A Multivariate Statistical Modeling of Geochemical Factors of Soils, Sediments and Ground Water By

Shri Sabyasachi Rout Bhabha Atomic Research Centre, Mumbai

A Dissertation Submitted to the Board of Studies in Engineering Sciences

In Partial Fulfillment of Requirements For the Degree of

Master of Technology
Of

Homi Bhabha National Institute

February, 2011

Homi Bhabha National Institute

Recommendations of the Thesis Examining Committee
As the members of Thesis examining Committee, we recommend that the dissertation prepared by Shri Sabyasachi Rout entitled A Multivariate Statistical Modeling of Geochemical Factors of Soils, Sediments and Ground Water be accepted as fulfilling the dissertation requirement for the Degree of Master of Technology.

Final approval and acceptance of this dissertation is contingent upon the candidates submission of the final copies of the dissertation to HBNI.

Date: July26, 2011 Place: Mumbai

II

DECLARATION

I, hereby declare that the investigation presented in the thesis has been carried out by me. The work is original and has not been submitted earlier as a whole or in part for a degree/diploma at this or any other Institution/University.

Sabyasachi Rout

III

ACKNOWLEDGEMENTS

I had the unique privilege of working under guidance of Dr. P. K. Sarkar, Head, Health Physics Division and Dr. A.G Hegde, Head Environmental studies section, Bhabha Atomic Research Center, Mumbai. I take this opportunity to express immense debt of gratitude for their relentless guidance and supervision. I wish to express my deep sense of gratitude to Mr. Ajay Kumar, for his day to day supervision at every stage of my work. It is indeed his constant encouragement and valuable advice, which enabled to me complete this thesis in present form.

I also thankful to Mr. Manish Kumar Mishra, Dr. (Smt) Usha Narayanan and Smt. Rupali K Health Physics Division for their valuable advice and help during my experimental works.

It would be incomplete if I do not acknowledge, Shri G.L Teli and Shri A.K.Kazi for giving me a helping hand during collection of samples and experimental works.

Sabyasachi Rout

IV

CONTENTS
Page. No.

Synopsis List of Figures List of Tables CHAPTER-1

1.1 1.2 1.2.1 1.2.2. 1.2.2.1 1.2.2.2 1.2.2.3 1.3 1.3.1 1.3.2 1.3.3 1.3.4 Genesis Multivariate statistical Analysis of Variance Factor analysis (FA) or Principal component analysis (PCA) Cluster Analysis Clustering Observations or type Distance Measures Possible Data Problems in the Context of Cluster Analysis Hydro geochemical Models and Computer programs Trilinear Piper diagram Gibbs- boomerang diagram Stability diagram between solid-liquid phases in aquatic system United states salinity laboratory classification for irrigation water diagram 1.3.5 1.3.6 1.3.7 1.4 PHREEQC hydrochemical code WATCLAST Hydrogeochemical model Ionic Equilibrium model (MEDUSA) Quality Assessment of Soil, Sediment and Groundwater in the terrestrial environment 1.4.1 1.4.2 1.4.3 1.5 Enrichment Factor of heavy metals Geo-accumulation Index (Igeo) of heavy metals Pollution Load Index (PLI) for sampling sites Objective

VIII X XI

Introduction
1

3 5 6 8 8 9 10 11 12 12

12 13 14 14

16 17 18 18

CONTENTS
Page. No.

CHAPTER-2
2.1 2.1.1 2.1.2 2.2 2.3 2.4 2.4.1. 2.4.2. 2.4.3 2.4.3.1 2.4.3.2

Materials and Methods

Context of Study area Geology and Hydrogeology Sampling Sites and Samples Collection Preliminary process of ground water, soil and sediment samples Sample digestion and analysis preparation Analysis Techniques Field Measurements Major cations and anions analysis Analysis of heavy metals Preparation of post column PAR Detection and separation of Cu, Fe, Mn, Ni and Co using ion chromatography 24 25 25 25 25 20 22 24 24

2.4.3.3

Determination of Pb and Cd using DPASV (differential pulse adsorptive stripping voltammeter

27

CHAPTER-3 3.1 3.2 3.3 3.4 3.5 3.6

Results and Discussions

Basic Statistical Analyses Hydro-geochemical evaluation of groundwater Pipers groundwaters classification Saturation Indices (SI) of minerals in ground water Speciation study of major chemical species in ground water of studied area Gibbs-Boomerang diagram for ground water of samples of study site 28 31 32 40 41 44

3.7 3.8

Stability diagrams of clay minerals in groundwater system United State Salinity Laboratory (USSL) classification diagram

45 49

VI

CONTENTS
Page. No. 3.9 3.9.1 3.9.2 3.10 Multivariate Statistical Analysis of water. Factor analysis Cluster analysis of ground water Variation in distribution of Heavy metals in soil and sediments of study area 3.11 Geochemical normalization and enrichment factors (EF) of heavy metals in soil and sediments with respect to continental upper crust Geo-accumulation indices of heavy metals in soil and sediments with respect to continental upper crust Textural analysis of soil Multivariate analysis of Soil Factor analysis Cluster analysis Multivariate Analysis of soils sediments and water 90 92 93 57 49 55 56

3.12 3.13 3.14 3.14.1 3.14.2 3.15

57 63

CHAPTER-4
4.1 4.1.1 4.1.2 4.2 4.2.1 4.2.2 Water

Conclusion
Hydrogeochemical model study Multivariate statistical analysis of ground water Soil Multivariate statistical analysis of soil. Textural, enrichment factor and Geoaccumulation index study of soil 97 98

96 97

4.3

Multivariate statistical study of soils, sediments and water

98

References

99

VII

Synopsis
The present study exclusively focuses on the multivariate analysis of geochemical factors of three matrices (i.e. soil, sediment and ground water) and their association for, a) evaluation of site specific geochemical factors of soils, sediments and groundwater, b) identification and assessment of the different factors influencing these matrices and d) identification of the mineralogy of the study site. In this study special emphasis is given to estuarine area of Mumbai (most populous city of India) due to fact that, monitoring the health of coastal and estuarine ecosystems has become increasingly important over the past decade as human activities continue to affect these systems, and as a result nation is becoming more aware of the need to take a more comprehensive approach to protecting the freshwater and marine water resources. Introductory part of the thesis consists of literature review, objective of the study and description of various hydrochemical models and/or codes for ground water modeling. It also includes a brief discussion of multivariate technique for geochemical data mining with associated drawbacks. Second chapter of the thesis includes sampling, sample processing and sample analysis using different analytical methods like ion chromatography and voltametry etc. An extensive sampling was carried out at estuarine area (formed by Ulhas river) of Mumbai in the month of March and April-2010. Total area covered was around 200 km2 along the both sides of Ulhas River nearest to the creek. Whole study site was divided into 25 locations based upon grid sampling method. Representative samples of soil, sediment (well) and ground water (well water) collected from each location as per protocols. In the third chapter of the thesis different multivariate statistical approaches like Cluster analysis and factor analysis were used in combination with hydrogeochemical programming like PHREEQC, WATCLAST and MEDUSA to access the geochemical parameters (Na+, K+, Mg2+, Ca2+, Fe, Cu, Ni, Cu, Cd and Mn) of soils, sediments and hydrogeochemical parameters (pH, EC, TDS, SAR, Na+ ,K+ ,Mg2+ ,Ca 2+, Cl-, NO3- , SO42, HCO3-, Fe, Cu, Si and Mn) of ground water of estuarine area. The geochemical models or diagrams like Piper diagram, USSL diagram, Gibbs boomerang diagram, stability diagram and saturation index value of different minerals present generated using PHREEQC were used to identify hydrochemical facies of ground water, mineralogy of the study area and ongoing geochemical processes etc.

VIII

Q-mode cluster analysis of hydrogeochemical data of ground water of all 25 locations leads to four distinct zones having similar type of hydrogeochemical evolution, where zone-1 having CaMg- SO42--Cl type, zone -2 is of Ca-Mg- HCO3- type, zone-3 is Na-K-Cl- SO4 type and zone -4 is Ca-Mg- SO42--Cl type with external input of Cu, Mn and Pb. Similarly Q-mode Cluster analysis of geochemical data of soils of the study area classify soils of 25 locations into four geochemically distinct zones, where zone-1 is controlled by anthropogenic input of Cu and Cd, zone-2 is affected by weathering of dolomite minerals, zone-3 is almost unaffected by any of the process and zone-4 is purely lithogenic (affected by weathering process) in nature contaminated by external input of Co. Factor analysis of soil revealed that natural weathering and anthropogenic input of Cu and Cd are important factors controlling the soil type of the study area. Similarly factor analysis of ground water conclude that, there are four factors controlling hydrogeochemical evolution of the ground water, where first factor is lithogenic in origin, factor-2 is anthropogenic in nature, factor-3 is mineralization of ground water by Jorasite-K dissolution and use of NPK fertilizers and the last one is dissolution of sulphate and bicarbonates minerals. Stability diagrams of ground water shows that the studied site is predominated with kaolinite minerals, on the other hand geochemical diagrams like Gibbs-boomerang diagram, Piper diagram etc. suggest that ground water chemistry of the study area is controlled by weathering as well as dissolution of salts of marine origin. There is no evidence of saline water incursion to local aquifer system. Textural, enrichment factor and geoaccumulation index studies reveal that soils of study area is practically uncontaminated w.r.t. Fe, Mn and Pb (except location 1, 2 and 21), moderately contaminated by Co and Ni at few locations. All the locations are contaminated with Cu and Cd. Multivariate statistical study of soils, sediments and water, revealed that Fe in soils, sediments and water, Mn, in soils and sediments have common origin (i.e., soils and sediments have common parent rock and chemical compositions of ground water is controlled by chemical composition of nearby soil and sediment of the well. Similarly Cu in water and sediments, Pb in soil and sediments have common in origin, Cu (soil) is isolated in last factor indicates its external input to the different systems. The difference in association of Mn (soils and sediments) with Mn (water), Cu (water and sediment) with Cu (soil), and Pb (soil and sediment) with Pb (water) may be due to different migration rate of these species from one system to another.

IX

List of Figures
Figure 1: Figure 2: Figure 3: Figure 4: Figure 5: Figure 6: Figure 7: Figure 8: Figure 9: Figure 10: Figure 11: Figure 12: Figure 13: Figure 14: Figure 15: Figure 16: Figure 17: Figure 18: Figure 19: Figure 20 Figure 21: Figure 22: Figure 23: Figure 24 Figure 28: Figure 29 Figure 40 Figure 43: Factor Analysis. Flowchart Piper-tri-linear diagram Output of simulation of groundwater data generated using PHREQC Hydrogeology map of greater Mumbai Map of Study Site Chromatogram (mAu Vs Retention Time) of Fe, Cu, Ni, Co and Mn Differential pulse voltammograms of Cd, Pb and Cu Box and Whiskers plot of major elemental concentration of soil Whiskers plot for major ionic concentration in ground water Box and Whiskers plot of distribution of heavy metals in soil Box and Whiskers plot of major elemental concentration in sediment Whiskers plot of distribution of heavy metals in sediment Trilinear Pipers plot for ground waters classification of study site Hydrogeochemical facies in ground water pH- dependent calculated species distribution of Na in the groundwater at the various range of [SO4] & [Cl] pH- dependent calculated species distribution of Mg and Ca in the groundwater at the various range of [SO4] & [Cl] pH- dependent calculated species distribution of Mg and Ca in the groundwater at the various range of [CO3] pH- dependent calculated species distribution of Fe and Mn in the groundwater at the various range of [CO3] Gibbs-Boomerang diagram for cations and anions in ground water of study site (a, b, c, d):Stability diagram for K, Na, Ca and Mg system Stability diagram in presence of sea water impact USSL diagram for classification of ground water Scree plot for ground water -27: Factor score plot of F1 to F4 of ground water Dendrogram of Q-Mode cluster analysis of water samples -39:Bar graph of geoaccumulation indices of soil fraction-1 to11 -42: Factor score plot of F1 to F3 of soil Dendrogram of Q-Mode cluster analysis of soil samples

List of Tables
Table 1: Table 2: Table 3: Table 4: Table 5: Table 6: Table 7: Table 8: Table 9: Table 10: Table 11: Table 12: Table 13: Table 14 Table 15: Table 16: Table 17: Table 18 -28: Table 29-39: Table 40: Table 41: Table 42: Table 43: Table 44: Table 45: Description of different section of diamond field of Piper diagram Ground Water Data Sheet Descriptive statistics of ground water samples Soil Data Sheet Descriptive statistics of soil samples Chemical characteristic data sheet of ground water Saturation level of different minerals in groundwater of all locations Standardized data set of water parameters Correlation matrix chart for different species in ground water Eigen value for factor analysis of ground water Factor loading matrix of ground water Sediment Data Sheet Soil enrichment factor Data sheet : Sediment enrichment factor data sheet Geoaccumulation Index of Soil Geoaccumulation Index of Sediment. Classification of geo-accumulation index based on sediment/soil quality Soil data sheet fraction-1 to 11 Soil enrichment factor Data sheet fraction-1 to 11 Eigen value for factor analysis of soil Factor loading matrix of soil Correlation Matrix for soil parameters Eigen value spread sheet soil sediment and water Factor loading matrix of soils, sediments and water Correlation Matrix for soils, sediments and water.

XI

CHAPTER-1
INTRODUCTION
1.1 Genesis

tudy of chemical and physical evolution of soils, sediments and ground water is very complex due to multiple interactions between these matrices and various controlling

parameters. Water plays a major role in controlling the geochemistry of soils and sediments as it is the interface between soils and sediments. To understand hydrochemistry and to analyze natural as well as man-made impacts on aquatic systems, hydrogeochemical models have been used since the 1960s and more frequently in recent times. Numerical groundwater flow, transport and geochemical models are important tools besides classical deterministic and analytical approaches. Solving complex linear or non-linear systems of equations, commonly with hundreds of unknown parameters, is very complex and hectic task for researchers. Modeling hydro-geochemical processes requires a detailed and accurate water analysis, as well as thermodynamic and kinetic data as inputs with physical parameters of soil. Thermodynamic data, such as complex formation constants and solubility-products are often provided as databases within the respective programs. However, the description of surface-controlled reactions (sorption, cation exchange, surface complexation) and kinetically controlled reactions requires additional input data. Unlike groundwater flow and transport models, thermodynamic models, in principal do not need any calibration. Nevertheless, considering surface-controlled or kinetically controlled reaction models might be subject to calibration, typical problems for the application of geochemical models are as follows a) Speciation b) Determination of saturation indices c) Adjustment of equilibria /disequilibria for minerals or gases d) Mixing of different waters e) Modeling the effects of temperature

f) Stoichiometric reactions (e.g. titration) g) Reactions with solids, fluids, and gaseous phases (in open and closed systems) h) Sorption (cation exchange, surface complexation) i) Inverse modelling j) Kinetically controlled reactions k) Reactive transport Hydrogeochemical models depend on the quality of the chemical analysis, the boundary conditions presumed by the program, theoretical concepts (e.g. calculation of activity coefficients) and the thermodynamic data. For this, a basic knowledge about chemical and thermodynamic processes is required. Several models and methods of data analysis have been devised to simplify interpretation and presentation such as trilinear diagram, Gibbs Boomerang diagram, Stability diagram, Duorv diagrams etc. for hydrogeochemical studies [1]. The existing methods may provide some information. Nevertheless, these conventional techniques are generally limited to major constituent ions. They ignore many parameters which are otherwise important for studies. The limitation that is coupled for using the traditional graphical methods has been discussed by several authors [2]. Although enrichment factor and geoaccumulation indices [3] studies reveal the extent of pollution of soil and sediments, it is unable to present source approximation. In view of the limitation of the existing methods and increasing number of chemical and physical variables measured in different systems (groundwater, soils and sediments) investigations, multivariate analysis comes into play as a rather essential tool for explaining chemistry of soils, sediments and water. A lot of work has been done to identify the sources of different chemical species and geochemistry of ground water, soil and sediment, consequently to formulate the conceptual models of geochemical parameters distribution and to identify the source of heavy metal contents in different kinds of soil using multivariate analysis [4-8]. Some work has also been done on application of multivariate analysis of chemical composition of soils, sediments and ground water all together which is very important because all these three systems are inter linked to each other, one of the work which highlights the application of multivariate analysis of heavy metals contents in soils, sediments and water in the regions of Meknes (central Morocco) reveals association of heavy metals in different systems have common origin [9]. Hence,

multivariate statistical methods are found to be very useful tools for exploration of hydrogeochemical evolution of ground water and geochemistry of soil and sediments. 1.2 Multivariate statistical Analysis of Variance 1.2.1 Factor analysis (FA) or Principal component analysis (PCA) The main use of PCA/FA is to reduce the dimensionality of a data set by replacing the old coordinate of the factor space. It computes a compact and optimal description of the data set. The first step in factor analysis is computation of correlation coefficient matrix which requires normal distribution of all variables. The correlation coefficient is computed by the eigen values and percent of trace or the amount of variance which describes that all the variables are common or shared. The following series of procedure are required for analysis of geochemical data using factor analysis. a) Data reduction using replacement of the large number of variables by small number of factors in terms of the information content of data matrix. b) Identify the structure underlying a set of variables by removing redundancy. c) Develop a scale using several variables d) Identify uncorrelated factors e) Calculation of a correlation matrix f) Extraction of initial factors g) Rotation of factors h) Interpretation i) Conducting factor analysis R-mode factor analysis gives the interrelationship between variables and Q-mode is devoted exclusively to interrelationship between samples. In R-mode, the number of original variables is reduced by detecting the variables. It provides several positive factors that allow interpretation of the data set. By examining the factor loadings, communalities and eigen values of those variables whose specific chemical process can be identified and the importance of major elements can be evaluated in terms of factors. Communalities are an indicator of error term. The equation for FA and /or PCA is as follows;

X T .P E .. (1)
Where, X = original data matrix, T = Score matrix (sampling points), P =loading matrix parameters), E = Errors.

Fig-1. represents flow chart for factor analysis starting from problem formulation to prediction of model for interpretation of data Problem formulation

Construction of the correlation matrix (R-type and Q-type)

Method of factor analysis (PCA)

Determination of number of factors (eigen values >1)

Rotation of factors using varimax rotation for easy interpretation

Interpretation of factors by calculation of factor scores and selection of surrogate variables

Determination of model fit based on residuals Fig. 1 Factor Analysis Flowchart

The new variables (X), being linear combinations of previous variables are called latent factors or principal components. The interpretation of new factors gives the vital information about latent relationships within the data set. The new principal components (latent factors) explain a substantial part of total variance of the system for adequate statistical models. Usually, first principal components (PC1/F1) explains the maximal part of the system variation and each additional PC has a respective contribution to the variance explanation but less significant. In our model, we have applied the Varimax rotation mode for FA that allows a better explanation of the system in consideration since it strengthens the role of latent factors with higher impact on the variation explanation and diminish the role of PCs with lower impact. The application of PCA to the data set aimed the identification of latent factors responsible for the data structure and possibly representing the emission of source. The results are indicated by two sets: factors loading providing information on the relationship between the variables and factor. Whereas factor scores giving the new coordinate of the factor space with the location of the objects. Only statistically significant factor loadings (> 0.7) are important for the modeling procedure. But the

some researchers consider the factor loading (> 0.6) as significant contributor and 0.3-0.5 as possible contributor [2]. The significant factor loading may be positive (+) or negative (-). The positive loadings indicate that the contribution of variables increases with increasing loading in a dimension and negative loadings indicate a decrease [2]. Since the factor scores are calculated for each sample and reflect the importance of a given factor at the sampling site, Dalton and Upchurch have shown that factor scores can be related to intensity of the chemical process described by each factor. Extreme negative number ( -1) reflect areas essentially unaffected by the process and positive scores (+ 1) reflect areas most affected. Near 0 score approximate areas affected to an average degree by the chemical process of that factor. 1.2.2 Cluster Analysis The principal aim of cluster analysis is to partition observations into a number of groups. A good outcome of cluster analysis will result in a number of clusters where the observations within a cluster are as similar as possible while the differences between the clusters are as large as possible. Cluster analysis must thus determine the number of classes as well as the memberships of the observations to the groups. To determine the group membership most clustering methods use a measure of similarity between the observations. The similarity is usually expressed by distances between the observations in the n-dimensional space of the variables. Cluster analysis is still a popular technique, in part because as a complicated statistical technique it appears to add a scientific component to a publication. Readers of papers using cluster analysis should be very aware of the problems cluster analysis can be applied as an "exploratory data analysis tool" to better understands the multivariate behaviour of a data set. It can, however, never be a "statistical proof of a certain relationship between the variables or observations. Clustering methods also exist that are not based on distance measures, like model-based clustering [10]. These techniques usually find the clusters by optimising a maximum likelihood function. The implicit assumption is that the data points forming the single clusters are multivariate normally distributed, and the algorithm tries to estimate the parameters from the normal distribution as well as the membership of each observation to each cluster. With geochemical data cluster analysis can be used in two different ways: it can be used to cluster the variables (e.g. to detect geochemical relations between the variables) and it can be

used to cluster the observations (e.g. to assign soil samples to certain parent materials) to come to more homogenous data subsets for further data analysis. 1.2.2.1 Clustering Observations or Types One of the main problems with cluster analysis is that a multitude of different clustering methods exists. The observations need to be grouped into classes (clusters). If each observation is allocated into only one (of several possible) cluster(s) this is called "partitioning". Partitioning will result in a pre-defined (user defined) number of clusters. It is also possible to construct a hierarchy of partitions, i.e. group the observations into 1 to n clusters (n = number of observations). This is called hierarchical clustering. Hierarchical clustering always delivers n cluster solutions, and based on these solutions the user has to decide which result is most appropriate. a) Hierarchical Methods Input to most hierarchical clustering algorithms is a distance matrix (distances between the observations). The widely used agglomerative techniques start with single object clusters (each observation forms an own cluster) and enlarge the clusters stepwise. The computationally more intensive reverse procedure starts with one cluster containing all observations and splits the groups step by step. This procedure is called divisive clustering. At the beginning of an agglomerative algorithm each observation forms its own class, leading to n single object clusters. The number of clusters is reduced by one by combining (linking) the most similar classes at each step of the algorithm. The similarity of the combined pair, a new class, can be measured to all other classes, and the next two most similar classes linked, and so on. At the end of the process there is only one single cluster left, containing all the observations. A number of different methods are available for linking two clusters and the best known are Wards method, average linkage, complete linkage and single linkage. Wards method is much successful to form clusters that are more or less homogeneous and geochemical distinct from other clusters, compared to other method, uniqueness of wards method is, it uses analysis of variance approach to evaluate distance between cluster to perform CA. Because the cluster solutions grow tree-like (starting with the roots and ending upwards with the trunk) results are often displayed in a graphic called the dendrogram. Horizontal lines indicate the linkage of two objects or clusters, and thus the vertical axis presents the associated height or similarity as a measure of distance. The objects are arranged in such a way that the branches of the tree do not overlap. Linking of two groups at a large height indicates strong dissimilarity (and vice versa).

Therefore, a clear cluster structure would be indicated if observations are linked at a very low height, and the distinct clusters are linked at a considerably higher value (long roots of the tree). The dendrogram does not provide cluster assignments by itself, as the number of clusters to be formed must be chosen by the user. This exibility is one of the subjective points in CA, because the user is free to achieve a certain desired result cutting the dendrogram at the height (phenon line) corresponding to this visible number of clusters allows assigning the objects to the clusters. Visual inspection of a dendrogram is often helpful in obtaining an initial idea of the number of clusters to be generated by a partitioning method. b) Partitioning Methods: In contrast to hierarchical clustering methods, partitioning methods require the number of resulting clusters to be pre-determined. As noted above, when nothing is known about the observations it can be useful to first carry out a hierarchical clustering. The other possibility is to partition the data into different numbers of clusters and evaluate the results for regionalised data a more subjective but still reasonable approach of evaluation is to visually inspect the location of the resulting clusters in a map. This exploratory approach can often reveal interesting data structures. A very popular partitioning algorithm is the k-means algorithm. It attempts to minimise the average squared distance between the observations and their cluster centres or centroids. Starting from k initial cluster centroids (e.g. random initialisation by k observations) the algorithm assigns the observations to their closest centroids (using e.g. Euclidean distances) recomputes the cluster centres, and iteratively reallocates the data points to the closest centroid. Several algorithms exist for this purpose; those of Hartigan [11] and MacQueen [12] are the most popular. There are also some modifications of the k-means algorithm. Manhattan distances are used for k-medians and the centroids are the medians of each cluster. Hard competitive learning works by randomly drawing an observation from the data and moving the closest centre towards that point [13]. Martinetz et al. [14] have introduced "neuralgas", this method is similar to hard competitive learning, but in addition to the closest centroid also the second closest centroid is moved at iterations. Kaufmann and Rousseeuw proposed several clustering methods which are implemented in a number of software packages. The result of all these algorithms depends on the initial cluster centres, which are often a random selection of k of the observations. If bad initial cluster centres are selected, the iterative partitioning algorithms can lead to a local optimum that can be far away from the global optimum.

1.2.2.2 Distance Measures A key issue in most cluster analysis techniques is how best to measure distance between the observations (or variables). Note that "distance" in cluster analysis has nothing to do with geographical distance between two observations but is rather a measure of similarity between observations in the multivariate space defined by the entered variables. Many different distance measures exist [15]. Modern software implementations of cluster algorithms can accommodate a variety of different distance measures because the distances rather than the data matrix are taken as input and the algorithm is applied to the given input. For clustering the observations the Euclidean distance, correlation based distance measures and Manhattan distance is the most frequent choice. Other distance measures like the Gower distance, Canberra distance and a distance measure based on the random forest proximity measure [16] can give completely different cluster results. To demonstrate the effect of the distance measure used for clustering geochemical data the average linkage clustering algorithm has been applied to the present data. 1.2.2.3 Possible Data Problems in the Context of Cluster Analysis a) Data Outliers: Regional geochemical data sets practically, always contain outliers. The outliers should not simply be ignored but they have to be accommodated because they contain important information about data quality and unexpected behaviour in the region of interest. In fact, finding data outliers indicative of mineralisation (in exploration geochemistry) or of contamination (in environmental geochemistry), are one of the major aims of geochemical surveys. Outliers can have a severe influence on cluster analysis, because they can affect proximity measures and obscure clustering tendencies. Outliers should thus be removed prior to entering a cluster analysis or statistical clustering methods capable of handling outliers should be used. This is rarely done. Finding data outliers is not a trivial task, especially in high dimensions. One way of identifying such outliers is to compute robust Mahalanobis distances, i.e. Mahalanobis distances on the basis of robust estimates of location and scatter. b) Censored Data: A further problem that often occurs when working with geochemical data is the detection limit problem. For some determinations a proportion of all results are below the limit of detection of the analytical method, i.e. the data are censored. For statistical analysis, these results are often set to a value of the detection limit. However, a sizeable proportion of all data with an identical value can seriously influence any cluster analysis procedure. It is very questionable as to whether or not such elements should be included at all in a cluster analysis.

The elements of greatest interest that contain the highest number of censored data, the temptation to include these in a cluster analysis is thus high. In that case, the elements with below detection can be omitted from cluster analysis. c) Data Transformation and standardisation: Cluster analysis in general does not require that the data be normally distributed. However, it is advisable that heavily skewed data are first transformed to a more symmetric distribution. If a good cluster structure exists for a variable, we can expect a distribution, which has two or more modes. A transformation to more symmetry will preserve the modes but removes large skewness. Most geochemical textbooks still claim that for geochemical data a log-transformation is most suitable. Recently Reimann and Filzmoser have shown that very few geochemical variables will indeed follow a (log)-normal distribution. Each single variable needs, unfortunately, to be considered for transformation and different transformations, with the Box-Cox transformation [17] being the most universal choice, need to be considered. The most practical decision guides whether to transform or not and how to transform should be dependent upon the data distribution and it should be close to symmetry prior to entering cluster analysis. Even Box-Cox transformations of all single variables do not guarantee symmetry of the resulting multivariate data distribution, but more closeness to symmetry (or removal of strong skewness) will in general improve the cluster results. An additional standardisation is needed if the variables show a striking difference in the amount of variability in major, minor and trace elements. Different methods, all having advantages and disadvantages, exist to accommodate this requirement. The most universal method is the ztransformation, which builds on the mean and standard deviation of the data. When working with geochemical data, a robustified version, using median should be preferred.

1.3 Hydro geochemical Models and Computer programs Hydrogeochemical models and diagrams are aimed at facilitating interpretation of evolutionary trends, particularly in groundwater systems, when they are interpreted in conjunction with distribution maps and hydrochemical sections. A trilinear diagram to describe water chemistry was first attempted by Hill [18] and refined by Piper [19], Gibbs diagram, stability diagram etc. used to assess the water type. But almost all the diagrams are based upon major cations/anions of the aquatic system.

1.3.1 Trilinear Piper diagram In the Piper diagram, major ions are plotted in the two base triangles as cation and anion mill equivalent percentages. Total cations and total anions are each considered as 100%. The respective cations and anions locations for an analysis are projected into the diamond field, which represents the total ion relationship. The Piper diagram has been widely used to study the similarities and differences in the composition of waters and to classify them into certain chemical types. The water types demonstrated by the Piper diagram, as described by Karanth [20] shows the essential chemical character of different constituents in percentage reacting values, expressed in milligrams equivalent. Piper diagram allow comparisons to be made among numerous analyses, but this type of diagram has a drawback, as all trilinear diagrams do, in that it does not portray actual ion concentration. The distribution of ions within the main field is unsystematic in hydrochemical-process terms, so the diagram lacks certain logic. Piper suggested the method of encircling the plotted points in the central diamond field with its area proportional to the absolute concentration. This method is not very convenient when plotting a large volume of data. Nevertheless, this shortcoming does not lessen the usefulness of the Piper diagram in the representation of some geochemical processes. Fig.2 is the piper-tri-linear diagram which represents different ionic composition of water. The classification based on chemical characterization of aquatic system is presented in Table-1.

Legends A- Calcium type B- No Dominant type C- Magnesium type D-Sodium potassium type E- Bicarbonate type F- Sulphate type G- Chloride type and

Fig. 2 Piper-tri-linear diagram

10

Table 1. Description of different section of diamond field of Piper diagram Different divisions Of piper Diagram 1. 2. 3. 4. 5. 6. 7. 8. 9. Chemical Composition Type Alkaline earth (Ca+Mg) Exceed alkalies (Na+K) Alkalis exceeds alkaline earths Weak acids (C03+HCO3) exceed Strong acids (SO4+Cl) Strong acids exceeds weak acids Magnesium bicarbonate type Calcium-chloride type Sodium-chloride type Sodium-Bicarbonate type Mixed type (No cation-anion exceed 50%)

1.3.2 Gibbs- boomerang diagram Gibbs-boomerang diagram is an important tool to analyze geochemical processes [21]. Gibbs studying the salinity of world surface water concluded that three natural mechanisms control the chemistry of waters: atmospheric precipitation, rock dominance or rock weathering, and evaporationcrystallization process. Gibbs diagram, a boomerang-shaped envelope, is obtained when the weight ratio Na+/ (Na++Ca2+) on the X- axis is plotted versus TDS values on the Yaxis (for cations). Similarly for anions of Cl-/ (Cl-+HCO3-) on X -axis versus TDS values on Yaxis. When the dominant process is rock weathering, waters produce calcium and bicarbonate as predominant ions, TDS values are moderate and sample data plot in the middle region of the Gibbs boomerang. Low salinity waters of sodium chloride type are due to the atmospheric precipitation process and sample data plot in the lower right corner of the boomerang. The processes mentioned above do not exclude each other, and many water present chemical compositions between the two extremes. It seems better to consider rock weathering and atmospheric precipitation as the ends of a continuous series. The third mechanism that controls the water chemistry is the evaporationcrystallization process, important in arid areas, where evaporation is larger than precipitation. The evaporation process increases TDS and the relation

11

Na+/ (Na++Ca2+), the latter principally due to calcite precipitation. The surface waters that respond to this process are on the right upper side of the Gibbs boomerang in a continuous series between those whose chemical composition is derived from rock weathering and seawater composition.

1.3.3 Stability diagram between solid-liquid phases in aquatic system Stability diagrams are graphical representations of equilibrium between minerals and aqueous solution (water); it reveals which mineral is in equilibrium with water at ambient temperature. Hence stability diagram gives idea about, what happens when water of various compositions interact with solid phase (minerals), what will happen during chemical weathering of silica and what will happen if there is change in the concentration of constituent ions by addition or removal. It is a general practice to draw the stability diagram by plotting the graph between log [M+] / [H+] versus log [H4SiO4], where M is metal of interest in most of the cases, Ca, Mg, K, and Na is taken as these four metal ions are major constituent of water.

1.3.4 United states salinity laboratory classification for irrigation water diagram The diagram (Fig.20) is the plot of specific conductance of water (micromho/cm) versus sodium adsorb ratio (SAR ), consist of sixteen regions based upon SAR and specific conductance values which revels the sodium hazard and salinity hazard of the water samples. Water with high low value of SAR and sp.conductance has low salinity and sodium hazards than water with high SAR and specific conductance which has high sodium hazard and salinity hazard. 1.3.5 PHREEQC hydrochemical code PHREEQC (ver. 2) is a computer program written in the C programming language that is designed to perform a wide variety of low-temperature aqueous geochemical calculations. PHREEQC is based on an ion-association aqueous model and has capabilities for (1) Speciation and saturation-index calculations; (2) Batch-reaction and one-dimensional (1D) Transport calculations involving reversible reactions, which include aqueous, mineral, gas, solid-solution, surface-complexation, and ion-exchange equilibria, and irreversible reactions, which include specified mole transfers of reactants, kinetically controlled reactions, mixing of solutions, and temperature changes; and (3) Inverse modeling, which finds sets of mineral and gas mole

12

transfers that account for differences in composition between waters, within specified uncertainty limits. Fig-3 represents the output file of the simulation data of this study.

Fig. 3 Output of simulation of groundwater data generated using PHREQC It is specially used for simulating chemical reactions and transport processes in natural or polluted water. PHREEQC uses ion-association and Debye Hckel expressions to account for the non-ideality of aqueous solutions. This type of aqueous model is adequate at low ionic strength but may break down at higher ionic strengths (in the range of seawater and above). An attempt has been made to extend the range of applicability of the aqueous model through the use of an ionic-strength term in the Debye Hckel expressions. These terms have been fit for the major ions using chloride mean-salt activity-coefficient data [22]. Thus, in sodium chloride dominated systems, the model may be reliable at higher ionic strengths. For high ionic strength waters, the specific interaction approach to thermodynamic properties of aqueous solutions should be used [23-25], but this approach is not incorporated in the other limitation of the aqueous model is lack of internal consistency in the data in the databases. 1.3.6 WATCLAST hydrogeochemical model Its a DOS based computer programming which is used for calculating ionic activity, saturation indices and different physical parameters of the water like sodium adsorb ratio(SAR), residual sodium carbonate (RSC) used to plot different hydrogeochemical graphs like, stability diagram,
13

Gibbs boomerang diagram, USSL diagram etc. which in turn are helpful to characterise the water type. 1.3.7 Ionic Equilibrium model (MEDUSA) MEDUSA stands for Make Equilibrium Diagrams Using Sophisticated Algorithms. It is a Windows interface to the MSDOS programs, which perform the calculations needed to create chemical equilibrium diagrams. It can also call HYDRA (Hydrochemical Equilibrium Constant Database) to make diagrams based on equilibrium constants retrieved from a database. 1.4 Quality Assessment of Soil, Sediment and Groundwater in the terrestrial environment With the rapid industrialization, infrastructure development, tourism increase and economic development in urban areas over the last few decades, heavy metals are continuing to be introduced in the terrestrial environment through various routes. Heavy metals are natural constituents of the earths crust and are present in varying concentration in all ecosystems. These metals can be transferred from soil to the other ecosystem components, such as underground water or crops and can aect human health. The natural input of several heavy metals to soils due to pedogenic processes has been exceeded in some local areas by human activity; even on regional scale in particular agricultural soils can be a long-term sink for heavy metals. These soils have also been inuence by other pollutant activities such as the use of manures, sewage sludge disposal or aerial fallout from industrial activities [26]. As a consequence, potentially toxic elements have accumulated in the soil prole. This can result in loss of soil functions concerning environmental quality protection, maintenance of human health and productivity, which are relevant aspects of soil quality [27]. In some areas with heterogeneous lithology, heavy metal contents can be highly variable, determined by the parent material and soil properties. For example, organic matters, clay and carbonates play a crucial role in the availability of heavy metals in calcareous soils [28] as the heavy metals cannot be degraded or destroyed they tend to accumulate in different compartments of the systems like water, soil and sediment . Various studies have demonstrated for quality assessment for soil, sediments and ground water in the terrestrial ecosystem, which are highly contaminated by heavy metals. Therefore, the evaluation of metal distribution in soil and sediments is useful to assess pollution in the terrestrial environment. These heavy metals participate in various biogeochemical mechanisms that have significant mobility, which affects the ecosystems through bioaccumulation and bio-

14

magnification processes and are potentially toxic for environment and human life. Metals such as Fe, Ni, Cu, Co, Mn, Cd and Pb etc. are used in contamination studies in the systems due to their relationship with anthropogenic activities. Sediments are important carriers of trace metals in the hydrological cycle because metals are partitioned with the surrounding waters; they reflect the quality of an aquatic system. Thus, geochemical characteristics of the soil and sediments can be used to infer the weathering trends and the sources of pollution. Because of their large adsorption capabilities, fine-grained sediments represent a major repository for trace metal and a record of the temporal changes in contamination. Over the last few decades, the study of soil and sediment quality has shown to be an excellent tool for establishing the effects of anthropogenic and natural processes on depositional environments. A number of recent pieces of work have used sediment profiles to describe the contamination history of different environments. Metals enter the environment by two means: natural processes (including erosion of ore-bearing rocks, wind-blown dust, volcanic activity and forest fires) and processes derived from human activities by means of atmospheric deposition, rivers and direct discharges or dumping. The composition of groundwater sediments is dependent on local geology as well sediments actively interact with emerging groundwater. All the above factors influence ground water quality. Additional anomalies of associations of several ore-related elements are attractive targets for follow-up study. Single-element anomalies may be caused by local pollution i.e. anthropic input. In most cases if the soil is contaminated the sediment also is contaminated, as sediments are derived from soil. Groundwater is the main source of irrigation water supply and drinking water for many settlements. Hydro geochemical evaluation of ground water varies from place to place as water derives its composition from the parent rock in the weathering region; sediments owe their mineralogical composition partly to the chemical reactions between rock and water. When such reactions reach thermodynamic equilibrium with certain mineral assemblages would coexist in sediment phase, provided the chemistry of water remains same [28] with respect to the other factors like quality of water, interaction with other water systems (lake, river and sea) and human activities (agricultural, industry, urbanization and increasing exploitation) [29]. Groundwater may be contaminated upon leaching of chemicals in the soil surface towards the aquifer. The agricultural irrigation effluents, industrial wastewater discharge and domestic effluents have largely contributed to groundwater. The changes in agricultural practices during the last fifty

15

years (use of fertilizers, simplication of the landscape, mechanization, drainage etc.) have signicantly contributed to increase the concentrations of pollutants in surface and shallow groundwater to such an extent that it has become detrimental to aquatic ecosystems which present evident signs of eutrophication [30]. Non-point sources of pollution by agriculture activities and livestock have appeared as major risks to the planets groundwater resources [31, 32]. The main non-point source pollutants are agrochemicals, fertilizers and salts contained in irrigation leaching. These are the major pollutants in the water that percolates through the root zone into the shallow aquifer, limiting urban, industrial, agricultural and ecological uses [33]. Nowadays there is a great threat of saline incursion to the costal aquifers which will become more problematic in future due to over exploration of ground water with rise in mean sea level. The measurement of trace element concentrations and distribution in terrestrial environment leads to better understanding of their behaviour in the aquatic environment and is important for detecting sources of pollution. Hence, the pollution status of soil and sediments of any area can be predicted by evaluating the enrichment factor (EF), Pollution Load Index (PLI) and Geoaccumulation Index (Igeo) of heavy metals.

1.4.1 Enrichment Factor of heavy metals The nature and relative importance of various sources of heavy metals and other species of environmental interest are determined in number of ways. The most common discrimination techniques use elemental, molecular and isotopic signatures to characterize anthropogenic, crustal and marine sources. The enrichment factor represents the amount of a particular element in excess of that expected from natural rock or soil source. It is often assumed that aluminium content of a particulate is due solely to crustal sources. Iron, scandium, titanium and silicon may also be reasonable choices for elements of totally crustal origin. Hence, Fe or Al can be chosen as reference element. The crustal source can either be average crust or local rock or soil. Normalizing elements relative to Al is widely used to compensate for variations in both grain size and composition, since it represents the quantity of aluminosilicates, which is the predominant carrier phase for adsorbed elements in soil and sediments. Therefore, this method is a powerful tool for the regional comparison of trace metal content in sediments, soils and can also be applied to determine enrichment factors [34]. When assessing metal sediment and/or soil concentrations for environmental studies, one major problem is the choice of methods of data

16

analyses. One may attempt to evaluate the data on the basis of absolute metal concentrations, or choose between varieties of other methods, ranging from relatively simple ones like elemental ratios to more sophisticated, such as discriminate analysis. Helz and others calculated enrichment factors (EF) for the data using A1 as the reference metal and average crustal by the relations: EF = (X/A1) sediment (or soil)/ (X/A1) continental upper crust ---------------(Eq.1)

Where, X/A1 is the ratio of the concentration of element X to A1. Using Fe-based enrichment factors, Helz and others compared their data pertaining to a particular environment with that of similar environment in other places of the country/ world [35]. Formulae used for calculation of enrichment factor for this study is as follows. EF = (CX /Fe) sediment (or soil) / (CX / Fe) continental upper crust -------------(Eq.2)

Where, Cx is the concentration of metal x in sediment or soil. When enrichment factors (EFs) of heavy metals are close to unity then it is assumed that metals have originated from crustal origin while those greater than 10 are considered to be non-crustal source. EF values lower than 0.5 can reflect mobilisation and loss of these elements relative to Fe, or indicate an over estimation of the reference metal contents. The worlds continental upper crust value is considered as reference element for bottom sediment and soil. But in general, the textural characteristic of the sediments and soils in our present investigation was sandy, silty-sand type nature so the use of Al as a normalisation element is not of much significance for the universal comparison of the sediments. As stated by Forstner, Wittmann and Jenne [35] in the case of Fe, particularly the redox sensitive iron-hydroxide and oxide under oxidation constitute significant sink of heavy metals in aquatic systems. Even a low percentage of Fe (OH)3 has a controlling influence on the heavy metal distribution in an aquatic system. Because of importance, Fe could be used as normalisation element for the sedimentary and soil geochemistry, which would provide better result and also help universal composition. 1.4.2 Geo-accumulation Index (Igeo) of heavy metals Geo-accumulation index (Igeo) has been used widely to evaluate the degree of metal contamination or pollution in terrestrial, aquatic and marine environment and to quantify the metal accumulation, which compare the present status with the pre-civilized background values proposed by Muller [3]. Igeo = log2 [Cx /1.5Bn] ------------------------------------------------ (Eq.3)

17

Where, Cx = concentration of element and Bn = geochemical background value Based on worlds average continental upper crust value and worlds average suspended sediment value, the Igeo values are calculated. Igeo may be classified in seven grades. An Igeo of 6 indicates a 100-fold enrichment of an element above the background [3]. Igeo value for 0-1 indicates slight pollution and less than zero (0) means no pollution. Classes 1-2 and 2-3 indicate moderate to strong pollution.

1.4.3 Pollution Load Index (PLI) for sampling sites Pollution load index is used in order to find out the mutual effect of different studied metals. Pollution load index (PLI), for a particular site, can be evaluated following the method proposed by Tomilson et al. This parameter is expressed as: PLI = (CF1x CF2 x CF3 x .. x CFn) 1/n ---------------- (Eq.4) Where, n is the number of metals and CF is the contamination factor. The contamination factor can be calculated from the following relation: CF (Contamination factor) = Metal concentration in the sediments/ Background value of the metal 1.5 Objective The geochemical characteristics of soils, sediments and groundwater of any area are controlled by many factors, which include local geology of the area, mineralogy of the area, precipitation, meteorological changes and topography. All these factors combine to generate diversified types of soils, sediments and groundwater in terrestrial ecosystem. In addition to various geochemical processes (mineralization, weathering etc.) some anthropogenic activities like rapid industrialisation; urbanisation etc. can also be responsible for changes in chemical characteristics of all the three interlinked matrices. Due to complexity of chemical and physical evolution of soils, sediments and water, interpretation of results are often insufficient to provide a clear picture of the systems under study [36]. The purpose of present study is exclusively focused on application of multivariate analysis to geochemical factors (major cations, anions, heavy metals and physical parameters of ground water like, pH, EC and TDS etc.) of three matrices i.e. soils, sediments and ground water of estuarine region (formed by Ulhas river) at north of Mumbai. In this study special emphasis was given to estuarine area which is a semi-enclosed costal body of water that has free connection ----------- (Eq.5)

18

with the open sea (Arabian Sea) and within which sea water is measurably diluted with freshwater derived from river (Ulhas River). Monitoring the health of coastal and estuarine ecosystems has become increasingly important over the past decade [37]. The study involves establishment of the relations, associations and causes for the interdependence among the various chemical species present in the groundwater, sediment and soil profile and to identify and assess, possible sources of their origin using different geochemical models like PRHEEQC, WATCLAST, Trilinear Pipers diagram, Gibbs Boomerang diagram, etc. As the study of the hydrogeochemistry of groundwater and geochemistry of soils and sediments requires handling of a large data set the classification, modeling, and interpretation of the data are the most important steps in the assessment of soil, sediment and water quality. Therefore the main purpose of data analysis is to detect inter-elemental relationships of geochemical data which reflect the mineralogy, chemical species interactions and different geological processes, then isolate a typical observations or groups of observations that are potentially identified with processes of interest (mineral deposits, hazardous environment) and finally recognize the pattern or trend in data analysis. In order to achieve this objective, multivariate statistical technique such as factor analysis (FA) as well as cluster analysis (CA) has been used successfully. These statistical techniques can provide a powerful tool for analyzing the multivariate geochemical data of water, sediment and soil. Since, multivariate data exists in multidimensional space which is clearly impossible to visualize above 3D. Therefore, the factor analysis is used to simplify the complex and diverse relationships which exist among a set of observed variables by revealing common and unobservable factors. It also explains the correlations between the variables in terms of the underlying factors, which are not apparent. Usually, CA is carried out to reveal specic links between sampling points, while FA/PCA is used to identify the ecological aspects of pollutants on environmental systems [1]. In this study, STATISTICA software package (Statsoft India, version 7) has been used for the basic statistical analyses, Hierarchical cluster analysis (HCA), correlation matrix and factor analysis (using Principal component extraction method).

19

CHAPTER 2
MATERIALS AND METHODS
2.1 Context of Study area 2.1.1 Geology and Hydrogeology

he physiographic feature of the study area is broad and flat terrain flanked by north south trending hill ranges. The hill ranges from almost parallel ridges in the eastern and western

part of the area. The site is located in the north-east part of Mumbai between latitude 1805933 N- 1900112 N and longitude 720 5445 - 720 5711E at an average elevation of 13 m from the sea level. The northern part of Mumbai is hilly. Climate of Mumbai is fluctuating one as it is a coastal area and the weather is highly influenced by Arabian Sea. Generally May is the hottest month of the year and the average temperature ranges between 320C- 400C. January is the coldest month in Mumbai and the average temperature remains about 180C. The average annual rainfall in this region is 2170 mm. Because of the southwest monsoon winds, more than 95% of the annual rainfall occurs during four months period of June to September. This city has a highly humid climate with an annual average relative humidity of more than 60%. Two types of soils have been observed in this area viz. medium to deep black and reddish colour soil. The soil type is predominantly sandy due to its proximity to the sea. In the suburbs, the soil cover is largely alluvial and loamy. The underlying rock of the region is composed of black Deccan basalt flows, and their acid and basic variants dating back to the late Cretaceous and early Eocene eras. [38]. The Pahoehoe flow in the area consists of highly vesicular bottom layer having closely spaced horizontal joints but the thickness is generally less. The vesicles are generally filled with secondary minerals and green earths. In such cases, they do not serve as aquifer. Such vesicular zones are weathered in most part of the area, thus, making them moderately permeable. But if, vesicles are not filled, they act as highly permeable aquifers. The simple and compound Pahoehoe flow comprises a basal vesicular zone, middle relatively massive portion followed by a vesicular top. The vesicles of Pahoehoe flows are generally not interconnected and thus there is a variation in water holding capacity from the base to the top of the flow. The ground water exists in fractures, joints, vesicles and in weathered zone of Basalt. The occurrence and

20

circulation of ground water is controlled by vesicular unit of lava flows and through secondary porosity and permeability developed due to weathering, jointing, fracturing etc., of Basalt. The ground water occurs under phreatic, semi confined and confined conditions. The leaky confined conditions are also observed in deeper aquifers. Generally, the phreatic aquifer can be found in the range down to a depth of 15 m bgl. The water bearing zone down to depth of 35 m bgl forms the semi confined aquifer and below this deeper down to depth of 60 m bgl is observed. It is expected that the potential of deeper aquifers would be much more limited as compared to the unconfined/phreatic aquifer. River alluvium patches along the course of rivers and marine alluvium in the coastal area, highly potential aquifer but with limited areal extent. The ground water occurs under water table condition in sandy gritty layers. The alluvial fill of low lying areas underlain by weathered basalt has relatively better ground water potential.

Fig. 4 Hydrogeology map of greater Mumbai

Source Doc-1618/DB/2009.CGWB

21

Fig. 4 is the hydrogeology map of greater Mumbai taken from document, groundwater information greater Mumbai district, Govt. of India Ministry of water resource Central groundwater board (CGWB) [38]. As per CGWB ground water is suitable for drinking purpose, but there occur pollution of many of the places due to dumping of sewage and industrial effluents. In addition to this various effluents from oil refineries, reactors, fertilizers have polluted the ground water. As a result the concentration of heavy metals in ground water and soil in the surrounding areas of creek has been observed beyond the prescribed limits. The entire sampling site is underlain by basaltic lava flows of upper cretaceous to lower Eocene age. The shallow alluvium formations of recent age also occur as narrow stretch along the river flowing in the area. 2.1.2 Sampling Sites and Samples Collection Since estuarine regions have their own importance due to its uniqueness in hydrogeology, as the aquifer of estuarine area is affected by both sea water and river water which leads to a very complex type of chemical evolution of ground water. Therefore, the ecology of the estuarine area is totally different from that of others. In our study, sampling sites were selected near the creek, where Ulhas River connects with an open Arabian sea of Mumbai area. This region receives the sewerage and effluents discharged from the chemical industries and factories. An extensive sampling was carried out at this area during the month of March and April, 2010. The total sampling area along the Ulhas River at the creek was covered to be about 200 km2. A grid sampling scheme was prepared with the help of topocity and a sub grid dimension of 2 km x 2 km was adequate for sampling. The sampling area was classified into 25 sub-locations. In these locations, representative samples of soil, sediment(well sediments) and ground water (well water) were collected as per standard protocols and proper care was taken to avoid the inter contamination of samples. Fig-5 represents the studied site with the sampling locations coded with L1 to L25.

22

Fig. 5 Map of the study site

23

2.2 Preliminary process of ground water, soil and sediment samples. Ground water samples were collected in duplicate from each well and filtered through 0.45 micron filter paper, stored in, acid washed, 200 ml capacity polypropylene bottles one of the sample was acidified with 0.01M of nitric acid (AR Grade, Merck, Mumbai, India) and kept for heavy metal and major cations analysis. The composite surface soil(S) samples (up to 15cm depth) from each location were collected using soil sampler and packed in WHIRL-PAK Sterile sampling bags with code from S1 to S25 at each geo referenced location. These samples were dried at 110C for 24 h, sieved through 2000 m test sieve. The sieved soil samples again subjected to sieving with the help of electromagnetic sieve shaker for textural analysis (i.e. 500, 355, 250, 188, 125, 106, 90, 75, 53, 25 and < 25 m). Sediment samples from each well were collected using Ekman Dredge sediment sampler. All the samples were packed in WHIRL-PAK Sterile sampling bags and processed as soil samples. 2.3 Sample digestion and analysis preparation Soil and sediment samples were digested in microwave digestion system (Milestone Srl, Model Ethos 1, Italy with pro-24 rotor) as per manufacturer specification. About 0.5 g of powdered and dried soil and sediment samples were placed in PTFE (Poly Tetra Fluoro ethylene) digestion vessels with 5 mL of HNO3 (MERCK, high purity), 3 mL of HF (MERCK) and 2 mL of hydrogen peroxide (H2O2). After that, samples were completely destructed in a closed microwave digestion system. The resulting solutions were then evaporated to near dryness after extracting with 0.25% HNO3. Finally, the aliquots were prepared in a 50 mL (by adding MilliQ water) standard flask for instrumental analysis. 2.4 Analysis Techniques 2.4.1 Field Measurements The measurement of the parameters like electrical conductivity (EC), pH and temperature for each water sample during sample collection using standard procedures employing field meters by Orion RDO meter. Measurements of pH were made with a glass sensor calibrated at the sample temperature and using pH 4, pH 7 and pH 9.2 buffers. The deviation of pH measurements was 0.2 pH units.

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2.4.2 Major cations and anions analysis The determination of major cations (Na+, K+, Mg++ , Ca++ ) and major anions ( F-, Cl- , SO4- -, NO3-) ground water samples and major cations in soils and sediments were estimated by conductivity suppressed Ion Chromatography System (DIONEX600) using an Ion Pac AS17 (anion-exchange column) as a stationary phase with 12 mM of NaOH as a mobile phase for anions and an Ion Pac CS17 (cation-exchange column) as a stationary phase with 6 mM of methane sulphonic acid (MSA) as a mobile phase for cations. The unknown sample was analyzed by measuring the peak area for the ions (identified by retention time), and comparing it with the standard curve, the concentration of unknown ion in the solution was calculated. The instrument was calibrated and standardized with the stock solution of ultra pure Fluka (Switzerland) standards for the above cations and anions. The eluent flow rate was confined at 0.25 ml/min under isocratic flow. HCO3- was estimated titrimetrically using autotitrator (Metrohm-798 MPT Titrino). Silica in ground water was determined by AAS (Atomic absorption spectrophotometer) and finally dissolved silica was quantified stoichiometrically. Quality assurance was made by spike recovery, replicate analysis and cross method checking. The relative standard deviation was calculated to be 812%. 2.4.3 Analysis of heavy metals 2.4.3.1 Preparation of postcolumn PAR (4-(2-pyridylazo) resorcinol) reagent and complexing agent (2, 6-Pyridyle dicarboxylic acid) for ion chromatography In a well ventilated fume hood, 0.12 g of PAR was thoroughly dissolved in 185 mL of NH4OH and 400 mL of Milli Q water. 58 ml of acetic acid was added in 600 mL of Mili Q water to prepare 1.7MCH3COOH which was added slowly to the PAR solution. For preparation of eluent, 1 gm of PDCA (2, 6-Pyridyle Dicarboxylic Acid), 3.2g of 50% NaOH and 5.4mLof glacial acetic acid were added in 1 L of Milli Q water and pH was maintained to 4.8. Fluka standards of Fe, Cu, Ni, Co and Mn were used for the calibration of the instrument. Prepared reagents were stored under an inert gas, such as nitrogen and used within two weeks of preparation. 2.4.3.2 Detection and separation of Cu, Fe, Mn, Ni and Co using ion chromatography Most hydrated and weakly complexed metals will precipitate in a suppressor and therefore, cannot be detected by conductivity. Also, with a few exceptions, transition metals cannot be detected by direct UV absorbance. Therefore, the metal complexing agent 4-(2-pyridylazo) resorcinol (PAR) is added post column to form a light-absorbing complex. Hydrated and weakly

25

complexed transition metals can be separated as cations on a cation exchange column. By adding a carboxylic acid chelating agent to the eluent, the net charge on the metal is reduced, since the carboxylic acids are anionic in solutions. The selectivity of the separation is actually due to the different degrees of association between the metals and the chelating agents producing different net charges on the metal complexes. If strong enough chelating agents are used in high enough concentration, the net charge of the metal complexes can be negative. These anionic metal complexes are separated by anion exchange. The IonPac CS5A column has, cation and anion exchange capacity, allowing metals to be separated as cations or anions on a single column. This is called a mixed mode separation. Finally, heavy metals were detected by measuring the absorbance at 530 nm of the complex formed with the post column PAR reagent. The concentration of Cu, Fe, Mn, Ni and Co in sediment and soil was analysed by Ionchromatography system (DIONEX-600) using UV-Visible detector under the following conditions: Columns: IonPac CS5A Analytical and CG5A Guard, Eluent: Met Pac PDCA eluent, Flow Rate: 0.35 mL/min, Injection Volume: 50 L, Mixing Device: 375- L knitted reaction coil, Post column Reagent: 0.5 mM PAR(0.25Mm for water analysis ),Reagent Flow Rate: 0.45 mL/min, Detector Wavelength: 530 nm. Fig.6 shows the Ion-chromatogram (mAu vs retention time) of Fe, Cu, Ni, Co and Mn.

Fig. 6 Ion-chromatogram (mAu Vs Retention Time) of Fe, Cu, Ni, Co and Mn

26

2.4.3.3 Determination of Pb and Cd and Cu using DPASV (differential pulse anodic stripping voltametry) Pb, Cd and Cu in soil, sediment and water samples were analyzed using DPASV. Sample size for soil, sediment analysis has been fixed at 0.5 mL and for water 5mL. Sodium acetate buffer (pH4.75) was used as supporting electrolyte. Fig.7 shows the voltammogram of Cd, Pb and Cu in soil. DPASV measurements were made under following conditions a) Potential ranges of 0.8 to 0.2 V b) Mode-Differential c) Electrode-HMDE(Hanging mercury drop electrode) d) Calibration Standard addition method to remove matrix interference

Fig.7 Differential Pulse Voltammograms of Cd, Pb and Cu

27

CHAPTER-3
RESULTS AND DISCUSSIONS

3.1 Basic Statistical Analyses

ig. 8, 10 and 11 represents box and whiskers plots with different percentile (1%-99%) of ionic concentration in groundwater, major elements in soil and sediment. Fig-9 and 12

shows whiskers plots of concentration of heavy metals in soil and sediment. A Box plot consists of a box, whiskers and outliers. Box covers middle half (50%) of the data, the bottom of the box is at 1st quartile (Q1) at the 25th percentile and the top is at the 3rd quartile (Q3) value at 75th percentile. The median, the midpoint of the data set is shown as a solid point in the box. The outer parts of the data set or tails are the Whiskers, which show the range of the data. The whiskers are plotted by lines that extend from the top and bottom of the box to extreme data values (maximum and minimum) that are not under taken to be outliers. An outlier is any values that lay more than one and a half times the length of the box from either end of the box. That is, if a data point is below Q1 1.5IQR or above Q3 + 1.5IQR, it is viewed as being too far from the central values to be reasonable. Outliers are points outside the lower and upper limits and are plotted with open dots whereas the extremes are the values that lies more than three times the length of box from either end of the box, i.e., data point is below Q1 3IQR or above Q3 + 3IQR. The box, whiskers and location of the mean indicates the symmetry. Closer the mean is to median, the more symmetrical the distribution. In case of skewed data, the box plot is not symmetric. It is obvious from Table 3 and 5 that the mean and median of all the measured concentration of elements in ground water and soil are significantly different indicating that their values were highly positively skewed about mean.

28

BOX Plot Median; Box: 25%-75%; Whisker: 1%-99% 70

60

Ionic concetration (meq/L)

50

40

30

20

10

0 Cl NO3 SO4 Na K Mg Ca HCO3

Median 25%-75% 1%-99% Outliers Extremes

Fig. 8 Box and Whiskers plot for major ionic concentration in ground water
Median; Whisker: Min-Max 400

350

concentration of heay metals (mg/kg)

300

250

200

150

100

50

0 Pb Cu Cd Ni Co Mn

Median Min-Max Outliers Extremes

Fig. 9 Whiskers plot of distribution of heavy metals in soil

Box Plot Median; Box: 25%-75%; Whisker: Min-Max 1E5

concentration of elements in soil (mg/kg)

80000

60000

40000

20000 Median 25%-75% Min-Max Outliers Extremes

0 Na K Mg Ca Fe

Fig. 10 Box and Whiskers plot of major elemental concentration in soil

29

Median; Box: 25%-75%; Whisker: Min-Max 60000

Concentration of elements in sediment (mg/kg)

50000

40000

30000

20000

10000 Median 25%-75% Min-Max Outliers Extremes Na K Mg Ca Fe

-10000

Fig. 11 Box and Whiskers plot of major elemental concentration in sediment

Median; Whisker: Min-Max 200 180 160 140 120 100 80 60 40 20 0 -20 Pb Cd Cu Ni Co Mn Median Min-Max Outliers Extremes

Fig. 12 Whiskers plot of distribution of heavy metals in sediment

Inter quartile range (Q3-Q1) of all the measured elements in soil and groundwater were also evaluated and found to be very high indicating that, the data of all elements in both matrices was highly dispersed. Because, it is well understood that larger the Inter quartile range (IQR), bigger the length of the box and higher the dispersion of the data. Box and whisker plot (Fig.8) shows that very large range of Na+ and Cl- in ground water. In soil among heavy metals (Fig.9) Cu and Mn have large ranges and among major elements (Fig.10) Ca and Fe have very wide ranges of variation. Similarly for sediments almost all the major

Concentration of Heavy metals in sediment (mg/kg)

30

elements exhibits wide range except K (Fig.11) and among heavy metals Cu and Pb shows very wide range of variation (Fig.12). 3.2 Hydro-geochemical evaluation of groundwater The statistical parameters (minimum, maximum, mean, median, 1st quartile, 3rd quartile) for different geochemical parameters distribution in groundwater samples are presented in Table 2. The pH of all groundwater samples ranged from 6.25 to 8.1 with an average of 7.37 (alkaline). The measured pH was found to be within the permissible range (6.5 to 8.5) recommended by Bureau of Indian standard guidelines [39] for drinking water. Some well water having higher value of pH may be due to weathering of plagioclase feldspar by dissolved atmospheric carbon dioxide that will release sodium and calcium which progressively increase the pH and alkalinity kind of result observed. Electrical conductivity and total dissolved solid are closely related to each other. Higher values of electrical conductivities recorded in groundwater at few locations is likely due to seawater influence. Although the studied site is nearby Arabian Sea the impact of saline water intrusion may be ruled out due to following reasons, a) Low Mg/Ca ratio (Table-6) at all locations, if it is due to saline incursion, Mg to Ca ratio in ground water should be high i.e. about five. b) Low Cl-/ HCO3 ratio (Table-6) at all locations of studied site except location 3, 7 and 24 which are at far distance from waterline. The mean of EC (Electrical Conductivity) and TDS (Total Dissolved Solids) of groundwater samples were in the range of 1174.9 S/cm and 745.3 mg/L respectively. The calculated ionic strength ranged from 0.004 to 0.105 with mean of 0.043. The possible reason behind high EC value at some locations might be impact of dissolution of salt of marine origin or formation of local saline pockets due to Base Exchange processes in weathered zone. The groundwater were dominated by the major ions like Na+, K+, Ca2+, Mg2+, Cl, NO3-, HCO3, CO32- and SO42. These ionic species may be attributed to the leaching of salts from the soil, chemical weathering process and also to anthropogenic activities. The excess content of ions in ground water may be due to the presence of variety of lithological components of natural origin in the sampling region. Cl- concentration is the most suitable parameter as a reference for the water because it is conservative (i.e. not lost from solution by sorption or precipitation) and shows the largest concentration range among other ions. Ions like K+ and NO3- in water samples have shown high enrichment, which might have originated from multi sources like leaching from soil, decay of organic matter, sewerages etc.

31

High content of K may be due to silicate minerals, orthoclase, microcline, hornblende, muscovite and biotite in igneous and metamorphic rocks and evaporate deposits gypsum and sulphate which releases considerable amount of potassium in to groundwater. Main reason for increasing potassium content in groundwater is due to agricultural activities. The other source of K+ may also be predicted from decomposition of primary minerals like K-feldspar and hydroxylapatite respectively by the chemical weathering process. A high mean ratio (> 2) of Ca/Mg was observed in groundwater indicating that there could be either high decomposition of calcium bearing minerals like calcite, dolomite etc. or calcium containing silicate and carbonate minerals might have dissolved congruently in the study area. Generally Ca and Mg do not behave equally in ground water system because Mg deteriorates the mineral structure particularly when waters are sodium dominated and highly saline due to high exchange with Na bearing minerals. Intrusion of saline water through the soil and chemical weathering of halite minerals is one of the important processes responsible for the higher concentration of Na+ and Cl- ions in groundwater. Some ground water showed the observed mean ratio (>1) of Na/Cl in ground water indicating that not only the congruent dissolution of halite by water is responsible for sodium but also incongruent dissolution of Na bearing silicate minerals like feldspar by acids. If halite dissolution is responsible for sodium, the Na/Cl ratio should be approximately equal to one whereas the ratio greater than one is typically interpreted as Na released from a silicate weathering reaction. Abnormal concentrations of Cl may result from saline residues in the soil or contamination by sewage. In this study, as the studied site is an estuarine area the ground water recharge also took place from river water which contaminated by discharge from various sources. The ratio of HCO3 to dissolved SiO2 in ground water was found to be greater than 10 indicates that carbonate weathering due to major waterrock interaction was the dominant process. To study the variability and homogeneity of ions in ground water of study area, coefficient of variation (%CV) was calculated. The calculated %CV for all ions showed very wide variation (42.5 to 230.26%) indicates that there is non-homogeneity of the distribution of ions contents throughout the studied area. A wide dispersion along the investigated area may be due to the consequences of weathering processes, mineralogical composition, anthropic input etc. 3.3 Pipers groundwaters classification Fig.13 shows a trilinear Pipers plot for ground water classification of studied site. In this diagram, cations and anions were normalized to 100% and plotted in their appropriate triangle.

32

The data plotted on each triangle are then projected in a central diamond-shaped field. In the cations triangular diagram of Pipers plot of groundwater, about 25% of the groundwater were strongly alkaline (Na++ K+ >50 mg/L %), 50% were Ca2+ type (Ca2+>50 mgL-1%) and remaining was without dominant cation type (Na+, K+, Mg2+ and Ca2+, < 50 mg/L %). Similarly for anions, 36% groundwater were bicarbonate type (HCO3-> 50 mg/L %), 36% were chloride type and remaining were without dominant anion type (Cl-, HCO3- and SO42 < 50 mg/L %). In addition to this, groundwater were also classified into three dominant chemical facies of (Na+K) (SO4+Cl) type (32%), (Ca + Mg) (SO4+Cl) type (40%), (Ca+Mg)HCO3 type (28%). Hence, for Ca2+ Mg2+ type water there are 18 locations (1, 4, 5, 8, 9, 10, 12, 13, 14, 15, 16, 17, 19, 20, 21, 22, 23 and 24) which can be divided as follows: 18= 10 (With anions SO42- and Cl- ) + 8 ( With anion type C032- and HCO3 -) And rest seven locations (2, 3, 6, 7, 11, 18, and 25) belongs to Na+ -K+ water type with anions as follows: 7= 6 (With anions SO42- and Cl- ) +1 ( With anion type CO32- and HCO3 -)

Fig. 13 Trilinear Pipers plot for ground waters classification of study site.

33

This wide variation of water types reflects the local variation of geology and geochemistry significantly which affects the groundwater compositions. Calcium-bicarbonate facies suggest that rock weathering is the major factor for controlling the water chemistry. NaHCO3 type water can be formed by the dissolution of plagioclase minerals, increasing the Na-concentrations in groundwater. Piper diagram revealed that, Ca and Mg are predominating cations in the ground water of study area with SO4+Cl as predominating anions. From the classification of hydrogeochemical facies in groundwater as shown in Fig.14 (Piper, Lawarence and Balsubramanian diagram), it was observed that 32% of ground water was predominated with gypsum, 32% were high content of Ca +Mg with SO4 and Cl and remaining were the combination of these cations with bicarbonate and carbonate. This diagram is well supported by simulated data (saturation index) generated using PHREQC hydrochemical code presented in Table.7.

Fig. 14 Hydrogeochemical facies in ground water

34

Table 2. Ground Water Data Sheet

Cl(mg/L) NO-3 (mg/L) SO42-(mg/L) Na+(mg/L) K+(mg/L) Mg2+(mg/L) Ca2+(mg/L) pH HCO-3(mg/L) Si(mg/L) Cu (g/L) Fe (g/L) Mn (g/L) Pb (g/L) TDS (mg/L) Ec (S/cm)

Location

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25
%CV

207.39 182.78 1960.88 18.64 88.27 387.86 1669.45 192.06 17.37 80.7 180.94 30.25 49.71 38.96 12.36 20.49 137.1 22.46 183.98 57.76 62.53 84.36 23.72 550.59 260.55
182.85

165.8 190.84 208.3 76.97 81.33 51.75 80.54 10.7 1 0.53 9.2 5.35 5.16 1.6 5.44 1.09 22.21 0.335 0.1 36.96 23.46 2.87 0.35 95.3 58.24
134.01

33.36 34.48 35.84 2.52 40.47 543.59 76.41 67.13 40.14 31.62 63.31 9.8 27.3 41.87 11.87 9.8 30.97 8.95 35.82 8.09 35.7 14.2 14.57 320.06 76.64
177.54

176.53 273.66 238.22 32.6 121.87 412.72 1493.84 15.06 25.08 21.93 86.32 14.7 15.87 30.41 9.07 18.49 41.28 31.65 74.21 25.76 32.55 28.325 25.55 29.34 132.46
215.48

12.78 21.27 20.87 10.23 6.085 19.92 11.88 0.64 3.54 1.94 6.43 1.62 1.93 1.85 0.59 1.51 6.12 1.59 9.11 2.86 3.16 2.17 1.27 1.963 9.59
98.69

66.88 18.71 15.28 7.64 18.95 32.56 76.01 4.49 7.24 10.31 15.85 3.99 5.68 10.58 5.4 4.41 9.48 3.98 15.66 6.4 14.85 16.82 5.4 9.92 19.97
108.389

66.95 111.65 105.62 85.25 89.99 71.31 138.47 21.5 62.75 49.01 41.09 18.99 22.86 50.18 18.137 24.47 69.14 13.78 87.35 26.9 71.38 64.91 45.68 64.77 65.57
53.38

7.25 7.6 7.51 7.71 7.6 8.1 6.87 7.26 7.92 7.11 7.84 7.92 6.95 7.12 7.19 7.23 7.29 6.26 7.53 6.25 7.39 7.85 7.73 7.17 7.48
6.17

127.14 130.27 166.58 207.98 200.84 323.4 217 120.9 131.45 66.66 72.2 133.66 76.78 104.1 145.43 78.13 206.04 40.23 194.56 177.33 128.25 139.89 72.3 160.41 150.8
42.5

2.46 1.74 3.39 1.17 1.64 1.44 4.25 5.73 3.73 3.85 8.67 3.41 3.86 3.51 6.43 4.85 3.59 3.16 3.52 2.59 6.28 10.17 3.92 5.54 3.96
50.65

18.66 1 4.5 2.05 3.5 16.53 2 24 4.75 2 1.55 1 5.55 1 2 7 2 2.5 2 1 2.42 1.4 2 1 5.65
125.68

5.04 34.6 14 29.5 60 1.36 116 57 61.25 61 56.1 14.2 60.8 60 13.2 1.2 17.7 46.5 23 34 53.2 46.5 47 42 61.5
63.09

557.1 11 3.5 16.5 14.5 14.33 2 467 7.2 15.2 22 42 18.2 17 31 16.8 26.25 29.05 17.3 17.2 26.24 18.8 17.1 17.71 37
230.26

13.66 BDL 1 BDL 1.1 0.46 1 1 0.6 BDL 0.85 BDL 0.7 BDL BDL 1 1.2 0.7 BDL 1 1.33 1.85 BDL 1.2 1.35
216.65

863.08 985.47 2776.52 600.91 677.79 1394 3767.9 484.07 279.14 451.32 234.34 204.06 283.3 213.46 116.12 534.18 148.78 602.2 362.13 362.26 357.08 210.13 1241.9 737.04 745.33
110.63

1530 810 4200 974 1450 2370 5890 756 488 446 769.5 361 1099 442 333 181 815 2401.5 940 566 577.86 557 327 2011 1140
111.5

35

35

Table 3. Descriptive statistics of ground water samples

Geochemical parameters Mean Median Minimum Maximum Lower Upper Percentile Percentile Range Quartile Std.Dev. Skewness Kurtosis

Cl (mg/L) NO3
-

260.85 45.417 64.580 136.29 6.436 16.258 59.508 7.36 142.89 4.115 4.682 40.66 58.48 33.520 745.30 1257.39

84.36 10.70 34.48 31.64 3.16 10.31 64.77 7.39 133.66 3.73 2.0 46.5 17.3 1.2 484.07 810.0

12.36 0.10 2.52 9.07 0.59 3.98 13.785 6.25 40.23 1.169 1.0 1.2 2.0 0.46 116.12 181

1960.88 208.3 543.59 1493.84 21.27 76.01 138.47 8.10 323.4 10.17 24 116 557.1 101.0 3767.9 5890

30.25 1.6 14.20 25.07 1.85 5.68 26.9 7.175 104.1 3.16 1.55 17.7 15.20 1.0 279.14 488.0

192.06 76.97 41.87 121.86 9.59 16.82 71.38 7.71 177.33 4.85 4.75 60.0 26.25 101.0 745.33 1450.

17.36 0.33 8.09 14.70 0.64 3.99 18.14 6.26 66.66 1.44 1.0 1.36 3.5 0.6 148.78 327

1669.45 190.84 320.06 412.72 20.87 66.88 111.65 7.92 217.00 8.67 18.66 61.50 467.00 101.00 2776.52 4200.00

1948.52 208.20 541.07 1484.77 20.68 72.03 124.68 1.85 283.17 9.0 23.00 114.80 555.10 100.54 3651.78 5709.00

161.81 75.37 27.67 96.79 7.74 11.14 44.48 0.535 73.23 1.69 3.20 42.30 11.05 100.00 466.19 962.00

486.78 62.12 117.01 299.76 6.48 17.98 32.42 0.464 61.97 2.13 6.00 26.18 137.44 47.31 841.53 1314.65

2.97 1.58 3.53 4.21 1.29 2.59 0.50 0.86 0.82 1.24 2.33 0.61 3.32 0.81 2.65 2.42

8.34 1.67 12.85 19.16 0.66 6.57 -0.051 0.94 1.59 1.94 4.75 1.34 10.04 -1.45 7.42 6.35

SO42Na K Mg Ca pH

36

HCO3 Si Cu(g/L) Fe Mn Pb TDS EC

36

Table 4. Soil data Sheet

Location 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 %CV
Pb

(g/g) 57.27 58.54 24.29 23.63 49.37 57.38 23.65 16.66 14.74 16.99 14.54 15.26 22.85 31.87 42.84 37.72 18.77 15.84 16.62 14.3 44 44.13 15.7 15.72 11.95 55.68

Cu (g/g) 99.32 106.92 167.7 167.04 103.75 345.47 110.79 106.43 101.14 107.16 102.04 103.33 110 68.33 159.53 151.91 111.54 99.42 103.57 96.25 81.76 171.95 144.05 94.87 89.61 43.54

Cd (g/g) 0.45 0.49 1.35 2.27 0.21 2.86 0.66 0.24 0.19 0.25 0.22 0.398 0.238 0.208 0.482 0.419 0.285 0.245 0.26 0.24 0.429 BDL 2.26 0.21 0.18 124.79

Fe (g/g) 61968 62073 33677.21 33675.9 34060.9 61893.6 33742.64 33541.7 33152.28 32912.28 32654.94 32760.74 33741.06 33875.26 61967.2 61841.53 61985 61771.55 61876.1 61736.9 61722.65 34265.36 33511.32 32702.23 32270.02 31.86

Ni (g/g) 32.12 40.65 37.85 39.07 41.87 28.6 40.12 37.53 34.08 31.54 30.3 31.19 38.54 40.08 39.4 37.25 39.75 38.24 37.21 36.77 18.85 40.95 37.72 30.57 27.72 15.29

Co (g/g) 2.85 1.24 62.68 61.37 63.41 7.6 66.94 61.49 59.14 61.03 60.94 61.04 65.36 65.24 0.19 0.11 0.56 0.5 0.466 0.402 0.24 68.59 61.29 60.08 57.63 80.54 37

Mn (g/g) 270.47 281.02 117.22 115.91 116.06 203 117.89 115.34 115.26 117.11 115.87 116.31 116.32 116.89 280.46 277.92 283.59 279.72 281.05 280.9 266.97 118.24 113.11 116.14 115.56 44.16

Na (g/g) 23919.2 24025 20096.31 20095 20099.5 30568 11533.26 2002.04 1705.04 1920.04 1865.69 2286.95 11531.68 20109.43 23919.34 23780.7 23781.78 23723.24 23239.78 23283.68 23678.98 26441.5 19940 1644.24 1430.24 61.25

K (g/g) 33019.8 33261.1 5781.31 5780 5782 15626 5470.58 1176.9 336.9 5743 5598.6 5741.1 5469 15557 33135.56 33010.36 33118.96 33020.42 32877.46 32023.96 32732.59 8130 5348.8 5848.76 5706.76 83.59

Mg (g/g) 3409.8 3465.28 3423.31 3422 3424 4834 30475.73 4986.17 4420.17 3747.25 3725.67 3835.87 30474.15 11191.4 3330.33 3203.59 3218.79 3193.201 3133.42 2640.59 3164.6 29410.4 3318 3850.33 3692.8 124.75

Ca (g/g) 14749.67 14960.67 5804 5802 5803.84 12015 68061.35 8339.24 7584.24 5869.87 5842.72 6077.22 68059.77 27717.75 14808.17 14594.22 14651.42 14626.01 14601.07 13963.48 14380.97 89994.27 7801.09 5895.32 5770.12 119.02

37

Table 5. Descriptive statistic of soil samples

Valid N Mean Median Minimum Maximum Lower Upper Percentile 5th Percentile 95th Range Inter Quartile Std. Dev. Skewness Kurtosis

Pb Cu Cd Fe Ni Co Mn Na K Mg Ca

25 25 25 25 25 25 25 25 25 25 25

28.19 124.16 0.601 44775.1 35.52 38.02 177.93 16264.82 15971.88 7079.63 18710.94

22.85 106.43 0.26 33875.26 37.53 60.08 117.22 20099.50 5848.76 3465.28 13963.48

11.95 68.33 0.18 32270.02 18.85 0.11 113.11 1430.24 336.90 2640.59 5770.12

58.54 345.47 2.86 62073.00 41.87 68.59 283.59 30568.00 33261.10 30475.73 89994.27

15.72 99.42 0.22 33511.32 31.54 0.56 116.06 2286.95 5706.76 3318.00 5895.32

42.84 144.05 0.482 61841.53 39.40 61.49 277.92 23780.70 32877.46 4420.17 14749.67

14.30 81.76 0.19 32654.94 27.72 0.19 115.26 1644.24 1176.90 3133.42 5802.00

57.38 171.95 2.86 61985.00 40.95 66.94 281.05 26441.50 33135.56 30474.15 68061.35

46.59 277.14 100.82 29802.98 23.02 68.48 170.48 29137.76 32924.20 27835.14 84224.15

27.12 44.63 0.262 28330.21 7.86 60.93 161.86 21493.75 27170.70 1102.17 8854.35

15.69 54.05 0.75 14264.24 5.43 30.62 78.57 9962.25 13351.64 8831.79 22270.44

0.86 3.08 2.16 0.43 -1.37 -0.42 0.52 -0.61 0.46 2.36 2.38

-0.76 11.83 3.66 -1.97 2.13 -1.95 -1.825 -1.32 -1.76 4.07 4.84

38

38

Table 6. Chemical characteristic data sheet of ground water (in meq/L)

LOCATIONS 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 Mg2+/ Ca2+ 1.66 0.28 0.24 0.15 0.35 0.76 0.91 0.35 0.19 0.35 0.64 0.35 0.41 0.35 0.49 0.30 0.22 0.48 0.29 0.39 0.34 0.43 0.19 0.25 0.51 SAR 3.65 6.31 5.74 0.91 3.05 10.16 25.33 0.77 0.79 0.74 2.9 0.80 0.77 1.02 0.48 0.9 1.24 1.94 1.92 1.16 0.92 0.81 0.95 0.89 3.67 Cl-/HCO32.84 2.45 20.52 0.15 0.76 2.09 13.40 2.76 0.23 2.10 4.36 0.39 1.13 0.65 0.15 0.46 1.16 0.97 1.65 0.57 0.85 1.05 0.57 5.98 3.01 Cl-/SO428.53 7.27 75.03 10.14 2.99 0.98 29.96 3.92 0.59 3.50 3.92 4.23 2.49 1.27 1.43 2.87 6.07 3.44 7.04 9.79 2.40 8.15 2.23 2.35 4.66

39

3.4 Saturation Indices (SI) of minerals in ground water The level of saturation of different minerals in groundwater of all locations as tabulated in Table. 7, were calculated using PRHEEQC version 2 geochemical model The saturation indices (S.I =log (IAP/KT).) of predominant minerals like chrysotile, chalcedony, sepiolite, gypsum and halite in all locations showed negative values indicating that the groundwater were significantly under saturated with respect to respective minerals. Groundwater of some locations were oversaturated with respect to minerals like aragonite, anhydrite, calcite, dolomite, talc and silica bearing minerals like quartz etc. because these minerals are dominated by soil and decomposed quickly by silicate weathering processes except quartz, which decomposed slowly due to limited buffering capacity of soil. The high SI of Ca and Mg bearing minerals indicates that there is depletion of Ca2+ and Mg2+ content due to their precipitation in the ground water system. However, the under saturation concluded that the elements were being removed from the mineral surfaces in presence of other dominant species and consequently increase their concentration. The dissolution of gypsum releases Ca2+ and increase in Ca2+ concentration leads to oversaturation of the water in calcite due to common ion effect. The other ion SO42- released during gypsum dissolution does not participate in the calcite equilibrium reaction. Dolomite is also present in the carbonate rocks and as calcite precipitates, dolomite dissolves. The combination of three reactions-gypsum dissolution, calcite precipitation and dolomite dissolution leads the observed increases in Mg2+ and SO42- concentration. This model underestimated the concentration of some ions like NO3- and K+ indicating that these ions were being added to the system and overestimated the concentration of other species.

Table 7. Saturation level of different minerals in groundwater of all locations Locations Under saturation 1,2,3,5,6,7,8,9,13,16,17,18, 20,21,22 and 25 Locations oversaturation

Mineral Anglesite Anhydrite Aragonite Calcite Cerrusite

Chemical Formula PbSO4 CaSO4 CaCO3 CaCO3 PbCO3

2 2,3,4,5,6,9,12,19,22 2,3,4,5,6,9,12,17,19,22 and 25 All

40

Mineral Chalcedony Chrysotile Dolomite Fe(OH)3(a) Goethite Gypsum Halite Hausmannite Hematite Jarosite-K Manganite Melanterite Pb(OH)2 Pyrochroite Pyrolusite Quartz Rhodochrosite Sepiolite Sepiolite-d Siderite SiO2 Talc

Chemical Formula SiO2 Mg3Si2O5(OH)4 CaMg(CO3)2 Fe(OH)3 FeOOH CaSO4:2H2O NaCl Mn3O4 Fe2O3 KFe3(SO4)2(OH)6 MnOOH FeSO4:7H2O Pb(OH)2 Mn(OH)2 MnO2 SiO2 MnCO3 Mg2Si3O7.5OH:3H2O Mg2Si3O7.5OH:3H2O FeCO3 SiO2 Mg3Si4O10(OH)2

Locations Under saturation All All

Locations oversaturation

2,4,5,9,19 and 22 16,18,20,23,24 All All All All All All All All All All All 11,15,16,22 1 and 8 All All All All 11 and 22

3.5 Speciation study of major chemical species in ground water of studied area The speciation study of major chemical constituents of ground water of study site was done using the thermodynamic data base and calculations with HYDRA (Hydrochemical Equilibrium Constant Database) speciation program. Fig. 15 -18 depicts the pH dependent calculated species distribution of metals in ground water under the varying amount of complexing ions. Speciation study revealed that most of the groundwater belonged to the predominant species like, Na(SO4+Cl), (MgCa)SO4, MgCa(OH), CaCO3 and CaMg(CO3)2. However, among heavy metals, Fe and Mn bearing minerals were dominating. Fe(OH)3, goethite [FeO(OH)], hematite (Fe2O3) also indicates oversaturation, this is supported by the fact that Basalt (Deccan trap) contains

41

ferromagnesian elements i.e., rich in Fe and Mg minerals. In this case rhodochrosite (MnCO3). and mangnite [MnO(OH)] seems to be contributing to Mn.

Fig. 15 pH- dependent calculated species distribution of Na in the groundwater at the various range of [SO4] = 2.610 -5M- 5.6710-3M, [Cl] = 3.510 -4M- 5.5210-2M and [Na] =4 10-4 6.5 10 -2M

Fig. 16 pH- dependent calculated species distribution of Mg and Ca in the groundwater at the various range of [SO4] = 2.610 -5M- 5.6710-3M, [Cl] = 3.510 -4M- 5.5210-2M and [Mg] =1.6 10-4 3.16 10 -3M and [Ca] =3.45 10-4 3.46 10 -3M

42

Fig. 17 pH- dependent calculated species distribution of Mg and Ca in the groundwater at the various range of [CO3] = 6.610 -8M- 5.310-3M, [Mg] =1.6 10-4 3.16 10 -3M and [Ca] =3.45 10-4 3.46 10 -3M

Fig. 18 pH- dependent calculated species distribution of Fe and Mn in the groundwater at the various range of [CO3] = 6.610 -8M- 5.310-3M, [Fe] =2.16 10-8 2.1 10 -6M and [Mn] =3.6 10-8 1 10 -5M

43

3.6 Gibbs-Boomerang diagram for ground water of samples of study site. Gibbs-Boomerang diagram ( Fig.19.a & 19.b) of ground water of study site shows majority of the water samples of study sites were fall in region-2 [e.g., Weathering] and water samples of few locations falls outside the boomerang ( i.e., water samples having weight ratio of Na+/(Na++ Ca2+) >0.6, and TDS values > 800 mg/L ). From this result it can be concluded that, the chemical composition in most of the ground water is largely controlled by rock weathering. However the water samples which are out of the curve area, rock weathering and evaporation-crystallization processes alone cannot explain the chemical characteristics of ground water of that locations. Moreover, no data plot in the lower right side of the boomerang shows that atmospheric precipitation is not an important process in determining the chemical composition of these water samples. Since the average amount of Na+ (meq/L) in ground water is lower than that of Cl(meq/L) and absence of Na-HCO3- hydrochemical facies, it may be predicted that dissolution of ancient salts of marine origin is the predominate process, cause for deviation rather than cation exchange process. However few locations also show cation exchange causing the deviation, as when a sodium bearing clay minerals [e.g., Na-Montmorillonite and albite (NaAlSi3O8), in basalt albite is less than Ca-plagioclase] interacts with calcium dominant ground water, each couple of absorbed sodium ions is replaced by solubilised calcium, which enriches groundwater into sodium, thus changing it from a calcium bicarbonate type, into a sodium bicarbonate type. Therefore, the groundwater become enriched in sodium leading to increase the weight relation Na+/ (Na++Ca2+) values and data plot outside the Gibbs boomerang. Study of Boomerang suggest that location 6, 7 and 18 exhibits cation exchange as controlling process causing deviation from general pattern. On the other hand, the weight relation Cl- /(Cl- +HCO3-) (x axis) was plotted against TDS values represented in Fig.19.b called as Gibbs anionic diagram shows that data plot inside the boomerang shape envelope in the upper side, being rock weathering and evaporation crystallization processes controlling the hydrochemistry. No data plot in the lower-right side of the boomerang, where chemical composition is determined by atmospheric precipitation process. The evaporationcrystallization process increases TDS and promotes calcite precipitation which is supported by oversaturation of ground water of study site w.r.t calcite (Table.7). Locations affected by dissolution of ancient salt of marine origin are 1, 3, 8, 10, 13, 15, 11, 21, 22, 23 and 25.

44

(a)

(b)

Fig. 19 Gibbs-Boomerang diagram for cations and anions in ground water of all sampling locations 3.7 Stability diagrams of clay minerals in groundwater system Stability diagrams are graphical representations of equilibria between minerals and aqueous solution. Such diagrams are very useful in inferring what will happen when waters of various compositions interact with solid phases. Fig.20 (a, b, c and d) show the stability diagram of K, Na, Ca, Mg-systems respectively. The process of constructing the diagrams from thermodynamic data and then use the diagram to make interferences during silicate minerals weathering have been carried out. Plagioclase and K-feldspar along with quartz are among the most abundant minerals in the earths crust. The stability diagrams can be used to understand the chemical breakdown of Na-plagioclase to a variety of weathering products. The other stability diagrams of interest involve weathering of Ca-plagioclase and K- feldspar. The phases of interest in aqueous system are gibbsite, kaolinite, Na-montmorillonite and albite. In this study stability diagram was plotted for all the four systems i.e., Na, K, Ca and Mg The stability diagram also helps to

45

understand the chemical changes that occur during water-rock interactions. The conversion of albite to gibbsite involves the consumption of hydrogen ions and release of silicic acid and sodium ions. Thus both silicic acid activity and ratio of sodium/hydrogen ions increases. When the gibbsite to kaolinite boundary is encountered, gibbsite is converted to kaolinite. 2Na Al Si3O8 ( albite) + 2H+ + 4 Al (OH)3(gibbsite) Al2Si2O5(OH)4 (kaolinite) + H2O + 2Na+ As long as gibbsite and kaolinite are present, the reaction will occur at constant silicic acid activity. After all the gibbsite is converted into kaolinite, the following reaction takes place: 2Na Al Si3O8 (albite) + 2H+ + 9H2O Al2Si2O5 (OH)4 (kaolinite) + 4 H4SiO4 (aq) + 2Na+ During the reaction, hydrogen ions are consumed and silisic and sodium ions are released to solution. The result is an increase in the Na+/H+ ratio and increase in the activity of silicic acid. For the open system, the important variable is the rate at which water moves through the weathering environment. This is sometimes referred to as the flushing rate. In case of high rainfall and good infiltration, the concentration of silicic acid and various ions in solution will be low. Under this condition, albite will weather to gibbsite. This is the situation observed in tropical settings where there is deep weathering and weathered materials largely consist of Al (gibbsite) and iron hydroxides. In regions of lower rainfall and less rapid infiltration, the concentration of ions in solution is greater and albite will weather to kaolinite or Montmorillonite clays. This is the situation usually in temperature setting. The variation in clay minerals content is related to climatic conditions in the continental source region and high kaolinite content representing humid conditions. This inference is related to the flushing rates. In our study, most of the groundwater were dominated by kaolinite mineral suggesting that the chemical weathering is the predominate process controlling the chemistry of ground water. The possible reaction controlling the mineral stability is as follows. a) K-feldspar Kaolinite- Gibbsite formation 2KAISi3O8 + H+ + 9H20 A12Si205(OH)4 + 2H4Si04 + 2K+ (k-feldspar/microcline) (Kaolinite) The potassium can also be incorporated into the formation of more potassium feldspar, illitic mica, or the mixed-layer clay illite/smectite [40] A12Si205 (OH)4 +5H20 A12 (OH)6 + 2H4Si04 (Kaolinite) (Gibbsite)

46

b) CaAl14Si22060 (OH) 12 + 2H+ + 23H20 = 7Al2Si2O5(OH)4, + 8H4SiO4 + Ca2+ .(5) [41] (Ca-Montemorilonite) (Kaolinite) The climatic condition of Mumbai (tropical wet climate-humid) supports the dominance of kaolinite at sampling site. Absence of muscovite at sampling site revealed that there may not be any interaction between ground water of studied aquifer system and sea water. As Clay minerals (e.g., kaolinite) in contact to sea water tend to take up K+ and are converted to illite (muscovite.), presented in fig.21. (Taken from Faure ch. 12, fig. 12.1, p. 174)

Fig. 20 a. Stability diagram for K-system

Fig. 20 b. Stability diagram for Na-system

47

Fig. 20 c. Stability diagram for Ca-system

Fig.20 d. Stability diagram for Mg-system

Fig. 21 Stability diagram in presence of sea water impact (source-Faure ch. 12, fig. 12.1, p. 174)

48

3.8 United State Salinity Laboratory (USSL) classification diagram of groundwater. For the purpose of diagnosis and classification, the total concentration of soluble salts (salinity hazard) in ground water can be expressed in terms of specific conductance. Based on salinity hazard, as presented in Fig.22, the USSL classification revealed that, about 50% water samples (dotted symbol in diagram) were found to be under high salinity with low sodium hazard and 45% were under moderate with low sodium hazard and 5% were under very high salinity with high sodium hazard. High salinity of ground water may be due to sea water incursion, evaporation process and uptake of water by hydration reaction. But in this study, chemical weathering is the predominating process in the most of the ground water as explained earlier.

Fig. 22 USSL classification of ground water 3.9 Multivariate Statistical Analysis of water. 3.9.1 Factor analysis: In order to find most significant processes controlling chemistry of the groundwater of study area, factor analysis was applied to standardized/transformed (e.g., mean=0 and standard deviation=1, shown in Table-8) values of thirteen chemical parameters of water. Factors were extracted using principal components extraction method and subjected to varimax normalization rotation. Factor analysis extract four factors (factors having Eigen value>1; Kaiser criterion and loading >0.55) which accounts for 80% variance of total variance. The correlation matrix chart which gives idea about the nature of association of different species and eigen value of four factors are presented in Table -9 and 10 respectively.

49

Table 8. Standardized data set of water parameters Cl1 2 3 4 5 6 7 8 9 -0.10981 -0.16037 3.492345 -0.49756 -0.35451 0.260921 2.893666 -0.14131 -0.50018 -0.37007 -0.16415 -0.47371 -0.43373 -0.45582 -0.51046 -0.49376 -0.25421 -0.48971 -0.15791

NO-3
1.937888 2.340974 2.62204 0.507929 0.578115 0.101945 0.565398 -0.55887 -0.71501 -0.72258 -0.58301 -0.64499 -0.64805 -0.70535 -0.64354 -0.71356 -0.37358 -0.72572 -0.7295

SO42-0.26683 -0.25722 -0.2456 -0.53034 -0.20608 4.093461 0.101096 0.021792 -0.2089 -0.28166 -0.01085 -0.46813 -0.31858 -0.19407 -0.45044 -0.46813 -0.28722 -0.47539 -0.24577

Na+
0.13421 0.458233 0.340006 -0.34594 -0.04815 0.922134 4.528727 -0.40445 -0.37104 -0.38153 -0.16675 -0.40565 -0.40175 -0.35324 -0.42443 -0.39301 -0.31698 -0.34912 -0.20713

K+
0.978379 2.287807 2.226115 0.585088 -0.0542 2.079594 0.83957 -0.894 -0.44672 -0.69349 -0.00099 -0.74285 -0.69504 -0.70738 -0.90171 -0.75981 -0.04881 -0.74748 0.412348

Mg2+
2.814526 0.136307 -0.0544 -0.47918 0.149651 0.906358 3.322148 -0.65431 -0.50142 -0.33073 -0.02271 -0.68211 -0.58815 -0.31572 -0.60372 -0.65876 -0.37687 -0.68267 -0.03327

Ca2+
0.229515 1.608173 1.422193 0.793932 0.940125 0.363988 2.435369 -1.17228 0.099976 -0.3238 -0.56807 -1.24969 -1.13033 -0.28771 -1.276 -1.08067 0.29706 -1.41023 0.858701

HCO-3
-0.25418 -0.20367 0.382204 1.050211 0.935004 2.912564 1.195753 -0.35486 -0.18472 -1.23005 -1.14066 -0.14898 -1.06676 -0.62594 0.040939 -1.04498 1.018908 -1.65659 0.833673

Si
-0.77776 -1.11622 -0.34058 -1.38463 -1.16322 -1.25724 0.063687 0.761287 -0.18076 -0.12435 2.141444 -0.33118 -0.11964 -0.28417 1.088463 0.345735 -0.24657 -0.4487 -0.27947

Cu
2.327213 -0.6131 -0.03037 -0.43828 -0.19686 1.972576 -0.44661 3.2163 0.011255 -0.44661 -0.52153 -0.6131 0.144452 -0.6131 -0.44661 0.385871 -0.44661 -0.36336 -0.44661

Fe
-1.3606 -0.23167 -1.0184 -0.42644 0.738387 -1.50114 2.877088 0.623813 0.786126 0.776578 0.589441 -1.01077 0.76894 0.738387 -1.04896 -1.50725 -0.8771 0.222807 -0.67468

Mn
3.628058 -0.34547 -0.40004 -0.30545 -0.32 -0.32124 -0.41095 2.972474 -0.37312 -0.31491 -0.26543 -0.11991 -0.29308 -0.30181 -0.19994 -0.30327 -0.23451 -0.21413 -0.29963

Pb
4.69585 -0.45225 -0.07537 -0.45225 -0.03769 -0.27889 -0.07537 -0.07537 -0.22612 -0.45225 -0.13191 -0.45225 -0.18844 -0.45225 -0.45225 -0.07537 -1.7E-16 -0.18844 -0.45225

50

10 11 12 13 14 15 16 17 18 19

50

Cl20 21 22 23 24 25 -0.4172 -0.4074 -0.36255 -0.48712 0.595214 -0.00061

NO-3
-0.13614 -0.35346 -0.68488 -0.72548 0.803 0.206419

SO42-0.48274 -0.2468 -0.43051 -0.42737 2.183248 0.103061

Na+
-0.36876 -0.3461 -0.3602 -0.36946 -0.35681 -0.01281

K+
-0.5516 -0.50533 -0.65848 -0.79745 -0.68995 0.486379

Mg2+
-0.54812 -0.07831 0.031225 -0.60372 -0.35241 0.206362

Ca2+
-1.00573 0.366147 0.166596 -0.4265 0.162278 0.186952

HCO-3
0.55566 -0.23627 -0.04845 -1.13905 0.282648 0.127586

Si
-0.71665 1.017951 2.846566 -0.09144 0.670091 -0.07264

Cu
-0.6131 -0.37668 -0.54651 -0.44661 -0.6131 0.161101

Fe
-0.25458 0.478687 0.222807 0.241902 0.050947 0.795673

Mn
-0.30036 -0.23458 -0.28871 -0.30108 -0.29664 -0.15629

Pb
-0.07537 0.048994 0.244968 -0.45225 -1.7E-16 0.056531

Table 9. Correlation matrix chart for different species in ground water

ClCl
-

NO-3

SO42-

Na+

K+

Mg2+

Ca2+

HCO-3

Si

Cu

Fe

Mn

Pb

1.00 0.58 0.18 0.69 0.56 0.50 0.62 0.33 -0.04 0.02 0.20 -0.07 0.03 1.00 0.13 0.32 0.79 0.47 0.64 0.30 -0.39 0.14 -0.17 0.21 0.41 1.00 0.22 0.35 0.21 0.15 0.58 -0.13 0.35 -0.16 -0.05 -0.04 1.00 0.46 0.80 0.65 0.42 -0.12 0.03 0.46 -0.06 0.05 1.00 0.51 0.72 0.55 -0.45 0.19 -0.22 0.01 0.18 1.00 0.60 0.37 -0.13 0.29 0.23 0.35 0.61 1.00 0.55 -0.26 -0.14 0.25 -0.16 0.07 1.00 -0.36 0.16 -0.19 -0.10 -0.03 1.00 -0.12 0.20 -0.01 -0.06 1.00 -0.22 0.81 0.50 1.00 -0.15 -0.23 1.00 0.76 1.00

NO3SO42Na
+

51

K+ Mg2+ Ca2+ HCO3Si Cu Fe Mn Pb

51

Table 10. Eigen value for factor analysis of ground water

Factors 1 2 3 4 Eigen value 4.692 2.657 1.824 1.268 % Total variance 36.096 20.442 14.03 9.759 Cumulative Cumulative Eigen value % 4.692 7.349 9.174 10.443 36.096 56.537 70.568 80.328

Table-11 represents the factor loading matrix and Figure-23 represents the scree plot of the factor analysis (plot of Eigen value versus factor). Table-10 and 11 indicates that these four factors are hydrochemically meaningful, which seems to describe the existing conditions of groundwater chemistry. For obtaining an interpretation of the nature of the retained factors, these factors are discussed as follows. Factor-1: (F1), it accounts for 36.09% of total variance it has high loading for Cl, Na, Mg, and Ca and moderately loaded with Fe. F1 may be assumed to be due to two reasons one is lithogenic in nature other one is saline incursion as the study area is a costal aquifer. But saline incursion is rejected due to following reasons, a) locations from 1 to 5 are moderately affected by F1 and locations 20 to 25 least affected by F1, although these locations are neared by sea. In the other hand location 7 is highly affected by F1 (factor score-4.15 Fig.24) situated far way from water line. b) Other indicators of saline water incursion are high Cl-/HCO-3 ratio, high Mg2+/Ca2+ and high Cl-/SO42-ratio are not followed (Table-6). Table-6 elucidate that, the Cl-/HCO-3 ratio varies between 0.15 to 20.5 with mean value 2.8 and Mg2+/Ca2+ ratio lies in the range of 0.15 to 1.66 with mean value of 0.43, if there occur sea water incursion then Mg2+/Ca2+ ratio should be in the range of 1 to 5 as Mg concentration in sea is about five times more than calcium concentration c) The topographic condition of study area also does not supports the intrusion of sea water as rocky structure of the area with high elevation cause low permeability and high fresh water potential than sea water. Hence, F1 is purely lithogenic origin. Factor-2: (F2), Its accounts for 20.44 % of total variance, which is highly loaded with Cu, Mn and Pb the factor is anthropic in origin good correlation between Cu, Mn and Pb (from Table-9) revealed that source of these heavy metals are vehicular activity. Factor score plot of factor-2 (Fig-25) shows that almost all the locations are unaffected by this factor except location-1, 6, 8

52

and 16. All these locations situated nearby to road and agricultural fields hence most probably affected by vehicular pollution. Table 11. Factor loading matrix of ground water

Variables Cl NO-3 SO42Na+ K+ Mg2+ Ca2+ HCO-3 Cu Fe Mn Si Pb

-

Factor 1 0.768 0.464 0.086 0.914 0.488 0.794 0.788 0.314 -0.071 0.581 -0.051 -0.005 0.128

Factor 2 -0.042 0.234 0.054 0.004 0.072 0.474 -0.144 -0.074 0.823 -0.202 0.957 0.008 0.866

Factor 3 0.233 0.763 0.080 -0.038 0.744 0.097 0.440 0.384 0.007 -0.587 -0.010 -0.671 0.208

Factor 4 0.088 -0.085 0.901 0.215 0.263 0.121 0.082 0.726 0.403 -0.194 -0.062 -0.156 -0.185

Fig. 23 Scree Plot Factor-3: (F3) its accounts for the 14.03% of total variance and loaded with NO3- , K+ positively and with Si, Fe negatively. The factor attributed due to combination of both anthropic as well as natural. Good correlation between nitrate and potassium indicates leaching of fertilizer (NPK)

53

from soil. Factor score plot (fig-26) shows that location no 1 to 6, and 12,17,19 and 20 are affected by factor-3.out of these location 1 to 6 are nearby agricultural field, due to high precipitation at this area there is maximum chance of leaching of fertilizers from land to ground water. Negative loading of Fe and Si revealed that there occurs incongruent weathering [42] of jarosite-K. Jarosite-K mineral is the weathered product of basalt due to water rock interaction
[43]. As Jarosite-K is very unstable in humid condition it rapidly decomposes to produce ferric

oxihydroxide (Goethite) [44]. Other evidences in supports of the Jorasite-K decomposition are a) All the locations are over saturated with goethite (Table-7).b) Predominance of kaolinite at study area, as under most conditions jarosite is accompanied by kaolinite and gypsum [44]. Factor-4: (F4) loaded with sulphate and bicarbonate although these are produced by mineralization product of ground water and sulphate act as source of oxygen for oxidation of dissolved organic carbon (DOC) to carbon dioxide which in turn increases the concentration of bicarbonates the reason of association in factor is still not clear.

Fig. 24 Factor-1 score plot

Fig. 25 Factor-2 score plot

54

Fig. 26 Factor-3 score plot 3.9.2 Cluster analysis of ground water

Fig. 27 Factor-4 score plot

There are several clustering techniques are exists, but hierarchical clustering is the most widely applied in earth science [45]. Q-mode Cluster analysis was performed on the data sets considering Wards method as linkage rule and correlation distance as distance major. Qmode cluster analysis of chemical parameters of ground water classified all the 25 sampling locations into four groups or cluster as shown in dendrogram (Fig-28) assuming similar type of ground water evolution. The different clusters are as follows; C1(Location no.-18,13,10,9,14 and 23) predominated with Ca-Mg cation and anions SO4+Cl-.all these locations are less affected by four factors as shown in factor score plot (Fig-24 to27) C2 (Locations-22, 21, 19, 17, 20, 16, 15, 12, 5 and 4) predominance of cations (Ca-Mg) with majority of location is dominated by bicarbonate. C3 (Locations 25, 11, 7, 24, 3, 6 and 2) is dominated by alkali metal ion (Na+K) and Cl+SO4 anions. C4 (Location-1 and 8) predominated by Ca-Mg SO4-Cl type water form a distinct group as it is highly affected by factor 2,i.e., Cu, Mn and Pb. (factor score plot. Fig-25). These spatial variation and grouping of locations suggest that, ground water of locations under cluster C2 and C3 are natural in origin. Where C1 and C4 influenced by external factors which may be natural (i.e., weathering) and anthropic (human activity) which is based upon fact that free sodium-bicarbonate and chlorides of calcium and magnesium on the other hand do not exist in natural water[46].
55

Fig. 28 Dendrogram of Q-Mode cluster analysis of water samples 3.10 Variation in distribution of Heavy metals in soil and sediments of study area From Table -4 the mean concentrations of Pb, Cu, Cd, Fe, Ni, Co and Mn in soils were found to be 28.2mg/kg, 124.15 mg/kg, 0.6 mg/kg, 44775 mg/kg, 35.52 mg/kg, 38.01 mg/kg and 178 mg/kg respectively. However, in case of sediments, (Table-12) the mean concentration of these metals were found to be 18.22 mg/kg, 76.4 mg/kg, 0.26 mg/kg, 40885 mg/kg, 8.62 mg/kg, 0.77 mg/kg and 107.25 mg/kg respectively. Akin to ground water (Table-2), soils (Table-4) and sediments (Table-12) also shows high % CV for majority of species, this high value of %CV revealed non homogenous distribution of species at studied sites. There exist a number of reasons behind the non homogeneous distribution which might be due to anthropogenic and/or natural input. The concentration of Pb, Cu, Cd, Fe, Ni, Co and Mn in soil differed from sediment by a factor of 1.55, 1.63, 2.3, 1.1, 4.12, 49.4 and 1.66 respectively. Low content in sediment is due to their distribution in both phases i.e., between sediment and groundwater system. Fe is leached from the Fe-rich basalts of the Deccan Traps which could enrich the Fe content in the samples. Organic matter is known to contain up to 100 ppm of Co and has high flux rates of organic carbon, which apparently transfers high amounts of Co to the groundwater where C org is then re-mineralized and substantial proportions of Co and Ni can be retained by the sediments. High Cu and Ni contents in clay-minerals (Illite) that are derived from soils and trapping of these metals in strongly reducing sediments could increase the content in the sediment. Like Cu and Co, Ni concentrations are highest in ultramafic rocks. A third factor affecting Ni concentrations in sediments is its tendency to bind to metals, especially sulphides to Fe (pyrite).

56

3.11 Geochemical normalization and enrichment factors (EF) of heavy metals in soil and sediments with respect to continental upper crust In an attempt to compensate for the natural variability of heavy metals in soil and sediments, normalization was done so that any anthropogenic metal contributions could be detected and quantified. The equation -2 was used to estimate the EF of metals for each sampling location using Fe as a normalizer to correct for differences in sediments grain size and mineralogy. Enrichment factor of Pb, Cu, Cd, Ni, Co and Mn in soils of various locations is given in Table13. The mean enrichment factor of Pb, Cu, Cd, Ni, Co and Mn in soil was calculated to be 1.12, 4.15, 52.1, 1.52, 3.95 and 0.22 respectively. However, in case of sediment, the mean enrichment factor was worked out to be 0.84, 2.94, 25, 0.4, 0.07 and 0.16 for the same metals respectively. The EF values in soil samples were observed in the order of Cd > Cu > Co > Ni > Pb > Mn whereas in case of sediment the trend was found as follows: Cd > Cu > Pb > Ni > Co > Mn. In soils and sediments Cd has the highest enrichment factor followed by Cu revealed that they were from a common source. 3.12 Geo-accumulation indices of heavy metals in soil and sediments with respect to continental upper crust Table.17 represents the geo-accumulation indices based on soil and sediment quality. Geoaccumulation indices of metals with respect to continental upper crust in soils and sediments of various locations were calculated using equation-3. Using the geo-accumulation indices of heavy metal, the predominant class in soil was found to be as follows presented in table-15.from geoaccumulation indices value following conclusions can be derived: Cd was found to be in the highest Igeo class (6) indicating extremely contaminated, Mn remains in class 0 (uncontaminated), Fe and Ni are in class 1, Cu in class 3 (Moderately to strongly contaminated) and Co is in class 2. However for sediment (Table-16) Fe, Ni, Co and Mn were within the Igeo class (0-1) indicating uncontaminated sediment, whereas Cd belonged to the same class as soil. Geoaccumulation index and enrichment factor of Cd indicates that soil is contaminated with Cd, it may be contributed by fertilizer since phosphate fertilizers are Cd rich.

57

Table 12. Sediment Data Sheet

Location
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 Mean SD %CV

Na (mg/kg)
25614.3 40122.3 22486 15671.16 23970.7 28216.54 26228.62 10073.89 21541.51 24514.5 18547.5 35124.6 29457.1 24512.8 15435.5 27451.8 21354.2 22154.87 21421.6 18679.2 19854.3 26142.2 35214.2 28645.6 25462.2 24315.89 6583.14 27.07

K (mg/kg)
10589.5 11677.4 11358.4 10423.5 16926 9616.42 11434.72 6174.5 7856.5 4586.4 8214.8 4254.5 4682.4 4365.34 3512.7 4051 8651.5 4361.8 10246.8 5468.9 6128.4 5124.6 4982.7 5342.5 10845.3 7635.06 3405.34 44.6

Mg (mg/kg)
12354 12444.9 13452 13482.71 2385.41 17537.53 25764.58 53112.04 24541 45871.5 43512.5 32154.3 45123.6 26781.6 43512.2 21341.3 12351.6 24315.5 13524.2 12453.6 17543.6 24316.2 22431.5 10542.3 36251.5 24284.05 13494.6 55.6

Ca (mg/kg)
4261 8467.6 8431.5 6241.3 5567 4658.5 8315.5 2461.3 4463 3846 3843.2 4523.2 5426.5 5637 3192 3124.6 7594.9 3049.5 8564.5 2013.5 4317.8 4029.3 24351.2 23145.6 9861.6 6775.48 5539.4 81.75

Pb (mg/kg)
67.54 43.12 3.45 1.81 87.51 24.61 2.12 1.65 3.61 2.51 3.85 5.61 7.56 1.85 2.94 42.51 26.51 11.61 2.51 4.51 53.15 43.15 1.95 5.31 4.59 18.22 24.12 132.31

Cd (mg/kg)
1.59 1.43 0.004 0.008 0.002 0.045 0.042 0.0061 0.045 0.054 0.034 0.0024 0.0421 0.0046 0.085 0.0021 0.0315 0.054 0.053 0.014 0.58 0.042 2.15 0.125 0.025 0.258 0.574 221.66

Cu (mg/kg)
189.76 124.61 53.87 16.5 82.54 157.5 77.26 97.82 98.62 67.87 29.76 35.34 63.83 36.42 54.61 92.34 86.9 77.87 97.8 65.76 43.76 48.52 56.75 85.98 67.76 76.39 38.91 50.9

Fe (mg/kg)
27534.2 37614.3 36143.5 33163.8 48451 33145.12 52130.2 31642.4 30121.3 41245 48457.2 30431 51757 56153.4 55345.2 52314.2 33419.2 31461 34651 31536.1 32134.84 53821.1 51352.2 33481.6 54612 40884.71 10085.58 24.66

Ni (mg/kg)
11.7 12.6 6.7 6.8 8.9 5.3 10.87 9.5 7.58 8.99 7.65 7.5 8.85 11.73 12.61 7.82 8.81 10.71 7.83 7.66 5.61 11.83 7.3 6.22 4.48 8.62 2.32 26.88

Co (mg/kg)
0.023 0.02 2.1 1.3 1.5 0.056 1.7 1.65 0.97 0.845 1.56 0.827 0.7262 0.846 0.0027 0.0028 0.002 0.0062 0.003 0.0064 0.0076 0.978 1.4 1.8 0.95 0.77 0.71 92.32

Mn (mg/kg)
115.84 117.23 102.15 102.06 102.48 110.3 102.33 101.56 101.06 102.4 102.43 101.86 101.52 101.06 112.51 113.42 117.5 117 118.64 111.52 115.32 103.12 104 102.15 101.92 107.25 6.65 6.19

58

58

Table 13. Soil enrichment factor Data sheet

Location 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25

Pb 1.62 1.65 1.26 1.22 2.53 1.62 1.22 0.86 0.77 0.90 0.77 0.81 1.18 1.64 1.20 1.06 0.53 0.45 0.47 0.40 1.25 2.25 0.81 0.84 0.64

Cu 2.24 2.41 6.97 6.94 4.26 7.81 4.59 4.44 4.27 4.55 4.37 4.41 4.56 2.82 3.60 3.43 2.52 2.25 2.34 2.18 1.85 7.02 6.01 4.06 3.88

Cd 25.93 28.19 143.16 240.74 21.8 165.03 69.85 25.55 20.47 27.13 24.06 43.38 25.19 21.93 27.78 24.19 16.42 14.16 15.01 13.88 24.82 0 240.85 22.93 19.92

Ni 0.90 1.14 1.96 2.03 2.15 0.8 2.08 1.95 1.79 1.67 1.62 1.66 1.99 2.07 1.11 1.05 1.12 1.08 1.05 1.04 0.53 2.09 1.96 1.63 1.5

Co 0.16 0.06 6.51 6.37 6.51 0.42 6.94 6.41 6.24 6.49 6.531 6.52 6.77 6.74 0.01 0.006 0.031 0.028 0.026 0.023 0.013 7.00 6.4 6.43 6.25

Mn 0.25 0.26 0.20 0.2 0.19 0.19 0.20 0.2 0.2 0.20 0.20 0.20 0.20 0.20 0.26 0.26 0.26 0.26 0.26 0.26 0.25 0.20 0.19 0.20 0.20

59

59

Table 14. Sediment enrichment factor data sheet Location 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 Pb 4.3 2.00 0.16 0.095 3.16 1.29 0.071 0.091 0.209 0.106 0.139 0.322 0.255 0.057 0.093 1.42 1.38 0.64 0.12 0.25 2.89 1.40 0.066 0.27 0.14 Cd 206.24 135.77 0.39 0.86 0.14 4.84 2.87 0.68 5.33 4.67 2.50 0.28 2.90 0.29 5.51 0.14 3.36 6.13 5.46 1.58 64.46 2.77 149.5 13.33 1.63 Cu 9.65 4.63 2.08 0.69 2.38 6.65 2.07 4.33 4.58 2.30 0.85 1.62 1.72 0.90 1.38 2.47 3.64 3.46 3.95 2.91 1.90 1.26 1.54 3.59 1.73
60

Ni 0.74 0.58 0.32 0.36 0.32 0.27 0.36 0.53 0.44 0.38 0.27 0.43 0.29 0.36 0.39 0.26 0.46 0.59 0.39 0.43 0.30 0.38 0.25 0.32 0.14

Co 0.002 0.0018 0.203 0.137 0.108 0.006 0.114 0.182 0.112 0.071 0.112 0.095 0.049 0.052 0.0001 0.0001 0.0002 0.0007 0.0003 0.0007 0.00083 0.0636 0.095 0.19 0.0608

Mn 0.24 0.18 0.16 0.18 0.12 0.19 0.12 0.18 0.19 0.14 0.12 0.19 0.12 0.10 0.12 0.12 0.20 0.21 0.19 0.20 0.20 0.11 0.12 0.17 0.10

60

Table 15. Geoaccumulation Index of Soil

Location 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 Pb 0.93 0.96 -0.30 -0.34 0.72 0.94 -0.34 -0.84 -1.02 -0.82 -1.04 -0.97 -0.39 0.087 0.52 0.33 -0.67 -0.92 -0.85 -1.07 0.55 0.55 -0.93 -0.93 -1.33 Cu 1.40 1.51 2.16 2.15 1.46 3.20 1.56 1.50 1.43 1.51 1.44 1.46 1.55 0.86 2.08 2.01 1.57 1.40 1.46 1.35 1.12 2.19 1.9 1.33 1.25 Cd 4.94 5.05 6.52 7.27 3.82 7.60 5.48 4.02 3.69 4.08 3.90 4.76 4.02 3.82 5.04 4.83 4.27 4.06 4.14 4.03 4.87 0 7.26 3.84 3.61 Fe 0.24 0.24 -0.64 -0.64 -0.62 0.24 -0.64 -0.65 -0.66 -0.67 -0.68 -0.68 -0.64 -0.63 0.24 0.24 0.24 0.23 0.23 0.23 0.23 -0.61 -0.64 -0.68 -0.70 Ni 0.098 0.44 0.34 0.38 0.48 -0.068 0.42 0.32 0.18 0.07 0.014 0.05 0.36 0.42 0.39 0.31 0.40 0.35 0.31 0.29 -0.67 0.45 0.33 0.027 -0.11 Co -2.39 -3.59 2.063 2.03 2.07 -0.98 2.15 2.03 1.97 2.02 2.02 2.02 2.12 2.12 -6.30 -7.09 -4.74 -4.90 -5.0 -5.22 -5.96 2.19 2.03 2.00 1.94 Mn -1.73 -1.67 -2.94 -2.95 -2.95 -2.14 -2.93 -2.96 -2.96 -2.94 -2.95 -2.95 -2.95 -2.94 -1.68 -1.69 -1.66 -1.68 -1.67 -1.67 -1.75 -2.92 -2.992 -2.95 -2.96

61

61

Table 16. Geoaccumulation Index of Sediments

Location 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 Pb 1.17 0.52 -3.12 -4.04 1.54 -0.28 -3.82 -4.18 -3.05 -3.57 -2.96 -2.42 -1.98 -4.01 -3.35 0.5 -0.17 -1.37 -3.57 -2.73 0.82 0.52 -3.94 -2.49 -2.7 Cd 6.76 6.60 -1.87 -0.87 -2.87 1.61 1.51 -1.26 1.61 1.87 1.21 -2.61 1.52 -1.68 2.53 -2.80 1.09 1.87 1.85 -0.07 5.30 1.51 7.19 3.08 0.76 Cu 2.34 1.73 0.52 -1.18 1.13 2.07 1.04 1.38 1.39 0.85 -0.33 -0.08 0.76 -0.04 0.54 1.30 1.21 1.05 1.38 0.81 0.22 0.37 0.59 1.19 0.85 Fe -0.93 -0.48 -0.54 -0.66 -0.11 -0.66 -0.01 -0.73 -0.80 -0.34 -0.11 -0.78 -0.02 0.09 0.07 -0.005 -0.65 -0.74 -0.59 -0.74 -0.70 0.03 -0.03 -0.64 0.05 Ni -1.35 -1.25 -2.16 -2.14 -1.75 -2.5 -1.46 -1.65 -1.98 -1.73 -1.97 -2 -1.76 -1.35 -1.25 -1.94 -1.76 -1.48 -1.93 -1.97 -2.42 -1.34 -2.03 -2.26 -2.74 Co -9.35 -9.55 -2.84 -3.53 -3.32 -8.06 -3.14 -3.18 -3.95 -4.14 -3.26 -4.18 -4.36 -4.15 -12.43 -12.38 -12.87 -11.24 -12.28 -11.19 -10.94 -3.94 -3.42 -3.05 -3.98 Mn -2.95 -2.94 -3.14 -3.14 -3.13 -3.028 -3.13 -3.14 -3.15 -3.13 -3.13 -3.14 -3.15 -3.15 -2.99 -2.98 -2.93 -2.94 -2.92 -3.01 -2.96 -3.12 -3.11 -3.14 -3.14

62

62

Table 17. Classification of geo-accumulation index based on sediment/soil quality Igeo >5 4-5 3-4 2-3 1-2 0-1 <0 Igeo class 6 5 4 3 2 1 0 Description of sediment and soil quality Extremely contaminated Strongly to extremely strongly contaminated Strongly contaminated Moderately to strongly contaminated Moderately contaminated Uncontaminated to moderately contaminated Uncontaminated

Source: Igeo classification (Muller, 1979)

3.13 Textural analysis of soil Table-18 to 28 summarizes the concentration of different chemical species in different size fraction of soils of 25 locations. All the data sheet shows that, the distribution of Fe is homogenous in all the fractions of soil of all locations having CV>40%, except in soil texture 355 m <X<500 m. (Table-19). This elucidates that occurrence of iron is purely natural, which is also supported from fact that geoaccumulation indices of iron in all texture of soils of study area belongs to Igeo class 0 (i.e. uncontaminated) Other species shows high % CV in all the fraction indicates there is non-homogeneous distribution which may be due to natural processes or anthropogenic. Pb shows high enrichment in texture size 2mm>x>355m, and <90m suggest both natural and anthropic input of Pb to the soil. Pb in higher fraction is due to weathering basalt and in lower fraction is due to contamination of soils by bottom sediments of Ulhas River. Higher %CV value of Cu and Cd is in all fractions of soils of all locations accounts for its anthropogenic inputs to soil by mixing of excavated sediments of Ulhas River which contains high level of Cd and Cu. Enrichment factor in 11 fractions (texture) of soil presented in Table29-39 and geoaccumulation indices of Pb, Cu, Cd, Ni, Co, Fe and Mn in different texture of soil of all locations graphically presented in as follows (Fig-29-39). These graphs revealed that, all the locations are extremely contaminated w.r.t Cd (Igeo class-6) followed by strongly contaminated with Cu (Igeo class-3, which is moderately to strongly). Geochemical indices of

63

remaining heavy metals showed that all locations are uncontaminated with respect to these elements.

Fig. 29 Geoaccumulation indices of heavy metals in soil fraction-1

Fig. 30 Geoaccumulation indices of heavy metals in soil fraction-2

64

Fig. 31 Geoaccumulation indices of heavy metals in soil fraction-3

Fig. 32 Geoaccumulation indices of heavy metals in soil fraction-4

Fig. 33 Geoaccumulation indices of heavy metals in soil fraction-5

65

Fig. 34 Geoaccumulation indices of heavy metals in soil fraction-6

Fig. 35 Geoaccumulation indices of heavy metals in soil fraction-7

Fig. 36 Geoaccumulation indices of heavy metals in soil fraction-8

66

Fig. 37 Geoaccumulation indices of heavy metals in soil fraction-9

Fig. 38 Geoaccumulation indices of heavy metals in soil fraction-10

Fig-39 Geoaccumulation indices of heavy metals in soil fraction-11

67

Table 18. Soil data sheet fraction-1 (Soil texture 500 m <X<2mm)
Location 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 Mean SD %CV

Pb (g/g)
133.75 135.02 31.37 30.71 43.86 49.4 0.79 17.71 15.78 18.03 15.13 15.79 BDL 39.76 21.56 16.44 19.81 16.88 17.66 15.34 120.48 22.86 22.78 16.763 12.99 34.027 37.84 111.22

Cu (g/g)
75 82.61 164.70 164.05 108.65 506.4 111.66 134.79 129.51 135.53 130.79 131.92 110.87 93.09 55.91 48.28 139.91 127.78 131.94 124.62 57.45 68.33 141.06 123.25 117.97 128.64 85.03 66.09

Cd (g/g)
2.75 2.792 2.18 3.095 0.454 1.8 5.645 5 4.96 5.017 4.495 4.674 5.217 0.238 2.77 2.715 5.047 5.007 5.023 5 2.725 BDL 3.085 4.973 4.944 3.58 1.70 47.60

Fe (g/g)
42758.4 42863.4 36350.72 36349.41 36734.41 52123.6 36256.64 36215.21 35825.79 36845.58 36588.24 36694.04 36255.06 36389.26 42757.6 42631.93 42775.4 42561.95 42666.5 42527.3 42513.05 36412.06 36184.83 36635.53 36203.32 39284.77 4053.93 10.32

Ni (g/g)
8.5 61.71 58.91 60.13 62.93 81.8 61.56 58.59 55.14 52.6 50.24 51.13 59.98 61.52 60.46 58.31 60.81 59.3 58.27 57.83 4 60 58.78 51.63 48.78 54.52 15.80 28.98

Co (g/g)
19.8 21.04 35.65 34.34 36.38 52.19 36.94 34.46 32.11 34 33.91 34.01 35.36 35.24 19.99 19.11 19.56 19.5 19.46 19.40 19.71 37 34.26 33.05 30.6 29.88 8.63 28.88

Mn (g/g)
137.87 148.42 367.59 366.28 366.43 2086.31 451.007 365.707 365.627 367.477 366.237 366.677 449.427 450 147.86 145.32 150.99 147.12 148.45 148.3 134.37 451 363.48 366.507 365.927 368.97 377.81 102.39

Na (g/g)
16904.94 17010.74 5332.31 5331 5335.5 9909 1966.48 6352.17 6055.17 6270.17 6215.82 6637.08 1964.9 19705.48 16905.08 16766.44 16767.52 16708.98 16225.52 16269.42 16664.72 29506.7 5176 5994.37 5780.37 11110.24 6974.53 62.77

K (g/g)
25287.1 25528.4 7171.31 7170 7172 21044 2312.89 3121.53 2281.53 7008 6950.49 7092.99 2311.31 16826.7 25402.86 25277.66 25386.26 25287.72 25144.76 24291.26 24999.89 6306.4 6738.8 7113.57 6971.57 13767.96 9586.78 69.63

Mg (g/g)
2929.72 2985.2 4155.31 4154 4156 5596 757.43 15195.34 14629.34 4378.8 4352.22 4462.42 755.85 10620.6 2850.25 2723.51 2738.71 2713.121 2653.34 2160.51 2684.52 912.85 4050 4481.88 4324.35 4456.85 3686.93 82.73

Ca (g/g)
3458.01 3669.01 1779 1777 1778.84 12542.8 7391.26 3039.21 3014.21 5819.15 1792 1785.58 7389.68 9004.55 7516.51 7302.56 8359.76 8334.35 7309.41 8671.82 8089.31 7546.68 8022.11 2844.6 2719.4 5638.27 3071.44 54.47

68

68

Table 19. Soil data sheet fraction-2 (Soil texture (355 m <x<500 m)
Location 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 Mean SD %CV

Pb (g/g)
25.23 26.49 45.92 45.26 50.65 37.27 18.95 17.75 15.82 17.27 14.23 14.91 18.16 2.83 39.76 34.64 19.85 16.93 17.71 15.38 11.95 41.05 37.33 16.01 12.24 24.54 12.93 52.69

Cu (g/g)
55.45 63.05 381.97 381.33 122.83 691.36 98.42 142.25 136.96 142.98 137.87 138.99 97.63 6.875 108.89 101.27 147.37 135.25 139.4 132.08 37.91 121.32 358.33 130.69 125.44 165.43 144.42 87.29

Cd (g/g)
4.77 4.82 4.6 5.53 0.87 1.82 0.69 0.25 0.21 0.31 0.26 0.44 0.26 0.5 4.8 4.74 0.29 0.26 0.27 0.25 4.75 BDL 5.52 0.26 0.232 1.86 2.18 117.04

Fe (g/g)
19349 19454 55927.31 55926 56311 15897 54742.38 55791.8 55402.38 56542.5 56285.16 56390.96 54740.8 54875 19348.2 19222.53 19366 19152.55 19257.1 19117.9 19103.65 54897.8 55761.42 56332.45 55900.24 41003.81 18415.64 44.91

Ni (g/g)
60.73 19.38 16.58 17.8 20.6 39.9 18.56 16.26 12.81 10.27 9.58 10.47 16.98 18.52 18.13 15.98 18.48 16.97 15.94 15.5 56.23 12.51 16.45 9.3 6.45 19.61 13.21 67.35 69

Co (g/g)
14.78 16.02 1.31 BDL 2.04 BDL 1.7 0.12 0.09 1.98 1.89 1.985 0.12 BDL 14.97 14.09 14.54 14.48 14.446 14.382 14.69 1.56 BDL 1.03 0.58 6.11 6.84 111.94

Mn (g/g)
136.7 147.25 175 173.69 173.84 149.2 191.85 173.12 173.04 174.88 173.65 174.08 190.27 190.85 146.69 144.15 149.82 145.95 147.28 147.13 133.2 198.52 170.89 173.92 173.33 165.13 18.65 11.29

Na (g/g)
148254.6 148360.4 8841.55 8840.24 8844.74 3669 1815.5 7988.11 7691.11 7906.11 7851.76 8273.02 1813.92 17978.04 148254.8 148116.1 148117.2 148058.7 147575.2 147619.1 148014.4 26022.6 8685.24 7630.31 7416.31 58945.53 68356.04 115.96

K (g/g)
10899.4 11140.7 9651.31 9650 9652 9044 3540.58 3674.8 2834.8 9808 9699.8 9842.3 3539 20273.7 11015.16 10889.96 10998.56 10900.02 10757.06 9903.56 10612.19 8715.01 9218.8 9913.78 9771.78 9437.85 3433.38 36.378

Mg (g/g)
1082.01 1137.49 4437.31 4436 4438 2848 27573.28 21749.51 21183.51 4744 4723.42 4833.62 27571.7 21475.7 1002.54 875.8 891 865.411 805.63 506.4 836.81 29024.87 4332 4847.08 4689.55 8036.42 9870.63 122.82

Ca (g/g)
8757.11 8968.11 7787 7785 7786.84 6978.8 13301.25 38498.7 37743.7 7828.24 7801.09 8035.59 11299.67 8200.21 8815.61 8601.66 8658.86 8633.45 8608.51 7970.92 8388.41 20622.05 7845.03 7853.69 7728.49 11397.92 8497.23 74.66

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Table 20. Soil data sheet fraction-3 (Soil texture 250 m <X< 355 m)
Location 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 Mean SD %CV Pb (g/g) 50.44 51.72 30.65 30 35.68 33.96 4.19 27.25 25.32 27.57 24.93 25.59 3.41 63.57 34.62 29.49 29.35 26.43 27.21 24.88 37.16 35.91 22.06 26.31 22.52 30.1 12.6 41.95 Cu (g/g) 53.26 60.86 255.88 255.23 82.955 458.75 0.79 227.25 221.96 227.98 223.41 224.54 BDL 140.47 111.66 104.05 232.37 220.25 224.4 217.08 35.711 124.09 232.24 215.69 210.44 174.45 102.32 58.65 Cd (g/g) 1.52 1.56 2.04 2.95 1.14 1.66 0.65 0.25 0.21 0.27 0.24 0.42 0.23 0.714 1.55 1.48 0.29 0.25 0.27 0.25 1.49 BDL 2.94 0.22 0.19 0.92 0.869 95.2 Fe (g/g) 20512.92 20617.92 46767.11 46765.8 47150.8 41114.8 46925.38 46631.6 46242.18 46002.18 45744.84 45850.64 46923.8 47058 20512.12 20386.45 20529.92 20316.47 20421.02 20281.82 20267.57 47080.8 46601.22 45792.13 45359.92 36874.3 12641.73 34.28 Ni (g/g) 17.5 59.58 56.78 58 60.8 206.08 58 56.46 53.01 50.47 49.23 50.12 56.42 57.96 58.33 56.18 58.68 57.17 56.14 55.7 13 58 56.65 49.5 46.65 58.26 32.94 56.55 70 Co (g/g) 3.2 4.44 60.02 58.71 60.75 696.47 59.55 58.83 56.47 58.36 58.27 58.37 57.97 57.85 3.39 3.31 3.76 3.7 3.66 3.60 3.11 49.9 58.63 57.42 54.96 63.78 134.41 210.71 Mn (g/g) 145.65 156.2 107.39 106.08 106.23 100 111.56 105.51 105.42 107.27 106.03 106.47 109.98 110.56 155.64 153.1 158.77 154.9 156.23 156.08 142.15 111.52 103.28 106.31 105.73 123.523 23.056 18.67 Na (g/g) 16605.3 16711.1 1158609 1158608 1158613 23298 23588.48 8471.15 8174.15 8389.15 8334.8 8756.06 23586.9 21018.66 16605.44 16466.8 16467.88 16409.34 15925.88 15969.78 16365.08 23340.78 1158453 8113.35 7899.35 198191.2 427818.8 215.86 K (g/g) 11498.56 11739.86 10291.31 10290 10292 13051 15334.58 3457.5 2617.5 10602 10600.5 10743 15333 17950 11614.32 11489.12 11597.72 11499.18 11356.22 10502.72 11211.35 8671.88 9858.8 10707.41 10565.41 10915 3084.73 28.61 Mg (g/g) 1448.63 1504.11 4255.31 4254 4256 3965 113924.7 18166.27 17600.27 4821.46 4799.88 4910.08 113923.1 25662.71 1369.16 1242.42 1257.62 1232.031 1172.25 679.42 1203.43 29399 4150 4924.54 4767.01 14995.53 30765.98 205.1676 Ca (g/g) 7489.06 7700.06 8026.3 8024.3 8026.14 9649.6 116732.5 32527.5 31772.5 8049.26 8022.11 8256.61 116730.9 56757.6 7547.56 7333.61 7390.81 7365.4 7340.46 6702.87 7120.36 75015.55 7251.09 8074.71 7949.51 23074.25 32918.76 142.66

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Table 21. Soil data sheet fraction-4(Soil texture 250 m>X>188 m)

Location 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 Mean SD %CV Pb (g/g) 39.13 40.4 25.42 24.76 39.52 46.95 26.69 14.56 12.64 14.89 12.45 12.95 25.91 46.25 36.97 31.85 16.67 13.75 14.52 12.2 25.86 38.26 16.83 13.62 9.85 24.52 12.09 49.32 Cu (g/g) 64.56 72.17 255.89 255.24 98.09 260.44 81.47 145.22 139.93 145.95 140.84 142.02 80.68 115 213.88 206.26 150.34 138.21 142.36 135.05 47.02 226.30 232.25 133.66 128.40 150.05 62.3 41.52 Cd (g/g) 0.435 0.477 2.42 3.33 0.476 1.95 0.427 0.217 0.177 0.235 0.194 0.373 BDL 0.5 0.462 0.399 0.264 0.224 0.239 0.217 0.409 BDL 3.323 0.189 0.16 0.684 0.964 140.99 Fe (g/g) 22401 22506 51785.31 51784 52169 38277.15 51853.38 51649.8 51260.38 51020.38 50763.04 50868.84 51851.8 51986 22400.2 22274.53 22418 22204.55 22309.1 22169.9 22155.65 52008.8 51619.42 50810.33 50378.12 40436.99 14120.33 34.91 Ni (g/g) 24.37 58.15 55.35 56.57 59.37 215.45 56.12 55.03 51.58 49.04 48.24 49.13 54.54 56.08 56.9 54.75 57.25 55.74 54.71 54.27 19.87 211.54 55.22 48.07 45.22 64.10 45.95 71.67 71 Co (g/g) 10.55 11.79 1.31 BDL 2.04 32.29 1.7 0.12 1.29 3.18 3.09 3.185 0.12 BDL 10.74 10.66 11.11 11.05 11.02 10.95 10.46 0.25 0.09 2.23 1.78 6.04 7.23 119.7 Mn (g/g) 136.36 146.91 1190.38 1189.07 1189.22 482.76 1199.01 1188.49 1188.42 1190.27 1189.03 1189.47 1197.43 1198 146.35 143.81 149.48 145.61 146.94 146.79 132.86 1354.43 1186.27 1189.29 1188.72 792.21 517.23 65.29 Na (g/g) 9976.8 10082.6 7191.01 7189.7 7194.2 6948 33866.58 14989.02 14692.02 14907.02 14852.67 15274.12 33865 7309.56 9976.94 9838.3 9839.38 9780.84 9297.38 9341.28 9736.58 13938.4 7034.7 14631.22 14417.22 12646.82 7050.24 55.75 K (g/g) 14906.7 15148 12177.31 12176 12178 17121 16072.48 4544.46 3704.46 12505 11542.6 11685.1 16070.9 8510.84 15022.46 14897.26 15005.86 14907.32 14764.36 13910.86 14619.49 6656.6 11744.8 12610.77 12468.77 12598.06 3466.58 27.52 Mg (g/g) 1888.81 1944.29 4715.31 4714 4716 4955 6918.78 7224.48 6658.48 5017.23 4995.65 5105.85 86917.2 8122.87 1809.34 1682.6 1697.8 1672.211 1612.43 1119.6 1643.61 28493.2 4610 5120.31 4962.78 8332.71 17207.51 206.5 Ca (g/g) 5670.17 5881.17 7988 7986 7987.84 17581.55 23974.08 37834.28 37079.28 7869.18 7845.03 8079.53 23972.5 19128.63 5728.67 5514.72 5571.92 5546.51 5521.57 4883.98 5301.47 57342.6 8061.85 7894.63 7769.43 13520.6 13214.3 97.7

71

Table 22. Soil data sheet fraction-5 (soil texture 188 m>x>125m)
Location 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 Mean SD %CV Pb (g/g) 34.32 35.58 47.65 47 35.75 45.68 28.04 10.35 8.414 11.57 9.63 10.29 27.25 56.25 43.51 38.38 12.44 9.525 10.29 7.979 21.04 44.8 39.06 10.3 6.53 26.06 16.35 62.70 Cu (g/g) 60 67.61 26.92 26.25 96.25 357.04 98.79 95 89.71 95.73 90.62 91.75 98 120.5 111.57 103.95 100.12 87.99 92.15 84.83 42.45 124 3.26 83.44 78.18 93.04 62.46 67.13 Cd (g/g) 0.45 0.49 1.84 2.75 0.75 1.59 0.42 0.173 0.13 0.18 0.14 0.32 BDL BDL 0.48 0.41 0.21 0.17 0.19 0.17 0.42 BDL 2.74 0.14 0.116 0.57 0.78 137.04 Fe (g/g) 44209.5 44314.5 46947.23 46945.92 47330.92 31768.24 46936.38 46811.72 46422.3 46182.3 45924.96 46030.76 46934.8 47069 44208.7 44083.03 44226.5 44013.05 44117.6 43978.4 43964.15 47091.8 46781.34 45972.25 45540.04 45112.22 3054.95 6.77 Ni (g/g) 20.81 48.95 46.15 47.37 50.17 966.23 47.87 45.83 42.38 39.84 38.6 39.49 46.29 47.83 47.7 45.55 48.05 46.54 45.51 45.07 16.31 203.29 46.02 38.87 36.02 85.87 186.378 217.05 72 Co (g/g) 4.2 5.44 1.31 BDL 3.75 BDL 1.7 0.12 0.12 2.01 1.92 2.015 0.12 BDL 4.39 4.31 4.76 4.7 4.66 4.60 4.11 0.27 0.08 1.06 1.01 2.26 1.97 87.28 Mn (g/g) 933 943.55 922.73 921.42 921.57 389.23 991.53 920.85 920.77 922.62 921.34 921.82 989.95 990.52 942.99 940.45 946.12 942.25 943.58 943.43 929.5 1146.95 918.62 921.65 921.07 924.3 121.07 13.1 Na (g/g) 19971.69 20077.49 6663.71 6662.4 6666.9 61387.65 32428.92 9216.54 8919.54 9134.54 9075 9496.26 32427.34 13609.7 19971.83 19833.19 19834.27 19775.73 19292.27 19336.17 19731.47 20463.4 6507.4 8858.74 8644.74 17119.48 11923.43 69.65 K (g/g) 21798.48 22039.78 9897.31 9896 9898 10079 23734.58 2872.62 2032.62 10012 9865.54 10008.04 23733 14268 21914.24 21789.04 21897.64 21799.1 21656.14 20802.64 21511.27 5482.8 9464.8 10117.66 9975.66 14661.84 7124.22 48.59 Mg (g/g) 2996.13 3051.61 3726.11 3724.8 3726.8 3914 15786.1 9798.35 9232.35 4038.17 4018.59 4128.79 15784.5 6554 2916.66 2789.92 2805.12 2779.531 2719.75 2226.92 2750.93 19624.5 3620.8 4141.25 3983.72 5633.57 4729.9 83.9 Ca (g/g) 7041.53 7252.53 7184.9 7182.9 7184.74 10101 12390.5 2706.44 2951.44 7278.24 7251.09 7354.86 12388.9 16059.83 7100.03 6886.08 6943.28 6917.87 6892.93 6255.34 6672.83 8998.86 6751.45 7303.69 7178.49 7689.19 2723.8 35.42

72

Table 23. Soil data sheet fraction-6 (Soil texture 125m>X>106m)

Location 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 Mean SD %CV Pb (g/g) 43.16 44.43 28.15 27.5 44.25 25 41.02 21.66 19.74 21.99 19.25 19.92 40.23 47 38.71 33.58 23.77 20.85 21.62 19.3 29.88 40 19.56 20.72 16.95 29.13 9.86 33.86 Cu (g/g) 87.368 94.973 182.93 182.27 113.75 537.04 123.74 111.11 105.82 111.85 105.29 106.42 122.95 103.25 189.57 181.95 116.23 104.11 108.26 100.94 69.82 202 159.28 99.55 94.29 140.59 88.37 62.86 Cd (g/g) 0.53 0.57 2.72 3.63 1.25 1.29 0.427 0.185 0.145 0.202 0.162 0.345 BDL 0.25 0.553 0.491 0.233 0.193 0.207 0.185 0.501 BDL 3.626 0.157 0.128 0.719 1.02 142.19 Fe (g/g) 31001.5 31106.5 42186.96 42185.65 42570.65 49675 42293.98 42051.45 41662.03 40586.8 40329.46 40435.26 42292.4 42426.6 31000.7 30875.03 31018.5 30805.05 30909.6 30770.4 30756.15 42449.4 42021.07 40376.75 39944.54 38069.26 5634.29 14.8 Ni (g/g) 14.68 25.33 22.53 23.75 26.55 437.23 24.13 22.21 18.76 16.22 14.98 15.87 22.55 24.09 24.08 21.93 24.43 22.92 21.89 21.45 10.18 179.55 22.4 15.25 12.4 43.41 86.32 198.83 73 Co (g/g) 28.3 29.54 3.31 2 4.04 36.9 3.7 2.12 2.04 3.93 3.84 3.94 2.12 2 28.49 28.41 28.86 28.8 28.76 28.70 28.21 2.98 1.92 2.98 0.53 13.46 13.21 98.19 Mn (g/g) 361 371.55 102.61 101.29 101.45 100 111.26 100.72 100.64 102.49 101.25 101.69 109.67 110.25 370.99 368.45 374.12 370.25 371.58 371.43 357.5 110.55 101.54 101.53 100.95 198.99 127.24 63.94 Na (g/g) 8245.2 8351 9940.21 9938.9 9943.4 20430.06 5640.08 6342.78 6045.78 6260.78 6195 6616.26 5638.5 13476.4 8245.34 8106.7 8107.78 8049.24 7565.78 7609.68 8004.98 19380.6 9783.9 5984.98 5770.98 8786.97 3733.96 42.49 K (g/g) 502.5 743.8 11977.31 11976 11978 10651.34 3676.58 1760.17 920.17 11908 11754 11896.5 3675 13520.37 618.26 493.06 601.66 503.12 360.16 .342.5 215.29 6372 11544.8 12013.87 11871.87 6313.9 5337.23 84.53 Mg (g/g) 425 480.48 4670.01 4668.7 4670.7 422 26062.58 6945.73 6379.73 4947.34 4925.76 5035.96 26061 7067.04 345.53 218.79 233.99 208.41 148.62 215.3 179.8 26177.43 4564.7 5050.42 4892.89 6032.6 7957.9 131.92 Ca (g/g) 515.53 726.53 8070 8067.2 8069.04 2034.7 29028.58 18768.86 18013.86 8089 8061.85 8296.35 29027 16077.6 574.03 360.08 417.28 391.87 366.93 0.412 146.83 8432.88 10322.15 8114.45 7989.25 8445.63 8224.9 97.4

73

Table 24. Soil data sheet fraction-7(Soil texture 106m>X>90m)

Location 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 Mean SD %CV Pb (g/g) 20.47 21.74 31.15 30.5 39.75 21.45 35.79 17.17 15.24 16.27 13.82 14.49 35 52.4 57.65 52.53 19.27 16.35 17.12 14.80 7.21 58.94 22.56 15 11.23 26.319 15.25 57.95 Cu (g/g) 33.57 41.17 166.15 165.5 214.5 316.45 15.33 102.60 97.32 103.34 96.77 97.89 14.54 88 332.31 324.69 107.73 95.6 99.75 92.44 16.02 344.74 142.51 91.053 85.793 131.43 100.01 76.09 Cd (g/g) 0.47 0.52 2.34 3.25 2.5 1.46 0.43 0.25 0.17 0.23 0.18 0.36 BDL BDL 0.5 0.44 0.26 0.22 0.24 0.22 0.451 BDL 3.24 0.19 0.16 0.72 0.99 124.60 Fe (g/g) 30549 30654 48264.91 48263.6 48648.6 51115.55 48130.98 48129.4 47739.98 47499.98 47242.64 47348.44 48129.4 48263.6 30548.2 30422.53 30566 30352.55 30457.1 30317.9 30303.65 48286.4 48099.02 47289.93 46857.72 41739.24 8664.05 20.76 Ni (g/g) BDL 12.62 9.82 11.04 13.84 BDL 11.72 9.5 6.05 3.51 2.3 3.19 10.14 11.68 11.37 9.22 11.72 10.21 9.18 8.74 2.3 167.14 9.69 2.54 1.69 13.96 32.19 219.55 74 Co (g/g) BDL 1.24 2.61 1.3 3.34 237 3.55 1.42 0.97 2.86 2.77 2.865 1.97 1.85 0.19 0.162 0.612 0.552 0.518 0.454 0.08 2.09 1.22 1.91 1.26 10.91 47.11 422.77 Mn (g/g) 100 110.55 115.81 114.5 114.65 2031 118.85 113.92 113.84 115.69 114.45 114.89 117.27 117.85 109.99 107.15 112.82 108.95 110.28 110.13 100.35 120.56 111.7 114.72 114.14 189.36 383.71 202.63 Na (g/g) 11612.9 11718.7 11757.81 11756.5 5374.66 5370.16 6740.58 11373.3 11076.3 11291.3 11154 11575.36 6739 18839.6 11613.04 11474.4 11475.48 11416.94 10933.48 10977.38 11372.68 25269.04 11601.5 11015.5 10801.5 11373.24 3901.87 34.32 K (g/g) 16463.69 16704.99 16608.6 16607.29 8988 8986 3484.28 2498.77 1658.77 9596 9584.49 9726.99 3482.7 21971.41 16579.45 16454.25 16562.85 16464.31 16321.35 15467.85 16176.48 7853.7 16176.09 9701.75 9559.75 12147.19 5538.51 45.59 Mg (g/g) 1338.04 1393.52 1482.95 1481.64 2946.6 2944.6 29086.58 9348.1 8782.1 3288.51 3276.93 3387.13 29085 9644.08 1258.57 1131.83 1147.03 1121.44 1061.66 568.83 1092.84 21645.6 1377.64 3391.59 3234.06 5780.67 8349.31 144.43 Ca (g/g) 3098.6 3309.6 3345 3242.2 6939.84 6938 26556.98 26350.85 25595.85 6778.6 6751.45 6985.95 26555.4 25322.18 3157.1 2943.15 3000.35 2974.94 2950 2312.41 2729.9 3382.8 7856.55 6804.05 6678.85 8902.42 8946.14 103.28

74

Table 25. Soil data sheet fraction-8 (Soil texture 90m>X>75 m)

Location 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 Mean SD %CV Pb (g/g) 42.95 44.22 33.98 33.33 34.54 45.9 88.54 12.72 10.79 13.05 10.61 11.37 87.75 53.86 103.02 97.90 14.83 11.90 12.68 10.36 29.68 104.3 25.39 11.78 8.012 38.14 32.64 85.57 Cu (g/g) 97.95 105.56 268.51 267.85 78.64 480.68 111.29 85.91 80.62 86.64 81.52 82.65 110.5 91.59 385.30 377.68 91.02 78.90 83.05 75.73 80.40 397.72 244.86 74.35 69.09 159.52 126.92 79.56 Cd (g/g) 0.22 0.27 5.037 5.952 6.59 1.82 0.42 0.22 0.18 0.24 0.2 0.39 BDL 0.68 0.254 0.19 0.27 0.23 0.25 0.23 0.202 BDL 5.94 0.19 0.17 1.21 2.12 175.52 Fe (g/g) 36795.08 36900.08 44414.73 44413.42 44798.42 53407.04 44438.38 44279.22 43889.8 43649.8 43392.46 43498.26 44436.8 44571 36794.28 36668.61 36812.08 36598.63 36703.18 36563.98 36549.73 44593.8 44248.84 43439.75 43007.54 41794.6 4328.28 10.36 Ni (g/g) BDL 3.28 0.48 1.7 4.5 150.26 1.93 0.16 1.22 1.04 1.04 1.93 0.35 1.89 2.03 0.79 3.29 1.78 0.75 0.31 0.23 157.35 0.35 0.35 0.31 13.49 42.26 313.17 75 Co (g/g) BDL 1.24 50.32 49.01 51.05 42.67 52.68 49.13 46.78 48.67 48.58 48.675 51.1 50.98 0.19 0.11 0.56 0.5 0.466 0.402 0.45 57.55 48.93 47.72 45.27 31.72 24.08 75.93 Mn (g/g) 100 110.55 101.31 100 100.15 610 101.73 100.15 100.09 101.94 100.7 101.14 100.15 100 109.99 107.45 113.12 109.25 110.58 110.43 100.12 100.31 100.21 100.97 100.39 123.63 101.43 82.04 Na (g/g) 1254.5 1360.3 1314.71 1313.4 7866.85 7862.35 6589.38 10732.61 10435.61 10650.61 10652.58 11073.84 6587.8 11722.96 1254.64 1116 1117.08 1058.54 575.08 618.98 1014.28 35872.23 1158.4 10374.81 10160.81 6549.53 7533.31 115.02 K (g/g) 29971.4 30212.7 30031.61 30030.3 15227 15225 2985.61 2555.75 1715.75 16039 15981.49 16123.99 2947.7 17609.9 30087.16 29961.96 30070.56 29972.02 29829.06 28975.56 29684.19 7675.5 29599.1 16144.14 16002.14 20186.34 10545.2 52.24 Mg (g/g) 2994.2 3049.68 3054.41 3053.1 4062.7 4060.7 29574.48 8549.44 7983.44 4408.22 4386.64 4496.84 29572.9 8972.3 2914.73 2787.99 2803.19 2777.601 2717.82 2224.99 2749 27958.59 2949.1 4511.3 4353.77 7078.68 8475.63 119.73 Ca (g/g) 8011.67 8222.67 8072.57 8070.57 10243.84 10242 23032.38 25251.6 24496.6 10349.3 10322.15 9865.52 23030.8 22968.53 8070.17 7856.22 7913.42 7888.01 7863.07 7225.48 7642.97 26572.6 6955.45 10374.75 10249.55 12431.68 6882.2 55.4

75

Table 26. Soil data sheet fraction-9 (Soil texture 75m>x>53 m)

Location 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 Mean SD %CV Pb (g/g) 76.19 77.46 45.18 44.52 3.86 26.95 16.79 10.6 8.67 10.92 8.48 9.145 16 45.95 80.44 75.32 12.70 9.78 10.55 8.235 62.92 81.73 36.58 9.65 5.88 31.78 28.22 88.8 Cu (g/g) 144.52 152.12 391.13 390.47 102.27 396.52 86.04 72.4 67.11 73.13 68.02 69.14 85.25 107.14 322.35 314.73 77.52 65.39 69.55 62.23 126.97 334.78 367.4 60.84 55.58 162.51 129.03 79.40 Cd (g/g) 10 10.04 1.70 2.61 0.90 2.39 13.17 10.2 10.16 10.21 9.77 9.95 12.75 0.47 10.03 9.96 10.24 10.20 10.22 10.2 9.97 BDL 2.60 10.17 10.14 7.93 4.18 47.76 Fe (g/g) 42794 42899 60260.27 60258.96 60643.96 17037 60956.95 60124.76 59735.34 59495.34 59238 59343.8 60955.37 61089.57 42793.2 42667.53 42811 42597.55 42702.1 42562.9 42548.65 61112.37 60094.38 59285.29 58853.08 52114.41 11162.35 21.42 Ni (g/g) BDL 13.98 11.18 12.4 15.2 BDL 13.12 10.86 7.41 4.87 4.13 5.02 11.54 13.08 12.73 10.58 13.08 11.57 10.54 10.1 2.5 168.54 11.05 3.9 3.88 15.25 32.25 201.47 76 Co (g/g) BDL 1.24 2.2 0.89 2.93 99.65 3.22 1.01 0.13 2.02 1.93 2.025 1.64 1.52 0.19 0.182 0.632 0.572 0.538 0.474 0.09 1.96 0.81 1.07 1.025 5.12 19.71 377.19 Mn (g/g) 100 110.55 101.31 100 100.15 707.53 101.73 100.15 100.15 102 100.76 101.2 100.15 100 109.99 109.15 114.82 110.95 112.28 112.13 100.05 100.36 100.52 101.03 100.45 127.89 120.86 94.49 Na (g/g) 15255.88 15361.68 7889.91 7888.6 7893.1 5628.8 8162.88 5090.68 4793.68 5008.68 4954.33 5375.59 8161.3 14002.64 15256.02 15117.38 15118.46 15059.92 14576.46 14620.36 15015.66 25916.9 7733.6 4732.88 4518.88 10525.37 5465.81 51.93 K (g/g) 27578.74 27820.04 7552.31 7551 7553 4667 2832 2750.06 1910.06 7718 7660.58 7803.08 2855 23855.8 27694.5 27569.3 27677.9 27579.36 27436.4 26582.9 27291.53 6446.27 7119.8 7823.77 7681.77 14440.41 10724.49 74.26 Mg (g/g) 2629.09 2684.57 3851.31 3850 3852 4873 26468.98 21453.88 20887.88 4148.43 4126.85 4237.05 26467.4 10814.6 2549.62 2422.88 2438.08 2412.491 2352.71 1859.88 2383.89 22233.7 3746 4251.51 4093.98 7643.59 8343.2 109.15 Ca (g/g) 8437.17 8648.17 7674.5 7672.5 7674.34 12029 27745.6 19661.3 18906.3 7878.7 7856.55 8091.05 27848.6 26505.6 8495.67 8281.72 8338.92 8313.51 8288.57 7650.98 8068.47 20753 6738.55 7904.15 7778.95 11889.7 7027.5 59.1

76

Table 27. Soil data sheet fraction-10 (Soil texture 53 m>X>25m)

Location 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 Mean SD %CV Pb (g/g) 58.25 59.52 43.75 43.09 4.13 68.07 35.33 11.96 10.03 12.28 9.84 10.94 34.54 49.25 80.07 74.95 14.07 11.14 11.92 9.599 44.98 81.36 35.16 11.01 7.249 33.30 25.62 76.93 Cu (g/g) 130.25 137.85 255.89 255.24 10.65 411.54 147.83 79.46 74.17 80.19 74 168.12 147.04 103.25 161.89 154.27 84.58 72.45 76.61 69.29 112.7 174.31 232.24 67.90 62.65 133.78 85 63.54 Cd (g/g) 0.5 0.542 2.418 3.333 0.217 2.115 0.427 0.535 0.495 0.553 0.55 0.456 BDL 0.25 0.527 0.464 0.583 0.543 0.558 0.536 0.475 BDL 3.323 0.508 0.479 0.82 0.92 104.24 Fe (g/g) 51086.87 51191.87 67028.31 67027 67412 12496.06 67381.91 66892.8 66503.38 65824 65566.66 69899.96 67380.33 67514.53 51086.07 50960.4 51103.87 50890.42 50994.97 50855.77 50841.52 67537.33 66862.42 65613.95 65181.74 59005.37 12407.89 21.02 Ni (g/g) BDL 12.71 9.91 11.13 13.93 BDL 12.34 9.59 6.14 3.6 3.08 1116.92 10.76 12.3 11.46 9.31 11.81 10.3 9.27 8.83 0.25 167.76 9.78 2.63 2.545 58.65 222.81 363.88 77 Co (g/g) BDL 1.24 1.31 BDL 1.35 BDL 1.7 0.12 0.16 2.05 1.96 2.045 0.12 BDL 0.19 0.172 0.622 0.562 0.528 0.464 0.086 0.236 0.125 1.1 1.055 0.68 0.709 85.16 Mn (g/g) 100 110.55 101.31 100 100.15 100 101.73 100.15 100.1 101.95 100.69 101.26 100.15 100 109.99 108.45 114.07 110.2 111.53 111.38 100.2 100.28 100.6 100.98 100.4 103.44 4.84 4.68 Na (g/g) 16693.67 16799.47 7352.39 7351.08 7355.58 18513.4 5769.88 5976.03 5679.03 5894.03 5795 7526.76 5768.3 16746.5 16693.81 16555.17 16556.25 16497.71 16014.25 16058.15 16453.45 32511.32 7196.08 5618.23 5404.23 11951.19 6734.97 56.35 K (g/g) 36992.08 37233.38 9077.31 9076 9078 13008 5489 23171.7 22331.7 9299 9241.49 9793.28 2855 26722.3 37107.84 36982.64 37091.24 36992.7 36849.74 35996.24 36704.87 7603.44 8644.8 9404.27 9262.27 20640.33 13498.31 65.39 Mg (g/g) 1857.82 1913.3 4206.31 4205 4207 3106.4 43290.38 21925 21359 4788.45 4766.87 4518.62 43288.8 10845.95 1778.35 1651.61 1666.81 1641.221 1581.44 1088.61 1612.62 24415.34 4101 4891.53 4734 8937.65 12278.54 137.37 Ca (g/g) 6070.9 6281.9 6597 6590 6591.84 8179 27850.18 11296 10541 6982.6 6955.45 6973.05 6775.7 28505.5 6129.4 5915.45 5972.65 5947.24 5922.3 5284.71 5702.2 9536.5 BDL 7008.05 6882.85 8770.5 6159.59 70.043

77

Table 28. Soil data sheet fraction-11 (Soil texture X<25m)

Location 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 Mean SD %CV Pb (g/g) 67.5 68.77 58.83 58.18 51.52 78.79 19.19 11.57 9.641 12.42 10.28 0.665 18.4 58.09 56.66 51.54 13.67 10.75 11.53 9.206 54.23 57.95 50.24 11.15 7.38 34.33 25.41 74.01 Cu (g/g) 134.77 142.37 400.88 400.23 115.44 BDL 273.52 171.43 166.14 172.16 166.9 1.13 272.73 83.81 255.53 247.91 176.55 164.42 168.57 161.25 117.22 267.95 377.24 159.87 154.61 190.11 103.39 49.38 Cd (g/g) 0.68 0.72 2.26 3.18 0.65 1.89 5.65 0.28 0.24 0.30 0.26 0.18 5.23 BDL 0.71 0.64 0.33 0.29 0.31 0.28 0.65 0 3.17 0.26 0.23 1.14 1.57 134.29 Fe (g/g) 47692.3 47797.3 70697.82 70696.51 71081.51 70442.51 70852.94 70562.31 70172.89 70051.5 69794.16 105.8 70851.36 70985.56 47691.5 47565.83 47709.3 47495.85 47600.4 47461.2 47446.95 71008.36 70531.93 69841.45 69409.24 59421.86 16592.98 27.92 Ni (g/g) BDL 1126.38 1123.58 1124.8 1127.6 BDL 1153.84 1123.26 1119.81 1117.27 1116.03 0.89 1152.26 1153.8 1125.13 1122.98 1125.48 1123.97 1122.94 1122.5 BDL 1309.26 1123.45 1116.3 1116.22 953.91 426.48 44.71 78 Co (g/g) BDL 1.24 1.31 BDL 2.04 BDL 1.7 0.12 0.15 2.04 1.95 0.095 0.12 BDL 0.19 0.183 0.633 0.573 0.539 0.475 BDL 0.28 0.13 1.09 0.84 0.63 0.70 111.55 Mn (g/g) 100 110.55 101.31 100 100.15 100 101.73 5410.59 100.18 102.03 100.82 100.44 100.15 100 109.99 109.45 115.12 111.25 112.58 112.43 100 100.31 100.17 101.06 100.48 316.03 1061.38 335.85 Na (g/g) 19785.92 19891.72 7300.61 7299.3 7303.8 3069 7822.58 53105 52808 7154.58 7105.5 421.26 7821 19018.6 19786.06 19647.42 19648.5 19589.96 19106.5 19150.4 19545.7 29592.5 7144.3 6878.78 6664.78 16266.47 13253.88 81.48 K (g/g) 36207.5 36448.8 9406.81 9405.5 9407.5 2631 2949.28 2671.17 1831.17 9708 9650.78 142.5 3953.9 23220.4 36323.26 36198.06 36306.66 36208.12 36065.16 35211.66 35920.29 5566.71 8974.3 9813.47 9671.47 17755.74 14695.09 82.76 Mg (g/g) 3159.35 3214.83 4102.31 4101 4103 638.5 25769.72 23430.7 22864.7 4421 4408.42 110.2 25768.14 10379.67 3079.88 2953.14 2968.34 2942.751 2882.97 2390.14 2914.15 23660.58 3997 4524.08 4366.55 7726.04 8657.93 112.067 Ca (g/g) 8992.17 9203.17 6767 6765 6766.84 1835 6777.28 23529 22774 6775.7 6738.55 234.5 30768.7 27877.43 9050.67 8836.72 8893.92 8868.51 8843.57 8205.98 8623.47 9956.1 BDL 6801.15 6675.95 10002.42 7789.15 77.7

78

Table 29. Enrichment factor in Soil fraction-1 (500 m <X<2mm) Location 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 Pb 5.47 5.51 1.51 1.47 2.1 1.66 0.04 0.85 0.77 0.85 0.72 0.75 0 1.91 0.88 0.67 0.81 0.69 0.72 0.63 4.95 1.09 1.10 0.8 0.63 Cu 2.45 2.69 6.34 6.318 4.14 13.6 4.31 5.21 5.06 5.149 5.004 5.033 4.28 3.58 1.83 1.58 4.58 4.203 4.33 4.10 1.89 2.63 5.45 4.71 4.56 Cd 229.69 232.63 214.18 304.09 44.139 123.33 556.05 493.08 494.45 486.29 438.76 454.92 513.92 23.36 231.37 227.44 421.38 420.14 420.45 419.89 228.92 0 304.48 484.79 487.72 Ni 0.35 2.52 2.83 2.89 2.99 2.74 2.97 2.83 2.69 2.49 2.40 2.43 2.89 2.96 2.47 2.39 2.48 2.43 2.38 2.37 0.16 2.88 2.84 2.46 2.35 Co 1.62 1.71 3.43 3.31 3.46 3.51 3.56 3.33 3.16 3.22 3.24 3.24 3.41 3.38 1.63 1.56 1.6 1.60 1.59 1.59 1.62 3.55 3.31 3.15 2.95 Mn 0.188 0.202 0.589 0.587 0.581 2.334 0.725 0.589 0.595 0.581 0.583 0.583 0.723 0.72 0.202 0.198 0.206 0.203 0.202 0.203 0.184 0.722 0.585 0.584 0.59

79

79

Table 30. Enrichment factor in Soil fraction-2 (355 m >X>500 m ) Location 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 Pb 2.28 2.38 1.43 1.41 1.57 4.10 0.60 0.55 0.49 0.53 0.44 0.43 0.58 0.09 3.5 3.15 1.79 1.55 1.60 1.40 1.09 1.3 1.17 0.49 0.38 Cu 4.01 4.53 9.56 9.55 3.053 60.88 2.517 3.569 3.46 3.54 3.42 3.45 2.49 0.17 7.87 7.37 10.65 9.88 10.13 9.67 2.77 3.093 8.99 3.24 3.14 Cd 880.81 883.95 294.47 352.90 55.15 408.43 45.055 16.003 13.537 19.328 16.497 27.48 17.15 32.54 886.01 880.10 54.771 47.92 50.63 46.70 887.45 0 353.29 16.55 14.82
80

Ni 5.49 1.74 0.52 0.55 0.64 4.39 0.59 0.51 0.40 0.31 0.29 0.325 0.54 0.59 1.64 1.45 1.669 1.55 1.44 1.41 5.15 0.39 0.55 0.288 0.20

Co 2.67 2.88 0.082 0 0.12 0 0.108 0.007 0.005 0.122 0.117 0.123 0.007 0 2.708 2.56 2.627 2.646 2.625 2.63 2.691 0.099 0.005 0.064 0.03

Mn 0.41 0.44 0.18 0.18 0.18 0.54 0.20 0.18 0.18 0.18 0.18 0.18 0.2 0.20 0.44 0.43 0.45 0.44 0.45 0.45 0.41 0.21 0.17 0.18 0.18

80

Table 31. Enrichment factor in Soil fraction-3 (250 m <X< 355 m) Location 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 Pb 4.30 4.38 1.14 1.12 1.32 1.44 0.15 1.02 0.95 1.04 0.95 0.97 0.12 2.36 2.95 2.53 2.50 2.27 2.33 2.14 3.20 1.33 0.82 1.00 0.86 Cu 3.63 4.13 7.65 7.64 2.46 15.62 0.023 6.82 6.71 6.93 6.83 6.85 0 4.17 7.62 7.1 15.84 15.17 15.38 14.98 2.46 3.68 6.97 6.59 6.49 Cd 264.98 270.91 155.71 225.66 86.04 144.71 49.62 19.14 16.21 21.11 18.73 32.63 17.12 54.18 269.7 260.32 51.66 45.17 47.57 44.02 263.79 0 225.69 17.70 15.58
81

Ni 1.49 5.05 2.12 2.17 2.25 8.77 2.16 2.11 2.00 1.92 1.88 1.91 2.10 2.15 4.97 4.82 5.00 4.92 4.81 4.80 1.12 2.15 2.12 1.89 1.79

Co 0.54 0.75 4.49 4.39 4.50 59.28 4.44 4.41 4.27 4.44 4.45 4.45 4.32 4.30 0.57 0.56 0.64 0.63 0.62 0.62 0.53 3.70 4.40 4.38 4.24

Mn 0.41 0.44 0.13 0.13 0.13 0.14 0.14 0.13 0.13 0.14 0.13 0.13 0.14 0.14 0.44 0.44 0.45 0.44 0.45 0.45 0.41 0.14 0.13 0.13 0.14

81

Table 32. Enrichment factor in Soil fraction-4 (250 m >X>188 m)

Location 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 Pb 3.06 3.14 0.86 0.84 1.32 2.15 0.90 0.49 0.43 0.51 0.42 0.45 0.87 1.55 2.88 2.50 1.30 1.08 1.13 0.96 2 1.28 0.57 0.47 0.34 Cu 4.04 4.48 6.92 6.9 2.63 9.53 2.19 3.94 3.82 4.00 3.88 3.90 2.17 3.09 13.36 12.96 9.38 8.71 8.93 8.52 2.97 6.09 6.29 3.68 3.56 Cd 69.35 75.69 166.79 229.8 32.58 182.55 29.41 15.01 12.33 16.45 13.65 26.18 0 34.35 73.66 63.97 42.06 36.03 38.26 34.95 65.91 0 229.91 13.28 11.34 Ni 1.90 4.52 1.8 1.91 1.99 9.85 1.89 1.86 1.76 1.68 1.66 1.69 1.8 1.88 4.4 4.30 4.4 4.39 4.29 4.28 1.57 7 1.8 1.65 1.57 Co 1.64 1.83 0.08 0 0.14 2.95 0.11 0.01 0.08 0.22 0.21 0.22 0.01 0 1.67 1.67 1.73 1.74 1.73 1.73 1.65 0.017 0.006 0.15 0.12 Mn 0.35 0.38 1.3 1.33 1.32 0.74 1.35 1.34 1.35 1.36 1.36 1.36 1.35 1.34 0.38 0.37 0.38 0.38 0.38 0.38 0.34 0 1.34 1.36 1.37

82

82

Table 33. Enrichment factor in Soil fraction-5 (188 m>X>125m)

Location 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 Pb 1.3 1.40 1.77 1.75 1.32 2.5 1.04 0.38 0.32 0.4 0.36 0.39 1.02 2.09 1.72 1.52 0.49 0.38 0.41 0.32 0.84 1.66 1.46 0.39 0.25 Cu 1.9 2.13 0.80 0.78 2.84 15.73 2.94 2.84 2.70 2.90 2.76 2.79 2.92 3.58 3.53 3.30 3.17 2.79 2.92 2.7 1.35 3.68 0.09 2.54 2.40 Cd 36.67 40.05 139.5 209.2 56.59 178.7 32.53 13.19 10.15 14.62 11.51 25.37 0 0 38.94 33.95 17.68 14.52 15.78 14.04 34.85 0 209.18 11.26 9.09 Ni 0.82 1.93 1.72 1.76 1.85 53.22 1.78 1.71 1.59 1.51 1.47 1.50 1.73 1.77 1.88 1.81 1.90 1.85 1.80 1.79 0.65 7.55 1.72 1.47 1.38 Co 0.33 0.43 0.09 0 0.27 0 0.13 0.008 0.009 0.152 0.146 0.153 0.01 0 0.35 0.34 0.37 0.37 0.37 0.36 0.33 0.02 0.005 0.08 0.078 Mn 1.23 1.24 1.14 1.14 1.13 0.71 1.2 1.15 1.15 1.16 1.17 1.1 1.23 1.22 1.24 1.24 1.24 1.25 1.24 1.25 1.23 1.42 1.14 1.17 1.18

83

83

Table 34. Enrichment factor in Soil fraction-6 (125m>X>106m)

Location 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 Pb 2.44 2.49 1.16 1.14 1.82 0.88 1.69 0.90 0.83 0.95 0.83 0.86 1.66 1.94 2.18 1.90 1.34 1.18 1.22 1.09 1.7 1.65 0.81 0.89 0.74 Cu 3.95 4.27 6.07 6.05 3.74 15.14 4.09 3.69 3.55 3.85 3.65 3.68 4.07 3.41 8.56 8.25 5.24 4.73 4.90 4.59 3.17 6.66 5.31 3.45 3.30 Cd 60.59 65.21 230.35 307.82 104.86 93.17 36.06 15.71 12.43 17.77 14.34 30.47 0 21.04 63.71 56.79 26.82 22.37 23.92 21.47 58.17 0 308.17 13.88 11.44 Ni 0.83 1.43 0.93 0.98 1.091 15.40 0.99 0.92 0.78 0.69 0.65 0.68 0.93 0.99 1.35 1.24 1.37 1.30 1.24 1.22 0.58 7.40 0.93 0.66 0.54 Co 3.19 3.32 0.27 0.1 0.3 2.59 0.31 0.17 0.17 0.34 0.33 0.3 0.17 0.16 3.21 3 3.25 3.2 3.25 3.26 3.21 0.2 0.159 0.26 0.05 Mn 0.67 0.69 0.14 0.14 0.13 0.12 0.15 0.14 0.14 0.15 0.15 0.15 0.15 0.15 0.7 0.69 0.70 0.7 0.70 0.70 0.68 0.15 0.14 0.14 0.15

84

84

Table 35. Enrichment factor in Soil fraction-7 (106m>X>90m)

Location 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 Pb 1.17 1.24 1.13 1.12 1.42 0.73 1.30 0.62 0.55 0.59 0.51 0.53 1.27 1.89 3.30 3.02 1.10 0.94 0.98 0.85 0.42 2.14 0.82 0.55 0.42 Cu 1.53 1.88 4.82 4.8 6.17 8.66 0.44 2.98 2.85 3.05 2.86 2.89 0.42 2.55 15.23 14.94 4.93 4.41 4.58 4.27 0.74 9.99 4.14 2.69 2.56 Cd 55.65 60.35 172.78 240.49 183.53 101.87 31.68 16.10 13.24 17.66 13.90 27.38 0 0 58.92 51.77 30.96 26.35 28.02 25.5 53.15 0 240.57 14.27 12.19 Ni 0 0.72 0.35 0.4 0.49 0 0.42 0.35 0.22 0.13 0.08 0.12 0.37 0.42 0.65 0.53 0.67 0.58 0.53 0.50 0.13 6.06 0.35 0.09 0.063 Co 0 0.14 0.18 0.09 0.24 16.22 0.26 0.10 0.07 0.21 0.21 0.21 0.14 0.13 0.02 0.02 0.07 0.06 0.06 0.05 0.01 0.15 0.08 0.14 0.09 Mn 0.19 0.21 0.14 0.14 0.13 2.32 0.14 0.13 0.14 0.14 0.14 0.14 0.14 0.14 0.21 0.21 0.21 0.20 0.21 0.21 0.19 0.14 0.13 0.14 0.14

85

85

Table 36. Enrichment factor in Soil fraction-8 (90m>X>75 m) Location 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 Pb 2.04 2.09 1.34 1.31 1.35 1.50 3.48 0.50 0.43 0.52 0.43 0.46 3.45 2.12 4.9 4.67 0.71 0.51 0.61 0.49 1.42 4.09 1.00 0.47 0.33 Cu 3.73 4.00 8.46 8.44 2.46 12.6 3.51 2.7 2.57 2.77 2.63 2.66 3.48 2.87 14.66 14.42 3.46 3.02 3.17 2.89 3.08 12.48 7.75 2.39 2.25 Cd 22.03 26.04 405.03 478.62 525.37 121.57 34.31 18.31 15.22 19.96 16.70 32.59 0 54.65 24.65 18.7 26.67 22.83 24.23 22.17 19.73 0 479.67 16.36 14.12
86

Ni 0 0.155 0.018 0.066 0.175 4.923 0.076 0.006 0.048 0.042 0.042 0.077 0.013 0.074 0.096 0.037 0.16 0.085 0.035 0.014 0.011 6.17 0.014 0.014 0.012

Co 0 0.12 3.96 3.86 3.98 2.79 4.15 3.88 3.73 3.90 3.92 3.92 4.02 4.00 0.02 0.01 0.05 0.05 0.04 0.04 0.043 4.51 3.87 3.84 3.68

Mn 0.16 0.17 0.13 0.13 0.13 0.66 0.13 0.13 0.13 0.14 0.14 0.14 0.131 0.13 0.17 0.17 0.18 0.17 0.17 0.17 0.16 0.13 0.13 0.13 0.14

86

Table 37. Enrichment factor in Soil fraction-9 (75m>X>53 m) Location 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 Pb 3.11 3.15 1.31 1.29 0.11 2.77 0.48 0.31 0.25 0.32 0.25 0.26 0.45 1.32 3.3 3.09 0.52 0.40 0.43 0.33 2.58 2.34 1.07 0.28 0.17 Cu 4.73 4.96 9.08 9.07 2.36 32.58 1.97 1.68 1.57 1.72 1.6 1.63 1.95 2.45 10.54 10.3 2.54 2.15 2.28 2.04 4.17 7.67 8.56 1.43 1.32 Cd 834.56 836.01 100.99 155.22 53.532 501.22 772.03 605.88 607.44 613.31 589.02 598.75 747.03 27.82 836.83 834.0 854.83 855.76 854.92 855.87 837.27 0 155.05 612.77 615.54
87

Ni 0 0.57 0.32 0.36 0.44 0 0.37 0.32 0.22 0.14 0.12 0.15 0.33 0.37 0.52 0.43 0.54 0.47 0.43 0.42 0.10 4.82 0.32 0.11 0.11

Co 0 0.10 0.13 0.05 0.17 20.47 0.182 0.06 0.007 0.12 0.11 0.12 0.09 0.08 0.015 0.015 0.052 0.047 0.04 0.04 0.01 0.11 0.047 0.06 0.06

Mn 0.13 0.15 0.1 0.09 0.09 2.42 0.09 0.09 0.09 0.1 0.1 0.1 0.09 0.09 0.15 0.15 0.16 0.15 0.15 0.15 0.14 0.09 0.09 0.09 0.09

87

Table 38. Enrichment factor in Soil fraction-10 (53 m>X>25m)

Location 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 Pb 1.99 2.03 1.14 1.13 0.11 9.53 0.92 0.31 0.26 0.32 0.26 0.27 0.89 1.27 2.74 2.57 0.48 0.38 0.41 0.33 1.55 2.11 0.92 0.29 0.19 Cu 3.57 3.77 5.35 5.33 0.22 46.10 3.07 1.66 1.56 1.71 1.58 3.36 3.05 2.14 4.44 4.23 2.32 1.99 2.1 1.91 3.10 3.61 4.86 1.44 1.35 Cd 34.95 37.81 128.84 177.59 11.49 604.47 22.63 28.56 26.58 30.004 29.96 23.29 0 13.22 36.84 32.52 40.74 38.11 39.08 37.64 33.36 0 177.49 27.65 26.245 Ni 0 0.43 0.26 0.29 0.36 0 0.32 0.25 0.161 0.095 0.082 27.96 0.279 0.318 0.392 0.319 0.404 0.354 0.318 0.303 0.008 4.346 0.256 0.070 0.068 Co 0 0.085 0.068 0 0.07 0 0.088 0.006 0.008 0.109 0.104 0.102 0.006 0 0.013 0.012 0.042 0.038 0.0362 0.0319 0.006 0.012 0.006 0.058 0.056 Mn 0.11 0.13 0.08 0.08 0.08 0.46 0.08 0.08 0.08 0.09 0.09 0.08 0.08 0.08 0.12 0.12 0.13 0.12 0.12 0.12 0.11 0.08 0.08 0.09 0.09

88

88

Table 39. Enrichment factor in Soil fraction-11 (X<25m)

Location 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 Pb 2.47 2.52 1.45 1.44 1.26 1.95 0.47 0.28 0.24 0.31 0.25 10.99 0.45 1.43 2.08 1.89 0.50 0.39 0.42 0.34 2 1.43 1.25 0.28 0.18 Cu 3.95 4.17 7.94 7.93 2.27 0 5.4 3.40 3.31 3.44 3.35 14.94 5.38 1.65 7.50 7.29 5.18 4.84 4.95 4.75 3.46 5.28 7.48 3.20 3.12 Cd 51.07 54.09 114.47 160.69 32.76 96.13 284.99 14.43 12.47 15.45 13.41 6042.3 263.47 0 53.094 48.50 24.93 22.03 23.11 21.52 49.38 0 160.56 13.193 11.783 Ni 0 41.24 27.81 27.84 27.76 0 28.49 27.85 27.92 27.91 27.98 14.72 28.46 28.44 41.28 41.31 41.28 41.4 41.28 41.38 0 32.26 27.87 27.97 28.14 Co 0 0.090 0.065 0 0.1 0 0.083 0.0059 0.007 0.101 0.097 3.142 0.006 0 0.013 0.0134 0.046 0.042 0.03 0.035 0 0.013 0.006 0.054 0.042 Mn 0.12 0.13 0.08 0.08 0.08 0.08 0.08 4.47 0.08 0.08 0.08 55.37 0.08 0.08 0.13 0.13 0.14 0.13 0.14 0.14 0.12 0.08 0.08 0.08 0.08

89

89

3.14 Multivariate analysis of Soil 3.14.1 Factor analysis:-Factor analysis was applied to eleven chemical parameters of soil (Table-4). Factors were extracted using principal components extraction method and subjected to varimax normalization rotation to interpret factor loading. Factor analysis extracts three factors (factors having Eigen value >1) which accounts for 83.62% variance of total variance represented in Table.40 Therefore these three factors are assumed to represent adequately the overall variance of data set. Table 40. Eigen value for factor analysis of soil
Cumulative Eigen value 4.86 7.22 9.19 Cumulative%

Factor 1 2 3

Eigen value 4.86 2.35 1.98

% Total Variance 44.21 21.40 18.00

44.21 65.62 83.62

Factor-1(F1), it accounts for 44.21% of total variance as shown in Table-40, summarizes that F1 is highly loaded with Fe, Mn K, Na, Co and moderately loaded with Pb (Table-41). Where Fe, Mn K, Na and Pb show positive loading and Co shows negative loadings. Factor one is considered to be lithogenic factor with anthropogenic input of Co. This fact is supported by high enrichment and geoaccumulation index of Co. Co rapidly adsorbed on the oxides of Mn and Fe [47] thats why it gets associated to this factor. But negative loading of Co indicates that, continent of this metal either controlled by different geochemical mechanism (e.g., Mobilization from the matrix. As in oxidizing environment sulfides of iron leads to oxidation and, acidic solutions are created which tend to decrease adsorption and promote mobility of metals) or it has other source of origin. Factor-2 (F2), it accounts for 21.4% of total variance, highly loaded with Ca, Mg and moderately with Ni. F2 is considered to be purely lithogenic. And high correlation (correlation coefficient 0.96 .table correlation matrix tables) between Ca and Mg revealed that, they have common origin that is dolomite. The above interpretation is supported geomorphology of the sampling location (Presence of dolomite rich soil in Mumbai) and association of Ni with the Ca and Mg in the F2. Dolomite is an ore of Ni. [48].

90

Factor-3(F3), it accounts for 18% of total variance is loaded with copper and cadmium. F3 is considered to be anthropogenic in origin. All the locations are highly enriched with copper and cadmium. Geoaccumulation index (Table-15) shows that all the locations are highly contaminated with Cd and moderately by copper. High Cu and Cd concentration is in soil may be due to use of fertilizers and fungicides used in the agricultural field as most of fertilizers contains elevated concentration of Cu, Cd and Pb [49]. Sediments and water of Ulhas estuary posses an elevated concentration of Cd followed by Cu and Pb [38,49]and its regular practice to excavate the bottom sediments from the Ulhas river and spared it to nearby land. So this disturbance in natural pattern plays major role in soil contamination by Cd, Cu and Pb (to an average level) of the study area. Table 41. Factor loading matrix of soil Variables Pb Cu Cd Fe Ni Co Mn Na K Factor 1 0.497 0.059 -0.100 0.972 0.037 -0.962 0.981 0.744 0.983 Factor 2 0.268 0.050 -0.191 -0.117 0.575 0.205 -0.113 0.291 -0.056 Factor 3 0.473 0.923 0.908 0.098 0.003 -0.045 -0.059 0.481 -0.104

Table 42. Correlation Matrix for soil parameters

Pb Pb Cu Cd Fe Ni Co Mn Na K Mg Ca 1.00 0.40 0.19 0.45 0.03 -0.38 0.36 0.64 0.39 0.05 0.17 Cu Cd Fe Ni Co Mn Na K Mg Ca

1.00 0.76 0.18 -0.01 -0.13 0.02 0.43 -0.05 0.03 0.05

1.00 0.02 -0.05 0.01 -0.11 0.34 -0.15 -0.16 -0.20

1.00 -0.08 -0.99 0.98 0.70 0.95 -0.34 -0.15

1.00 0.12 -0.02 0.29 0.00 0.32 0.35

1.00 -0.99 -0.64 -0.95 0.41 0.23

1.00 0.64 0.98 -0.35 -0.15

1.00 0.68 -0.01 0.18

1.00 -0.31 -0.10

1.00 0.96

1.00

91

Fig. 40 Factor-1 score plot

Fig. 41 Factor-2 score plot

Fig. 42 Factor-3 score plot 3.14.2 Cluster analysis. The main result of HCA performed on soil samples of 25 locations is the dendrogram (fig.41).The Qmode cluster analysis (using Wards linkage rule and Euclidian distance as distance measure and phenon line 10 classifies all the 25 sampling locations in to four clusters. The dendrogram obtained was used to define four geochemical groups (that illustrate the study area). These clusters can be best explained with the help of factor score plot (Fig.38, 39 and 40). From the factor score plot different clusters can be explained as follows. C1 includes location: 22, 13 and 7, these locations are totally unaffected by F1 and F2 but highly affected by F3. C2 includes locations: 25, 12, 24, 11, 10, 9 and 8 affected by F2 but unaffected by F1 and affected to an average extent by F3.

92

C-3 includes locations: 14, 23, 5, 3 and 4.these locations are totally unaffected by F1 and F2 but affected to an average level by F3. C4 includes locations: 1, 2, 6, 15, 16, 17, 18, 19, 20 and 21.these locations are highly affected by F1 but have mixed result for F2 and F3.

Ward`s method 35

30

25

Linkage Distance

20

15

10

0 L22 L13 L7 L25 L24 L11 L12 L10 L9 L8 L14 L5 L23 L4 L3 L20 L19 L18 L17 L6 L21 L16 L15 L2 L1

Fig. 43 Dendrogram of Q-Mode cluster analysis of soil samples 3.15 Multivariate Analysis of soils, sediments and water. Factor analysis by means of principal factor method and varimax normalization rotation can shed more light and help understanding these data. Table-43 and 44 represents factor analysis spread sheets of the common chemical parameters of soil sediment and water samples simultaneously. Table-43 Shows those four factors accounts for more than 84% of total variance. Factor-1 (F1) highly loaded with Fe (soil), Mn (soil), Mn (sediment), moderately with Fe (water), this revealed that they were from common parent material. This is supported by the fact that, Fe and Mn are chemically associated and is usually found in the same geologic environments in the form of Fe-Mn nodules. Hence the possible source may be mangniferous minerals. A negative loading of Fe (water) indicates that, water soluble Fe is from soil and sediment. F1 shows weak negative loading (-0.45) of Fe (sediment) may be shows its depletion of Fe in sediment by any geochemical process.

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Table 43. Eigen value spread sheet soil sediment and water
Factors Eigen value % Total variance 40.81 19.66 12.57 11.35 Cumulative Eigen value 4.89 7.26 8.76 10.13 Cumulative % 40.81 60.47 73.05 84.40

1 2 3 4

4.89 2.36 1.51 1.36

Table 44. Factor loading matrix of soils, sediments and water

Variables Pb(Soil) Cu(Soil) Fe(Soil) Mn(Soil) Cu(Water) Fe(Water) Mn(Water) Pb(Water) Cu(Sediment) Fe(Sediment) Pb(Sediment) Mn(Sediment) Expl.Var Prp.Totl Factor-1 0.241 0.013 0.944 0.966 -0.070 -0.581 0.008 0.153 0.356 -0.450 0.235 0.960 0.241 0.013 Factor-2 0.175 -0.012 0.082 0.046 0.858 -0.182 0.941 0.778 0.680 -0.496 0.242 0.073 0.175 -0.012 Factor-3 0.839 0.120 0.197 0.159 0.048 0.010 0.056 0.357 0.287 0.431 0.834 0.177 0.839 0.120 Factor-4 -0.333 -0.965 -0.136 0.015 -0.347 0.541 0.119 0.189 -0.232 0.067 0.061 0.013 -0.333 -0.965

Factor-2 is highly loaded with Cu (water and sediments), Mn (water), Pb (water) suggesting their common source of origin which is already explained in factor analysis of water samples, i.e., vehicular pollution. Moderate negative loading (-0.496) of Fe (sediment) in F2 indicates sorption and desorption mechanism playing main role at study site i.e., in the oxidation of sulphides of Fe, acidic solutions are created which tend to decrease adsorption and promote mobility of metals. i.e., desorption [50]. But at the same time significant correlation between Cu(sediment) and Cu (water)(correlation coefficient 0.64; Table-45), positive loading of Cu(sediment) in F2 can be justified on the basis of the fact that, Cu sorbed on organic matter in preference to other heavy

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metals [51,52], which is attributed to its high charge/radius ratio enabling it to form stable complexes with humic substances [53,54] irrespective of other metal. Factor-3 is loaded with Pb (soils and sediments), suggest theire common source of origin which is purely natural because of very low geoaccumulation indices value. Factor-4 is loaded with Cu (soil) revealed its external input due to human activity.

Table 45. Correlation Matrix for soils, sediments and water.

Variable Pb (Soil) Cu (Soil) Fe (Soil) Mn (Soil) Cu (Water) Fe (Water) Mn (Water) Pb (Water) Cu (Sediment) Fe (Sediment) Pb (Sediment) Mn (Sediment)

Pb (Soil) 1 0.40 0.45 0.36 0.27 -0.33 0.19 0.38 0.49 0.06 0.76 0.37

Cu (Soil)

Fe (Soil)

Mn (Soil)

Cu (Water)

Fe (Water)

Mn (Water)

Pb (Water)

Cu (Sediment)

Fe (Sediment)

Pb (Sediment)

Mn (Sediment)

1 0.18 0.02 0.32 -0.45 -0.13 -0.11 0.26 -0.02 0.03 0.04 1 0.98 0.12 -0.56 0.10 0.23 0.49 -0.32 0.35 0.96 1 0.03 -0.52 0.10 0.23 0.41 -0.30 0.32 0.97 1 -0.22 0.81 0.50 0.64 -0.29 0.19 0.03 1 -0.15 -0.23 -0.31 0.36 -0.20 -0.50 1 0.76 0.53 -0.34 0.24 0.11 1 0.60 -0.26 0.49 0.25 1 -0.37 0.42 0.46 1 -0.04 -0.34 1 0.36 1

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CHAPTER-4
CONCLUSIONS

he results obtained in this work after multivariate analysis (MVA), clearly reflects that MVA is an important statistical tool to deal with the problems in environmental matrices as

they are very complex system (consisting of number of interlinked natural processes coupled with anthropogenic activity). Multivariate statistical methods also allow the defining of geochemical zonation of aquifer systems and soils of the studied area, which takes into account effects of lithologies, anthropogenic contests and hydrogeology contest when dealing with aquifer systems. The study leads to following conclusions. 4.1 Water 4.1.1 Hydrogeochemical model study The non homogeneous distribution of different chemical species attributed due to differential mineralization of ground water of the study area. Most of the locations are affected by dissolution of gypsum and dolomite minerals leading to the predominance of Ca-Mg cations and mixed HCO3--SO42-anions in ground water except few locations. Gibbs-Boomerang diagram study revealed that hydro geochemical evolution of ground water of study site is mainly controlled by the weathering process and few locations showing deviation from boomerang is due to dissolution of salts of marine origin i.e. dissolution of salt pockets and cation exchange reaction. Stability diagram suggests predominance of kaolinite mineral at the study site. From this we can predict that the study area has a tropical wet (humid) climatic condition. As in humid tropical conditions, kaolinite mineral is present as a result of plagioclase weathering. Important result from study is that, there is no evidence of saline incursion to the ground water system.

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4.1.2 Multivariate statistical analysis of ground water. Factor analysis revealed that four factors controlling hydrogeochemical evolution of ground water of the study area are, a) weathering process (lithogenic), b) anthropogenic inputs of heavy metals by agricultural practice and vehicular pollution, c) a combined effect of lithogenic as well as anthropogenic i.e., use of NPK fertilizer and weathering of Jarosite-K and d) Overall mineralization of ground water of study area by gypsum and dolomite. Cluster analysis spatially divided the study area in to four clusters (or zones), where zone 1(C1) was having a Ca-Mg-SO4-Cl hydrochemical facies. Zone-2(C2) having a Ca-MgHCO3 facies, zone-3 Na-K-SO4- Cl type water and zone-4 (C4) has predominant Ca-Mg SO4-Cl type but highly affected by factor-2 (anthropogenic input of heavy metals.). it shows very good matching with Pipers classification. . 4.2 Soil 4.2.1 Multivariate statistical analysis of soil. Factor analysis shows that a) The positive association of Fe, Mn K, Na and Pb indicating their lithogenic origin and negative loading of Co suggests that its depletion due to either by any undergoing geochemical processes or its different source of origin. b) Soils of study area are enriched with dolomite mineral and good association of Ni envisages that dolomite is also an ore of Ni. c) Strong association of Cu, Cd in factor-3 suggests that, study site is contaminated by heavy metal content sediments of Ulhas river coupled with application of fertilizer used in agricultural land Cluster analysis of soils of studying area divides it into four zones considering all the factors in to account. C1 (Zone-1) soils were contaminated by Cu and Cd to an average level. These locations are totally unaffected by factor 1 and 2 (i.e. soil is neither enriched with dolomite mineral nor affected by weathering by process). C2 (zone -2), soil is enriched with dolomite and affected by F3 to an average degree. C3 (Zone-3) soils were relatively not affected by any of these factors except location-14(of zone 3) which is contaminated by Cu, and Cd to an average degree. C4 (Zone-4) soils were although control by all the three factors (weathering

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process, enriched with dolomite as well as contaminated with Cu and Cd.) weathering is the predominating process controlling chemical composition of soil.

4.2.2 Textural, enrichment factor and Geoaccumulation index study of soil Textural ,enrichment factor and Geoaccumulation index study revealed that soils of study area is practically uncontaminated w.r.t Fe, Mn and Pb (except location 1,2 and 21), moderately contaminated by Co and Ni at few locations. All the locations are contaminated with Cu and Cd.

4.3 Multivariate statistical study of soils, sediments and water. Simulations multivariate study of three matrices revealed that Fe in soils, sediments and water, Mn, in soils and sediments has common origin (i.e., soils and sediments have common parent rock and chemical compositions of ground water are controlled by chemical composition of nearby soil and sediment of the well). Similarly the Cu in water and sediments, Pb in soil and sediments has their common source of origin. Cu (soil) isolated in last factor indicate external input of the metal into the system. Complex geochemical process also controls the concentration of Fe (sediment), Cu (sediments and soil). .

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