) where: CIA = [ Al2O3 / (Al2O3 + CaO + Na2O + K2O)] X 100 CaO : CaO in silicate form only (Nesbit et al. 1997). Here the molecular proportions of the above elements are used for the calculation of CIA of the samples. In case CaO in silicate form is not available then it is assumed to be equivalent to Na2O because Ca is lost more rapidly than Na during weathering and it will give lesser CIA values than that of Na (Singh, 2004). Since the study area dominantly contains calcrete in abundance therefore the values of CaO is invariably greater than that of Na2O.
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Because of this the values of CaO were assumed to be equivalent to Na2O. A CIA value of 100 indicates intense chemical weathering where all the alkali and alkaline earth elements are leached out of the system whereas CIA values of 45 55 indicate virtually no weathering . The fresh granodiorite composition is also considered to be very close to UCC and gives the CIA value of 47~50. With the initiation of weathering Ca and Na component of the sediments starts leaching out first, as both of these are highly mobile in nature and the trend of the weathering is seen parallel to A-CN line of the A-CN-K diagram. During the intermediate phase of weathering when the above trend reaches close to the formation of illite, K which was stable in the incipient phase of weathering also becomes mobile and the weathering trend starts moving towards the apex i.e., A corner of the A-CN-K diagram. The CIA values of the sediment samples of Marksnagar and Durgajkhera are given in Table 4. In Marksnagar the CIA value ranges from 54.4 to 63.2 while in Durgajkhera this value ranges from 53.2 to 63.6. It is indicative of the fact that at both the places the rate of weathering is almost same. In addition to this the bank sediments of Ganga River were also analysed and CIA values are calculated. The CIA value for Ganga River sediments ranges between 50.9 to 63.6. Singh et al. (2005) have done the geochemical analysis

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Fig.5. Relationship of Al2O3, Fe2O3 and K2O with TiO2

Fig.6. Relationship of TiO2 with SiO2 , Na2O and CaO.

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Fig.7. Relationship between Al2O3 with MgO, Fe2O3 and K2O.

Fig.8. Relationship between SiO2 with MgO, Fe2O3 and Al2O3

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Table 4. CIA values of Marksnagar (M1 to M15) and Durgajkhera (D1 to D11) Sl. No. M1 M2 M3 M4 M5 M6 M7 M8 M9 M10 M11 M12 M13 M14 M15 Mean CIA 60.634 60.9496 61.79 63.08 62.012 62.327 61.955 60.68 62.124 54.413 63.29 56.465 58.34 59.292 58.56 60.39411 Sl. No. Ganga B1 Ganga B2 Ganga K1 Ganga K2 Ganga K3 Mean CIA 50.86 56.03 51.93 63.55 59.12 56.298 Sl. No. D1 D2 D3 D4 D5 D6 D7 D8 D9 D10 D11 Mean CIA 59.15 57.595 53.23 54.54 59.54246 63.52664 61.80034 61.68221 62.8052 62.78137 63.60445 60.02342

Fig.9. Comparison between the CIA values of recent and ancient sediments.

for the channel sediments, flood sediments and suspended sediments of Gomati River which is about 80 km east of Ganga River, where the CIA value ranges between 53 to 68 with an average value of 60. The comparison of CIA values of the recent sediments of Ganga and Gomati Rivers (Table 5) suggests that the rate of weathering is more or less same for the sediments of both the rivers. However, Gomati River sediments show maximum value of CIA as 68 where as it is only 63.6 for Ganga River. This difference is due to the fact that the Gomati River is a ground water fed river and the sediments it carries are second cycle sediments (Kumar and Singh, 1978). In Marksnagar the minimum value of CIA was found to be 54.4 at the depth of around 30 m i.e., at this level there was virtually no weathering while the sediment at 33 m depth shows the maximum weathering with CIA value at 63.3 which is of incipient nature. The sediment samples of the Durgajkhera show lower CIA values up to a depth of 15 m with the minimum of 53.23 value at the depth of 9 m. After 15m the CIA values increase and reach maximum around 64 up to the depth of 33 m. To illustrate these results the ternary variation A-CN-K diagram was plotted for both the villages (see Figs. 10 and 11). This clearly indicates that the
Table 5. Range of CIA values for sediments of Gomati River, Ganga River, Marksnagar and Durgajkhera Location sites Min. Recent sediments (Gomati River, after Singh et al. 2004) Recent sediments (Ganga River) Ancient sediments I (Marksnagar village) Ancient sediments II (Durgajkher village) 53.0 50.9 54.4 53.2 CIA values Max. 68.0 63.6 63.2 63.6 Avg. 60.1 56.3 60.4 60.0

rate of weathering is not the prime factor for the release of fluoride in the groundwater rather it is the different mineralogical composition which is playing a key role in the release of fluoride. The detailed geochemical analysis of the sediments also shows more presence of mica minerals (especially biotite) at Marksnagar as compared to Durgajkhera. There is a loss of the most mobile elements i.e., Na and Ca in the sediments as compared to the UCC (Fig.11). The weathering trend was found running parallel to A CN line. As the chemical weathering progresses, the clay minerals are produced due to dissociation of primary minerals into secondary clay minerals. During the incipient weathering Na and Ca are rapidly lost to the weathering solution and thus are not retained by the clay minerals while K due to its nature of being adsorbed by the clay minerals retained as the weathering product. This is due to the specific size and charge characteristic of K that leads it to retain in the layer position of 2:1 type clay mineral i.e. illite thus making it present in the sediments till the weathering of illite also initiates. Thus, K is stable during the incipient and moderate weathering and is mobile at higher degree of weathering. The retention of K and loss of Na and Ca with the progress

Fig.10. A CN K diagram for Marksnagar.

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Trace Elements

Fig.11. A CN K diagram for Durgajkhera.

of chemical weathering leads to the general trend of A CN parallel weathering for both the sites. A-CN-K diagram was also plotted for the recent sediments collected from the bank of Ganga River at Kanpur and Bithur. This ternary variation diagram for the recent sediments is shown in Fig 12. There is a similar trend of weathering parallel to A-CN line for the recent sediments also. It is inferred that the weathering pattern is same on the surface sediments of Ganga River as well as for the ancient sediments of Marksnagar and Durgajkhera. Since the approximate age of the sediments as revealed by the carbon dating should be around 45,000 years at the depth of 45 m, it is suggested that there is no remarkable change in the weathering pattern since last 40 - 50,000 years. Moreover it is clear from the A-CN-K diagram for both ancient sediments and recent sediments that the weathering trend active in the area is A-CN parallel.

Trace element behavior in the sediments is influenced by weathering, diagenesis, sediment sorting and hydrogeochemistry. Tables 2 give the concentration of the trace elements. Zirconium is known to be least mobile and insoluble thus it remains in sediments. The higher concentration of Zr at Marksnagar is probably due to the higher degree of chemical weathering. Since the sediments of Marksnagar are mud dominated while that of Durgajkhera contains higher amount of sand so a general trend of higher concentration of trace elements is noted in Marksnagar in comparison to Durgajkhera indicating a marginal higher rate of weathering at Marksnagar. Fritz (1988) had stated that biotite and perthetic microcline are the important phases of fresh rocks which are enriched in Ba and Rb. He further added that the alteration of biotite results in the loss of Ba and enrichment of Rb. The average concentration of Ba in Marksnagar and Durgajkhera is 482 ppm and 441 ppm respectively while Rb is 135 ppm at Marksnagar and at Durgajkhera it is 125 ppm. Thus, the comparatively higher content of Ba and Rb at Marksnagar supports the higher amount of biotite and high rate of weathering. The relative higher average concentration of Cr and Ni suggests the higher content of clay in Marksnagar samples thereby giving a direct evidence of higher degree of weathering (Sharma and Rajamani, 2001). Slightly higher concentration of Sr at Durgajkhera confirms the formation of calcrete, which could act as barrier for the release of fluoride in the groundwater of Durgajkhera.
Chemical Mobility of Elements with respect to Weathering

Weathering involves redistribution of the major and trace elements present in the parent rock material. This mobilization and redistribution is facilitated by the process of dissolution of primary minerals, formation of secondary minerals, transportation of materials and its co-precipitation. According to Nesbitt (1979), titanium is relatively immobile during weathering and thus could be used for the calculation of the chemical mobility of the major and trace elements. The chemical mobility of an element is determined by plotting the CIA values against the percentage change of the element with respect to TiO2. The percentage change is calculated in terms of percentage increase or decrease of the element X (of samples) with respect to X in UCC. Percentage change =
Fig.12. A-CN-K diagram for the recent sediments.
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(X/ TiO2) sample (X/ TiO2)UCC 1}

x 100

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The increasing or decreasing trend of the variation diagrams plotted for percentage change of element X against its CIA value indicates the increase or decrease of chemical mobility of that element. The chemical mobility of the major elements of the sediments of the Marksnagar, and Durgajkhera is given in Fig. 13 (a and b). From Fig.13a it is clear that during the chemical weathering there is a definite mobility in the major element concentrations. The significant increasing trend of chemical mobility of Fe and Mg prove the instability of the biotite and muscovite content of the sediments as these two minerals are the most important host for Fe and Mg present in these sediments. This dissociation of biotite and muscovite is due to the weathering process active in the area. The increasing trend of CaO depicts that as the weathering progresses, the chemical mobility of Ca increases. This may be due to aqueous dissociation and coprecipitation of the calcrete during weathering. Al2O3 gives neither decreasing nor increasing trend, rather it is parallel to CIA and indicates that it is comparatively very stable during weathering (Fig.13b).

Silicon, sodium and potassium showed a decreasing trend of chemical mobility. The mobility of SiO2 is very important for understanding the weathering process as it plays an important role in soil formation. It can also be concluded that sodium decreases more rapidly than potassium. This is due to the greater alteration of plagioclase as compared to K feldspar, which is also shown in the A-CN-K diagram. Another reason for this could be that K is more preferentially adsorbed in the clay minerals and could also be incorporated with the silicate minerals.
Distribution of Major Elements with Depth

The variation in the concentration of major elements with the depth was plotted on the logarithmic variation diagrams. The value of the major elements is in percentage. However, the average concentration of fluoride (in ppm) for two years at the respective depth was also depicted in the graph to search for any correlation between the fluoride in the groundwater and the concentration of major elements in the sediments.

Fig.13a. Chemical mobility of the major elements during the weathering process.
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Fig.13b. Chemical mobility of the major elements during the weathering process.

The scatter plot shows (Fig.14) that pair SiO2 and CaO and TiO2 and Na2O3 are inversely proportional to each other. In Marksnagar as the SiO2 decreases with the depth there is an increase in CaO and simultaneously the fluoride content in the water of that depth zone (M2, M6, M11 and M15 at 6 m, 18 m, 33 m and 4 5m bgl respectively) also increases. While with the increase in SiO2 content there is a decrease of CaO and the fluoride content in the water in those depth zones also decreases (i.e. at M3 and M10, which are in the depth zone of 6-9 m and 27-30 m respectively). A positive correlation in the variation of the concentration of Al2O3,
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Fe2O3, MgO and K2O along with the depth suggests that the concentration of all these elements is controlled by the variation in grain size characteristic of the sediments and the change in the rate of weathering. Moreover, the increase in the content of Fe and Mg in the sediments indicates the higher content of biotite which is also probably releasing the fluoride in the ground water due to its alteration. The source of K and Al may be K feldspar or any other aluminosilicate. The positive correlation of fluoride with the variation of these elements confirms its release from the biotite, as fluoride is present in the lattice of biotite and could be

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Fig.14. Variation of major elements with depth.

released during the weathering of this mineral. There is a general trend of decrease in the concentration of all the major elements except for SiO2 and Na2O at the depth interval of 27-30 m (M10) suggesting a comparative dominance of SiO2. This zone also coincides with the low value of fluoride in the water. However, at depth interval of 30-33 m (M11) there is a remarkable decrease of SiO2 and increase of other major elements. The CIA value of M10 is 54 while that of M11 is 63 indicating the incipient weathering phenomenon in the depth zone M11 while this phenomenon is inactive in M10 resulting in much lower values of fluoride in the water at 27-30 m (M10) of depth as compared to the water at 30-33 m of depth. The TiO2 and Na2O gives a negative correlation as TiO2 is most immobile in nature while Na is very mobile, both of these elements vary with the depth as is shown in Fig.12.

The above finding were also confirmed when the fluoride concentration in the water was plotted against the trace elements like Ba, Ga and Rb (see Fig.15). From the above figure it can be seen that in Marksnagar as the concentration of Ba, Rb and Ga varies with the depth there is a variation in the fluoride content in the water. There exists a positive trend between the two. The variation in the concentration of Ba and Rb coincides with the variation in the biotite content of the sediments suggesting their source of origin to be biotite. This finding further supports the fact that the source of release of fluoride in the water is mainly due to the alteration of biotite. The variation in the concentration of major elements as well as the trace elements, along with the depth was also plotted for Durgajkhera and the similar trend was noted as it was seen for Marksnagar (Fig.14).
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Fig.15. Variation of trace element distribution and the fluoride content with the depth. Weathering and Release of Fluoride in Groundwater

The concentration and mobility of both the major elements and the trace elements are controlled by the weathering processes. This is because these elements are either the primary products or the secondary products of the weathering. So, an attempt was made to correlate the fluoride content in the ground water with the CIA value at that depth for the samples of Marksnagar. Shaji et al. (2007) suggests that high fluoride in groundwater is mainly derived from the hornblende biotite gneiss. The fluoride released into the groundwater could be the weathering product of mica minerals, probably of muscovite or biotite or both. It is also known that biotite is an alumino-silicate mineral containing magnesium, iron and potassium; thus the enrichment of these elements also suggests the active weathering of biotite. The chemical mobility and enrichment of Fe and Mg and enrichment of Al in the sediments indicates that the weathering of the mica minerals is still active. So, in order to understand the mobility of fluoride in the ground water with the changing trend of the chemical weathering intensity i.e. the CIA values, a graph is plotted (Fig. 16) and the correlation was established where the groundwater samples

were available at the respective sediment sample depth. As the CIA value increases the fluoride content of the ground water also increases indicating the positive correlation between the two. The correlation coefficient between the fluoride content in the ground water and the CIA value at that depth zone for Marksnagar was about 0.8. The maximum fluoride was released at 30-33 m (M11) of depth and the CIA value was also found maximum for this sample. The minimum fluoride was released at the depth interval of 2730 m (M10) which also coincides with the minimum CIA values. However, at the depth interval of 6-9 meters (M3) the fluoride content decreases with some increase in CIA. This might be due to difference in lithological character of the sediments at that depth. The CIA value at this depth interval also coincides with the sediment age of 20 to 30 thousand of years as revealed by the carbon dating. Moreover this period also happened to be the last event of global glaciations. So, the role of the last event of global glaciations in the weathering and ultimately in the release of fluoride could not be ruled out.
CONCLUSION

Fig.16. Relationship between F and CIA with the variation in depth at Marksnagar.
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The geochemical data indicates the dominant presence of quartz, feldspar and mica in the sediments of Marksnagar and Durgajkhera. The high percentage of CaO suggests the secondary formation of the calcium in the form of calcrete. The enrichment of Fe2O3 and MgO in the sediments indicates the presence of high content of biotite and the clay minerals like vermiculite and smectite (Murphy, 1998). The presence of Na in sediments is mainly due to the plagioclase (albite). The depletion of Na2O with loss of SiO2 indicates the preferential disappearance of plagioclase as weathering proceeds (Weijden and Weijden, 1995). The depletion of Na corresponds to the extensive weathering of plagioclase (albite) in the area (White et al. 1998) while the some depletion and some enrichment of K suggests that the active weathering of K-feldspar (microcline) is not very

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progressive. The presence of TiO2 confirms the presence of biotite as Murphy et al. (1998) suggest that Ti is the part of biotite and the trace elements Ni & Cr confirm the presence of vermiculite (Ramesam, 1979). Na, Ca and K are mainly concentrated in feldspar and the significant decreasing trend of Na and some depletion of K, therefore reflects the alteration of feldspar (Middelburg et al. 1988). Since Na decreases more rapidly than K, greater alteration rate of plagioclase than K-feldspar is suspected. Ca (in silicate form) is also present in feldspar and normally gets depleted along with Na. But in the present case due to its secondary precipitation as calcrete, enrichment of Ca is noted. The trace element Rb is known to be more contained in K-feldspar than biotite and is expected to be less depleted than K (Middleburg et al. 1988). In, Marksnagar some depletion of Rb was noted, confirming some alteration of K-feldspar. Since, according to Goldich cycle of weathering, K-feldspar is more resistant of weathering than biotite, so its alteration confirms the weathering of biotite. The CIA value also suggests the incipient weathering of the sediments in the area and support the weathering of biotite [K (Mg, Fe)3(AlSi3) O10 (OH, F)2] to be more progressive than

muscovite [KAl2(AlSi3)O10(OH, F)2]. A positive correlation between the CIA value and the fluoride content in the ground water was also noted. Thus, the rate of weathering active in the area is incipient in nature, suggesting more prominent weathering of Na feldspar and biotite. Probable reason for the high content of fluoride in the groundwater of the study area is mainly due to the dissociation/alteration of mica minerals, mainly biotite. Acknowledgement: We are thankful to the UP Council of Agricultural Research for the financial support in the form a research project, to Dr. Anupam Sharma for his help during the course of investigation and to Dr. A.K. Jauhri for extending working facilities in the Geology Dept., University of Lucknow, India. S. Kumar is indebted to the Alexander von Humboldt Foundation, Germany for the grant of a fellowship to work in the University of Erlangen, Germany. Authors are indebted to Prof. H.J. Tobschall for extending working facility to S. Kumar at the Institute of Geology and Mineralogy, University of Erlangen-Nurenberg and to Ms. M. Drr for the analytical assistance in XRF analysis.

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(Received:23 March 210; Revised form accepted: 21 September 2010)

JOUR.GEOL.SOC.INDIA, VOL.77, MAY 2011