CHAPTER-I INTRODUCTION 1.1 Groundwater Groundwater is water located under the ground surface in soil pore spaces and in the fractures of rock formations. Groundwater recharge can be made due to natural rainfall however natural discharge often occurs at springs and seeps, and can form oases or wetlands. Groundwater is often withdrawn for agricultural, municipal and industrial use by means of constructions and operations of extraction wells. The study of distribution and movement of groundwater in hydrogeology is called groundwater hydrology. The water cycle, also known as the hydrologic cycle describes the continuous movement of water on, above and below the surface of the Earth. The hydrologic cycle is used to model the storage and movement of water between the biosphere, atmosphere, lithosphere and hydrosphere. Water is stored in the reservoirs such as atmosphere, oceans, lakes, rivers, glaciers, soils, snowfields, and groundwater. Fig. 1.1 The hydrological (water) cycle 1 It moves from one reservoir to another by processes like: evaporation, condensation, precipitation, runoff, infiltration, transpiration, and groundwater flow as shown in Fig.1.1. The water moves from one reservoir to another, such as from river to ocean, or from the ocean to the atmosphere, by the physical processes of evaporation, condensation, precipitation, infiltration, runoff, and subsurface flow. The water goes through different phases like liquid, solid, and gas during these process and the key elements are discussed below: Evaporation: Evaporation is the process of a liquid becoming vaporized. In other words, a change in phase in the atmosphere occurs when substances change from a liquid to a gaseous, or vapor, form. Evaporation in the atmosphere is a crucial step in the water cycle. Condensation: The physical process by which a vapor becomes a liquid or solid, the opposite to evaporation is known as condensation. In meteorological usage, this term may be applied for the transformation from vapor to liquid. Condensation commonly occurs when a vapor is cooled and/or compressed to its saturation limit when the molecular density in the gas phase reaches its maximal threshold. Transpiration: It is the process by which moisture is carried through plants from roots to small pores on the underside of leaves, where it changes to vapor and then released to the atmosphere. Precipitation: It is the process of atmospheric discharge of water in the solid or liquid state on the earth surface. The various forms of precipitation are: rain, drizzle, snow, snow grains, snow pellets, diamond dust, hail, and ice pellets etc. Infiltration: It is the process by which water on the ground surface enters into the soil. Infiltration rate in soil science is nothing but the rate at which soil is able to absorb rainfall or irrigation. The rate of infiltration is affected by soil characteristics including ease of entry, storage capacity, and transmission rate through the soil. The soil texture and structure, vegetation patterns, water content, soil temperature, and rainfall intensity all these play a significant role in controlling the infiltration rate and capacity. For example, coarse-grained sandy soils have large spaces between each grain and allow water to infiltrate quickly. 2 1.2 Runoff: The portion of rainfall, which makes its way towards streams, rivers etc. after satisfying the initial losses etc. is known as runoff. The runoff may be classified as follows: Fig. 1.2 Different flow types (Musy, 2001) Surface Runoff: It is that portion of rainfall which enters the stream immediately after the rainfall. It occurs when all losses are satisfied and if rain is still continued, with the rate greater than infiltration rate then at this stage the excess water makes a head over the ground surface (surface detention). This tends to move from one place to another is known as overland flow. As soon as the overland flow joins to the streams, channels or oceans, termed as surface runoff. Sub-surface Runoff: The part of rainfall, which first leaches into the soil and moves laterally without joining the water-table to the streams, rivers or oceans is known as subsurface runoff. Base Flow: It is delays flow, defined as that part of rainfall which after talling on the ground surface infiltrated into the soil and meets the water table and flow to the streams oceans etc. The movement of water in this type of runoff is very slow and therefore it is also known as delayed runoff. It takes a long time to join the rivers or oceans. Sometimes base flow is also known as groundwater Thus, Total Runoff = Surface runoff + Base flow (Including sub - surface runoff) 3 flow. 1.3 Vertical Distribution of Groundwater: Water in the subsurface may be divided into two major zones: i) water stored in the unsaturated zone also known as vadose zone or zone of aeration and ii) water stored in the saturated zone. Soil pore spaces in the vadose zone, lying immediately below the surface. Here the small pore spaces between soil particles are filled with a mixture of water and air resulting in an area which is less than saturated zone. This zone may be divided with respect to occurrence and circulation of water into the uppermost zone of soil water, the intermediate zone and the capillary fringe, immediately above the water table. Water in this zone is called capillary water. This water moves upward from the water table by capillary action. Capillary water moves slowly in any direction. Water cannot be withdrawn from this zone for residential or commercial water supply purpose because the capillary forces hold it too tightly. The roots of trees, plants and crops, however, can tap into this water. The capillary fringe moves upwards and downwards together with the water table due to seasonal pattern. Fig 1.3a and 1.3b shows the distribution of water in the subsurface regions. Groundwater is water below the water table, falling entirely all rock interstices (void spaces) in the saturated zone. The water located in this zone can be withdrawn for various uses. The variation in the flow of groundwater depends on the type of rocks or other permeable material, the size of the pore spaces in the soil or rock, connectivity of pore spaces, and the configuration of the underground strata. Water Table: The upper surface of the zone of saturation is known as water table. At the water table, the water in the pores of the aquifer is at atmospheric pressure. The hydraulic pressure at any level within a water table aquifer is equal to the depth from the water table point and is referred to as the hydraulic head. When a well is dug in a water table aquifer, the static water level in the well stands at the same elevation as the water table. The groundwater table, sometimes called the free or phreatic surface, is not a stationary surface. This water table moves up and down due to various reason. It may rises when more water is added to the saturated zone by vertical percolation, and drops down during drought periods when the stored water flows out towards springs, streams, well and other points of groundwater discharge. 4 1.3a Subsurface distribution of water Fig. 1.3b Subsurface distribution of water 5 1.4 Groundwater Contamination: Groundwater contamination occurs when contaminants are discharged directly or indirectly into water bodies without adequate treatment to remove harmful compounds. The widespread use of chemical products, coupled with the disposal of large volumes of waste materials, poses the potential for widely distributed groundwater contamination. Hazardous chemicals such as pesticides, herbicides, and solvents, are used everywhere in everyday life. These and a host of other chemicals are in widespread use in urban, industrial, and agricultural areas. The largest potential source of groundwater contamination is the disposal of solid and liquid wastes. Waste disposal is not only the source of groundwater contamination but some additional sources like septic tank systems, agriculture, accidental leaks and spills, mining, artificial recharge, underground injection, and saltwater encroachment etc. are causes for groundwater contamination. 1.5 Sources of Groundwater Contamination: The contaminants can be introduced in the groundwater by means of natural occurring activities, such as natural leaching of the soil and mixing with other groundwater sources having different chemistry. These all are also introduced by planned human activities, such as waste disposal, mining, and agricultural operations. Almost every major industrial and agricultural site has in the past disposed of its wastes on site, often in an unnoticeable location. As we all know every municipality has had to dispose of its waste at selected locations within its proximity. Accidental spills of toxic chemicals have also occurred, often without particular attention to or concern for the consequences. Some practices of cleaning a toxic spill involve flushing it with water until it disappears into the ground. Past waste-disposal practices and dealing with spills have not always considered the potential for groundwater contamination. Factories and underground storage tanks are also a source of groundwater contaminantion. If a tank with water soluble liquid leaks the liquid travels down to the water table and then it dissolves in the groundwater. These pollutants flow as a plume along with the groundwater which can pollute wells and the plume path shown below in Fig. 1.4. 6 Fig. 1.4 Sources of pollution A problem of growing concern is the cumulative impact of contamination of aquifer from non-point sources such as those created by intensive use of fertilizers, herbicides, and pesticides. In addition, small point sources-such as numerous domestic septic tanks or small accidental spills from both agricultural and industrial source threaten the quality of aquifers. If the liquid that leaks is less dense than water, it floats on top of the groundwater table. Some of the liquid evaporates and travels upwards to the surface in the form of vapor fumes. Some of the liquid dissolves and travels as a plume in the groundwater. If the chemical is not very soluble in water then the major part of the liquid floats on the groundwater and flow along with the groundwater. With respect to mixing tendency the sources of contamination may be classified as follows: Point Sources: Point source contamination represents those activities where wastewater is routed directly into receiving water bodies. Point source contaminants in groundwater are usually found in a plume that has the highest concentration of the contaminants near by the source and diminishes concentration farther away from the source. The example of point source contaminantion can be enlisted as follows: Direct discharges from factories: raw materials and wastes may include pollutants such as solvents, petroleum products (e.g., oil and gasoline), or heavy metals etc. 7 Agriculture may also include point source contamination such as animal feeding operations, animal waste treatment lagoons, or storage, handling, mixing, and cleaning areas for pesticides, fertilizers and petroleum etc. Municipal point sources may include wastewater treatment plants, landfills, garages, motor pools and fleet maintenance facilities etc.. Other sources include mine discharge water and mine spoil run-off etc. Non-Point Sources: Non-point source contamination represents those activities where wastewater is routed indirectly into receiving water bodies due to environmental changes. The discharge from nonpoint sources are usually intermittent, associated with a rainfall or snowmelt event, and occur less frequently and for shorter periods of time than the discharges from point sources. Nonpoint sources of contamination are often difficult to identify, isolate and control. The example of non-point source contamination can be enlisted as follows: i) Automobile emissions, road dirt and grit, and runoff from parking lots etc. ii) Runoff and leachate from agricultural fields, barnyards, feedlots, lawns, home gardens and failing on-site wastewater treatment systems etc. and iii) Runoff and leachate from construction, mining and logging operations etc. 1.6 Aquifer and its Types: Aquifer: The word aquifer comes from two Latin words: aqua (water) and affero (to bring or to give). An Aquifer is geological formation, part of a formation or group of formations that contain sufficient saturated permeable material to yield significant quantities of water to well and springs. Water within the zone of saturation is at a pressure greater than atmospheric pressure. Sand and gravel deposits, sandstone, limestone, and fractured, crystalline rocks are examples of geological units that form aquifers. Aquitard: Aquitard is closely related to aquifer, is also derived from the two Latin words: aqua (water) and tardus (slow) or tardo (to slow down, hinder, delay). This means that aquitard does store water and is capable of transmitting it, but at a much slower rate than an aquifer so that it cannot provide significant quantities of potable groundwater to well and springs;e.g., sandy clay. 8 Aquiclude: Aquiclude is another related term, is also derived from two Latin words: aqua (water) and claudo (to confine, close, make inaccessible). Aquiclude is equivalent to an aquitard of very low permeability, which for all practical purposes; act as an impermeable barrier to groundwater and contaminant flow; clay is an example. Aquifuse: It is a relatively impermeable formation with no interconnected pores and hence neither containing nor transmitting water. It has very low porosity and very low permeability. For example, hard rock formations such basalts and granites which are free from fractures, faults or weathering. Aquifer may be broadly classified as follows: Confined Aquifer: A confined aquifer is located between layers of impermeable materials that restrict the flow of water into out of the aquifer. The pressure in this type of aquifer is high due to the confining layers that enable the water level in wells to rise above the typical water level of an aquifer. The pressure condition in a confined aquifer is characterized by a piezometric surface, which is the surface obtained by connecting equilibrium water levels in tubes or piezometers penetrating the confined layer. Unconfined Aquifer: An unconfined aquifer is a layer of water-bearing material without a confining layer at the top of the groundwater, called the groundwater table, where the pressure is equal to atmospheric pressure. The groundwater table, sometimes called the free or phreatic surface, is free to rise or fall. The groundwater table height corresponds to the equilibrium water level in a well penetrating the aquifer. Above the water table is the vadose zone, where water pressures are less than atmospheric pressure. The soil in the vadose zone is partially saturated, and the air is usually continuous down to the unconfined aquifer. Perched Aquifer: A perched aquifer refers to groundwater that is separated from the underlying main body of groundwater, or aquifer, by unsaturated rock or confine rock. The different types of aquifers discussed above are shown below in Fig. 1.5. 9 Fig. 1.5 Types of aquifers 1.7 Characteristics of Aquifer: Porosity: The void space in between the crystals or fragments that make up a rock represent porosity that can hold water. Porosity of an aquifer is the percentage of void spaces occupied by water or air in the total volume of rock which includes both solids and voids Vv 100% V (1.1) where Vv = The volume of all rock voids and V = The total volume of rock. Porosity can also be expressed as m d 1 d 100% m m where m = Average density of minerals particles 10 (1.2) d = Density of dry sample. Porosity is the most important property of rocks that enable storage and movement of water in the subsurface. It directly influences the permeability and the hydraulic conductivity of rocks and therefore the velocity of groundwater and other fluids that may present. In general, rock permeability and groundwater velocity depend on the shape, amount, distribution and interconnectivity of voids. On the other hand, voids depend on the depositional mechanisms of unconsolidated and consolidated sedimentary rocks, and on various other geologic processes that affect all rocks during and after their formations. Primary porosity is the porosity formed during the formation of rock itself, such as voids between the grains of sand, voids between minerals in hard (consolidated) rocks, or bedding planes of sedimentary rocks. Secondary porosity is created after the rock formation mainly due to tectonic forces (faulting and folding), which creates micro- and macro- fissures, fractures, faults and fault zones in the solid rocks. Factor Affecting the Magnitude of Porosity: In sediments or sedimentary rocks the porosity depends on grain size, the shapes of the grains, and the degree of sorting, and the degree of cementation. (i) 11 (ii) (iii) Fig. 1.6 Factor affecting the porosity of a sedimentary rock i) Well-rounded coarse-grained sediments usually have higher porosity than fine-grained sediments, because the grains do not fit together well. ii) Poorly sorted sediments usually have lower porosity because the fine-grained fragments tend to fill in the open space. iii) Since cements tend to fill in the pore space, highly cemented sedimentary rocks have lower porosity. Fig. 1.7 Types of rock intensities and the relation of rock texture to porosity Types of porosity with relation to rock texture a) Well-sorted sedimentary deposit having high porosity. b) Poorly sorted sedimentary deposit having low porosity. c) Well-sorted sedimentary deposit consisting of pebbles that are themselves porous, so that the deposit as a whole has a very high porosity. 12 d) Well-sorted sedimentary deposit whose porosity has been diminished by the deposition of mineral matter in the interstices. e) Rock rendered porous by solution. f) Rock rendered porous by fracturing. Permeability: Permeability is a measure of the degree to which the pore spaces are interconnected, and the size of the interconnections. Low porosity usually results in low permeability, but high porosity does not necessarily imply high permeability. It is possible to have a highly porous rock with little or no interconnections between pores. A good example of a rock with high porosity and low permeability is a vesicular volcanic rock, where the bubbles that once contains gas give the rock a high porosity, but since these pores are not connected to one another the rock has low permeability. It depends only on the physical properties of the porous medium, grain size, grain shape and arrangement, pore interconnection etc. Fig. 1.8 Characterization of permeability A thin layer of water is always attract to mineral grains due to the unsatisfied ionic charge on the surface. This is called the force of molecular attraction shown in Fig. 1.8. If the size of interconnections is not as large as the zone of molecular attraction, the water cannot move. Thus, coarse-grained rocks are usually more permeable than fine-grained rocks, and sands are more permeable than clays. 13 Factor Affecting the Magnitude of Permeability: i) Shape and size of sand grains: Rock composed of large and flat grain uniformly arranged with longest dimension horizontal then the permeability will be vary than the vertical permeability. ii) Lamination: Lamination of shale and platy minerals such as muscovite act as barrier to vertical permeability. iii) Cementation: Excess of cement in the pore space reduces the permeability. Intrinsic Permeability: The intrinsic permeability represents the physical flow properties of the geologic materials. It is a more rational concept as it is independent of fluid properties and depends on the properties of the medium. The larger the pore opening, the larger the intrinsic permeability of the medium. Hydraulic Conductivity: The hydraulic conductivity of a soil is a measure of the soil's ability to transmit water when submitted to a hydraulic gradient. It depends on the soil grain size, the structure of the soil matrix, the type of soil fluid, and the relative amount of soil fluid (saturation) present in the soil matrix. For a subsurface system saturated with the soil fluid, the hydraulic conductivity, K , can be expressed as follows (Bear 1972) K kg (1.3) where k is the intrinsic permeability of the soil, is the fluid density, is the fluid viscosity and g is the force due to gravity. 1.8 Darcy’s Law: In the mid-nineteenth century, Henry Darcy (1856) systematically studied the movement of water through sand columns. He was demonstrated from his experiment that the rate of flow, i.e., volume of water per unit time, Q is directly proportional to the crosssectional area, A , and head loss, h and inversely proportional to the length of the flow path, L shown in Fig. 1.9. 14 Fig. 1.9 Flow of water through an inclined porous media Q A h L Darcy’s law can be written as Q KA h L (1.4) where K Hydraulic conductivity of the porous medium and –ve sign indicates that Q occurs in the direction of the decreasing head. Here, h h Hydraulic gradient. L l Darcy’s law can also be written as: q Q h K A l (1.5) where q The Darcian velocity, also known as the specific discharge. Eq. (1.5) simply denotes that the specific discharge is the volume of water flow per unit time through a unit cross-sectional area normal to the direction of flow. Validity of Darcy’s Law: Darcy's law was established in certain circumstances: laminar flow in saturated granular media, under steady-state flow conditions, considering the fluid 15 homogenous, isotherm and incompressible, and neglecting the kinetic energy. Still, due to its averaging character based on the representative continuum and the small influence of other factors, the macroscopic law of Darcy can be used for many situations that do not correspond to these basic assumptions (Freeze and Cherry, 1979) saturated flow and unsaturated flow; steady-state flow and transient flow; flow in granular media and in fractured rocks; flow in aquifers and flow in aquitards; flow in homogeneous systems and flow in heterogeneous systems; flow in isotropic media and flow in anisotropic media. The most restrictive hypothesis of Darcy's law is one that consider the laminar flow, and the fluid movement as dominated by viscous forces. This occurs when the fluids are moving slowly, and the water molecules move along parallel streamlines. When the velocity of flow increases (for instance in the vicinity of a pumping well), the water particles move chaotically and the streamlines are no longer parallel. Therefore the flow is turbulent, and in that case the inertial forces are more influential than the viscous forces (Fetter, 2001). The ratio between the inertial forces and the viscous forces driving the flow is computed by the Reynolds number, which is used as a criterion to distinguish between the laminar flow, the turbulent flow and the transition zone. For porous media, the Reynolds number is defined as: Re vd (1.6) where is the fluid density, v is the velocity, d the diameter (of a pore), and the viscosity of the fluid. According to Bear (1972), Darcy' law with consideration of a laminar flow is valid for Reynolds number less than 1, but the upper limit can be extended up to 10 shown in Fig. 1.10. 16 Fig. 1.10 Range of validity of Darcy's law The inception of the turbulent flow can be located at Reynolds numbers greater than 60…100. Between the laminar and the turbulent flow there is a transition zone, where the flow is laminar but non-linear. In a general way, Darcy's law can be written: h q K L n (1.7) When n 1 , the law is linear and the flow is laminar which is the case of Darcy’s law given in Eq. (1.5). As per the Fig. 1.10, the hydraulic conductivity is the slope of the straight line in the interval of validity of Darcy's law. When n 1 and Re 100 , the law is non-linear and the flow is turbulent. 1.9 Contaminant Transport Mechanism Contaminant transport mechanisms usually concerned with movement in the saturated zone, however, in many cases the unsaturated zone may not be ignored. The details of contaminant transport mechanism are discussed below: Advection: - Advection (convection) is the movement of solute caused by the groundwater flow. The bulk movement of water through the aquifer causes solute transport via advection. Advection is the primary process by which solute moves in the groundwater system. Due to advection, non-reactive solute travel at an average rate equal to the seepage velocity of the fluid, 17 u vd (1.8) where u is the seepage or pore water velocity of the groundwater, is the porosity of the porous material, and vd is the flux of water (i.e., quantity of water per unit area per unit time). Diffusion: Diffusion is the transport process in which the chemical species migrate in response to a gradient in its concentration. This is a physical phenomena linked to the molecular agiation, and occurs in a fluid even at rest due to Brownian motion of particles. The result of this molecular agiation is that the particles are transferred from zones of higher concentration to those of lower concentration. A hydraulic gradient is not required for transport of contaminant by diffusion. The fundamental equation for diffusion is Fick’s first law which is, for one dimensional in free solution (i.e., no porous media), can be written as, J D D0 c x (1.9) where J D is the diffusive mass flux, x is the direction of transport and D0 is the ‘free solution’ diffusion coefficient. For diffusion in saturated porous material, a modified form of Fick’s first law is used, J D D 0 or where J D D c x (1.10) c x (1.11) is the dimensionless tortuosity factor and D is the effective diffusion coefficient. Dispersion: Dispersion is the spreading of the plume that occurs along and across the main flow direction due to aquifer heterogeneities at both the small scale (pore scale) and at the macroscale (regional scale). Dispersion tends to increase the plume uniformity as it travels downstream. Factors that contribute to dispersion include: faster flow at the center of the pores than at the edges, some pathways are longer than others, the flow velocity is larger in smaller pores than in larger ones. This is known as mechanical dispersion. 18 Hydrodynamic dispersion is the result of two processes, molecular diffusion and mechanical mixing or mechanical dispersion. Molecular diffusion is the process whereby ionic or molecular constituents move under the influence of their kinetic activity in the direction of their concentration gradients. Under this process, constituents move from regions of higher concentration to regions of lower concentration; the greater the difference, the greater the diffusion rate (Yong and Ahmed, 1999). Dispersion in porous material refers to the spreading of a stream or discrete volume of contaminants as it flows through the subsurface. For example, if a spot of dye is injected into porous material through which groundwater is flowing, the spot is enlarge in size as it moves down-gradient. Dispersion causes mixing with uncontaminated groundwater, and hence dispersion is a mechanism for dilution. Moreover, dispersion causes the contaminant to spread over a greater volume of aquifer than would be predicted solely from an analysis of groundwater velocity vectors. This spreading effect is of particular concern when toxic or hazardous wastes are involved. Dispersion is primarily importance in predicting transport away from point sources of contamination but is also influential in the spread of non point-source contaminants, although of lesser importance. Contaminants introduced into the subsurface from non-point sources spreads over a relatively large area because of the nature of the loading pattern. In this case, dispersion merely causes a relatively large zone of contaminated water to acquire some rough fringes. Dispersion is of interest because it causes contaminants to arrive at a discharge point (e.g., a stream or a water well) prior to the arrival time calculated from the average groundwater velocity. The accelerated arrival of contaminants at a discharge point is a characteristic feature of dispersion that is due to the fact that some parts of the contaminant plume move faster than the average groundwater velocity (Yong and Ahmed, 1999). Sorption: Sorption refers to the exchange to molecules and ions between the solid phase and the liquid phase. It includes adsorption and desorption. Adsorption is the attachment of molecules and ions from the solute to the rock material. Adsorption produces a decrease of concentration of the solute or equivalently, causes a retardation of the contaminant transport compared to the water movement. Desorption is the release of molecules and ions from the solid phase to the solute. 19 1.10 Advection-Dispersion Equation Hydrodynamic dispersion of solute through a porous medium is described by a partial differential equation known as advection-dispersion equation. This partial differential equation is of parabolic type (Guenther and Lee, 1988; Logan, 1994). Analytical solutions to advection-dispersion equations are of continuous interest because they present benchmark solutions to the problems in the assessment of degradation of hydro-environment (Bear and Verruijit, 1987). Let a solute be in the moving liquid which is entertained by the flow. Let us consider a small cubical element of volume dxdydz of sides PQ dx , PS dy , PA dz , surrounding a position P ( x, y, z ) in a Cartesian three dimensional frame of reference as shown below in Fig. 1.11. A B C D J ( x dx ) dydz Q P J x dydz S R Figure 1.11 Small cubical element Let the concentration at this position be C ( x, y , z ) . Mass entering the element through the face PADS is J x dydz . Mass leaving the element through the face QBCR is J ( x dx ) dydz . Net gain inside the element along x -axis J dydz J x J ( x dx ) dydz J x J x dxJ x .... dxdydz x x 20 (1.12) Similarly net gain inside the element along y -axis and z -axis can be obtained as J dxdydz y y J z , and dxdydz z , respectively. Total gain inside the element can now be written as J J J dxdydz x y z y z x By Fick’s law of diffusion, we have Jx C C C , Jy and J z x y z (1.13) where ve sign in first proportionality occurs because the x -axis direction is from higher concentration to lower concentration, and so on. The diffusive current densities J diff . ( J x , J y , J z ) and convective current density J conv. through the element are given as follows (Nield and Began, 1992) J x Dx and C C C ; J y Dy ; J z Dz x y z (1.14) J conv. uC (1.15) where Dx , D y , Dz are dispersion coefficients along x -axis, y -axis and z -axis, respectively and u (u x , u y , u z ) is the flow J ( J1 , J 2 , J 3 ) through the element can be written as J ( J1 , J 2 , J 3 ) J diff . J conv. velocity. Total current density (1.16) According to the conservation of solute mass inside the volume element, we have dxdydz or J J J C dxdydz 1 2 3 t x y z C J1 J 2 J 3 0 t x y z (1.17) (1.18) Using relationships (1.14-1.16), Eq. (1.18) becomes C C C C Dx Dy Dz (uxC) (u yC) (uz C) (1.19) t x x y y z z x y z 21 This equation is known as advection-dispersion equation in general form in three dimensions subject to the condtion that one of the axis coincides with direction of average velocity. In principle, the coefficients Dx , D y , and Dz may be function of position, time as well as concentration. If it is not then these components are called dispersion coefficients. In case all the coefficients in Eq.(1.19) are constants, the advection-dispersion equation becomes C 2C 2C 2C C C C Dx 2 Dy 2 Dz 2 u x uy uz t x y z x y z (1.20) The advection-dispersion Eq. (1.20) in one dimension along x -axis direction in general form becomes C 2C C Dx 2 u x t x x 1.10 (1.21) Initial and Boundary Conditions: Initial Condition: For transport problems, the initial conditions are represented by the extent and concentrations of an existent contaminant plume at the starting time of simulation. The measured concentration distribution of a plume may not be used as starting point for a transient transport simulation due to the scarce information. The monitoring program usually does not predict a large number of measuring points and frequently the highest-occurring concentrations are not even registered. A solution is to consider estimated source terms as starting point for the transport model. Boundary Conditions: The different types of boundary conditions are described as follows: i) First kind or Dirichlet condition: It is also named as concentration-type condition or concentration boundary is used to represent known recharge with known concentration (the advective flux) at the input end of the model. Usually, the transport model area is chosen large enough so that the contaminants do not reach the outflow end. In this way one avoids introducing unknown concentrations at the outflow boundary; at the same time, the dispersive flux at the boundaries is set to zero (Spitz and Moreno, 1996). Structures like leaking landfills, ponds, infiltration beds, injections wells can be modeled by a prescribed flux with associated concentration. The same conditions can be used for water losses from irrigation systems, sewage systems or industrial areas. To model a source of pure 22 contaminant (oil, mine waste) prescribed concentration can be imposed inside the model area. Surface bodies serving as output for contaminated groundwater can be modeled by using a prescribed head and concentration boundary; in this case, the value of the concentration corresponds to the concentration of the surface water body. ii) Second kind or Neumann condition: It is specifying the concentration gradient prescribes only dispersive flux, meaning it neither prescribes total mass flux (advective and dispersive flux combined), nor the advective flux alone (Spitz and Moreno, 1996). As shown before, at the boundaries the dispersive flux is set to zero. The same value is considered along the impervious boundaries. iii) Third kind, mixed or Cauchy condition: It prescribes the total contaminant flux on the boundary as a linear combination of the concentration (advective flux) and concentration gradient (dispersive flux). For large periods of time, due to mixing across the boundary the dispersive flux diminishes and the third kind condition reduces to first kind condition. When the advective flux tends to zero, the third kind condition is approaching the second type condition. 1.12 Literature Survey Subsurface water is generally divided into two major types: phreatic water or soil moisture in the unsaturated zone and groundwater in the saturated zone. Groundwater is a long-term reservoir of the natural water cycle, which originates from rainfall or snow. The groundwater resources are being utilized for drinking, irrigation and industrial purposes. Groundwater resources also play a major role in ensuring livelihood security across the world, especially in economies that depends on agriculture. India is now the biggest user of groundwater for agriculture in the world (Shah, 2009). Groundwater irrigation has been expanding at a very rapid pace in India since the 1970s. The data from the Minor Irrigation Census conducted in 2001 shows evidence of the growing numbers of groundwater irrigation structures (wells and tube wells) in the country (Shankar et al., 2011). The natural and generally high quality groundwater is under attack today by many sources and types of contaminants which are associated with human activities and land use (Gelhar and Wilson, 1974). Therefore, groundwater systems, planning, and management are needed for judicious use of groundwater. In recent years, an increasing threat to 23 ground- water quality due to human activities has become of great importance. The adverse effects on groundwater quality are the results of man's activity at ground surface, unintentionally by agriculture, domestic and industrial effluents, unexpectedly by subsurface or surface disposal of sewage and industrial wastes. The intensive use of natural resources and the large production of wastes in modern society often pose a threat to groundwater quality and have already resulted in many incidents of ground water pollution. Pollutants are being added to the groundwater system through human activities and natural processes. The groundwater pollution normally traced back to four main sources such as industrial, domestic, agricultural and environmental pollution by Sharma and Reddy (2004). Solid waste from industrial units is being dumped near the factories, which is subjected to reaction with percolating rain water and reaches the ground water level. Groundwater pollution caused by human activities usually falls into one of two categories: point-source pollution and non point-source pollution. Simultaneous movement of solute and water occurs in every imaginable natural flow system in soil (Waric et al., 1971). This phenomenon occurs during leaching of solutes, movement of fertilizers and pesticides, and land reclamation activities (Bresler and Hanks, 1969). Fertilizers and pesticides applied to crops finally may reach underlying aquifers, particularly if the aquifer is shallow and not "protected" by an overlying layer of low permeability material, such as clay. After infiltration through soil these pollutants reach the groundwater table. As soon as the pollutant reaches the groundwater table, it starts spreading along the groundwater flow in horizontal directions. Drinking-water wells located close to cropland sometimes are polluted by these agricultural chemicals. The percolating water picks up a large amount of dissolved constituents and reaches the aquifer system and contaminates the groundwater. The problem of groundwater pollution in several parts of the country has become so acute that unless urgent steps for detailed identification and abatement are taken, extensive groundwater resources may be damaged. The concentration of pollutants decreases due to the hydrodynamic dispersion and other attenuation effects, like adsorption, first order decay terms, etc. Coal mines are another major source of contaminants. When pyrite rocks associated with coal mining are exposed to oxygen they are oxidized to generate acid mine drainage. The waste then flows into streams and infiltrates into aquifers. A vast majority of 24 groundwater quality problems are caused by contamination, over-exploitation, or combination of these two. Most groundwater quality problems are difficult to detect and hard to resolve. The solutions are usually very expensive, time consuming and not always effective. Groundwater quality is slowly but surely declining everywhere. The wide range of contamination sources is one of the many factors contributing to the complexity of groundwater assessment. Groundwater Contamination is more complex than surface water mainly because of difficulty in its timely detection and slow movement. The cleanup of contaminated groundwater is very different from clean up of waste-water on the surface. The most obvious difference is that with groundwater clean-ups, the water body is actually being cleaned. In surface water cleanups, we control and treat the waste water that is entering a water body. The water body, river or lake actually cleans itself once we stop putting pollutants into it. Groundwater is not able to clean itself; hence we must clean-up the source of pollutants as well as the aquifer itself. With growing recognition of underground water resources efforts are increasing to prevent, reduce and eliminate groundwater contamination by the researchers in various discipline. The researchers and scientists from various disciplines like, Hydrogeology, hydrology, civil engineering, environmental science engineering etc. putting their best effort to solve this problem by various means. Mathematical modeling is one of the powerful tools to project the existing problems and its appropriate solution. These models are based on certain simplifying assumptions, have been used to predict groundwater flow and solute transport. A solute transport model is an essential tool for assessing environmental risks to groundwater resources. These processes are described by a partial differential equation (PDE) of parabolic type, and it is usually known as advective-dispersive equation (ADE). This transport equation is one of the fundamental equations in hydrodynamics and plays a significant role in water quality and solute transport modeling. A solute transport model have been solved analytically for simple cases and numerically for more complicated systems. Many solute transport problems have been solved numerically (Rastogi, 2007) but analytical solutions are still pursued by many scientists, because they can provide physical insights into problems (Batu, 2006). 25 Analytical solutions for solute transport equation were developed by many researchers (Gershon and Nir, 1969; Gelher and Collins, 1971; Marino, 1974; van Genuchten, 1981; Hunt, 1983) to describe one dimensional solute transport. Kumar (1983a) presented analytical solutions for dispersion (in a finite non-adsorbing and adsorbing porous media) which was controlled by flow (with unsteady unidirectional velocity distribution) of low concentration fluids towards a region of higher concentration. van Genuchten and Wierenga (1986) compiled analytical solutions of the advective-dispersive equation (ADE) for different boundary conditions in finite and semi-infinite domains. Lindstrom and Boersma (1989) obtained an analytical solution of the general onedimensional solute transport model for confined aquifers. Yates (1990) developed an analytical solution for describing the transport of dissolved substances in heterogeneous porous media with a distance-dependent dispersion relationship. An analytical solution for one-dimensional dispersion in unsteady flow in an adsorbing porous medium was obtained by Yadav et al. (1990). Fry and Istok (1993) derived an analytical solution for the advection-dispersion equations with rate limited desorption and first-order decay, using an eigenfunction integral equations method. An analytical solution of the one-dimensional time-dependent transport equation was also discussed by Basha and Habel (1993). Sim and Chrysikopoulos (1996) were presented analytical solutions of one dimensional virus transport in saturated, homogeneous porous media with time-dependent inactivation rate coefficients. Chrysikopoulos and Sim (1996) were also developed a stochastic model for one-dimensional virus transport inhomogeneous, saturated, semi-infinite porous media. Logan (1996) presented an analytical model of solute transport in porous media with scale dependent dispersion and periodic boundary conditions. An analytical solution for contaminant transport in non-uniform flow was presented by Tartakovsky and Federico (1997). Kumar and Kumar (1998) presented analytical and numerical solutions for homogeneous and inhomogeneous semi infinite aquifers respectively. The water table variation in response to time varying recharge was explored by Rai and Manglik (1999). Analytical solutions for solute transport in saturated porous media with semi-infinite or finite thickness were discussed by Sim and Chrysikopoulos (1999). Virus transport in unsaturated porous media was also discussed by Sim and Chrysikopoulos (2000). Kumar 26 and Yadav (2000) have discussed a solute dispersion along and against sinusoidally varying unsteady velocity through finite aquifers Analytical/Numerical solutions. A onedimensional transport model for simulating water flow and solute transport in homogeneous–heterogeneous, saturated–unsaturated porous media using the discontinuous finite elements method was presented by Diaw et al., (2001). Didierjean et al., (2004) was discussed some analytical solutions of one-dimensional macro-dispersion in stratified porous media by the quadrupole method with different types of heterogeneous porous medium. An analytical solution to transient, unsaturated transport of water and contaminants through horizontal porous media was discussed by Sander and Braddock (2005). Recently some more investigations have been carried out for one-dimensional solute transport in saturated or unsaturated porous media using different mathematical approaches. Analytical solutions for sequentially coupled one-dimensional reactive transport problems were discussed by Srinivasan and Clement (2008). Longitudinal dispersion with time dependent source concentration along unsteady groundwater flow in semi-infinite aquifer was presented by Singh et al., (2008). An analytical solution for onedimensional contaminant diffusion through multi-layered media is derived regarding the change of the concentration of contaminants at the top boundary with time by Chen et al., (2009). Taylor-Galerkin B-spline finite element method for the one-dimensional advectiondiffusion equation was also discussed by Kadalbajoo and Arora (2009). Jaiswal et al., (2009) presented an analytical solution for temporally and spatially dependent solute dispersion of pulse type solute concentration in one-dimensional semi-infinite media. Solute transport for one-dimensional homogeneous porous formations with time dependent point-source concentration was presented by Singh et al., (2009). Singh et al., (2010b) also presented an analytical solution for solute transport along and against time dependent source concentration in homogeneous finite aquifers. P´erez Guerrero and Skaggs (2010) were derived an analytical solution for one-dimensional advection-dispersion transport equation with distance dependent coefficients in heterogeneous porous media. Kumar et al., (2010) were derived analytical solutions for one dimensional advection-diffusion equation with variable coefficients in steady flow through an inhomogeneous medium, temporally dependent solute dispersion along uniform flow through homogeneous and temporally 27 dependent flow through inhomogeneous medium. Analytical solution for contamination diffusion in doubled layered porous media was also discussed by Li and Cleall (2010). An analytical solution of the convection–dispersion–reaction equation is obtained for a finite one-dimensional region with a pulse boundary condition was presented by Ziskind et al., (2011). Qiu et al., (2011) were explored a transient storage model with space-variable coefficients and solved using the generalized integral transform technique (GITT) coupled with Laplace transform method. Analytical solutions of one-dimensional advectiondiffusion equations (ADE) subject to an initially pollutant-free domain and varying pulsetype input conditions using Laplace integral transform technique (LITT) in semi-infinite heterogeneous medium presented by Singh et al., (2012). Multidimensional solute transport problems in saturated media have been attracting the attention of many researchers. Two-dimensional solute transport problems involve both longitudinal as well as transverse dispersion along with porous media flow in addition to advection. Bruce and Street (1967) presented both longitudinal and lateral dispersion in semi-infinite non-adsorbing porous medium in a steady flow field for a constant input concentration. van Genuchten et al., (1977) were discussed the simulation of twodimensional contaminant transport with isoparametric hermitian finite element. Hunt (1978 a, b) presented one, two and three-dimensional solutions for instantaneous, continuous, and steady-state pollution sources in uniform groundwater flow. Latinopoulos et al., (1988) presented a method to obtain the analytical solutions for chemical transport in twodimensional aquifers in which a constant velocity field, linear adsorption, and first-order decay were considered. A generalized two-dimensional analytical solution for hydrodynamic dispersion in bounded media with the first-type boundary condition at the source was discussed by Batu (1989). Batu and van Genuchten (1990) were discussed first and third-type boundary conditions in two-dimensional solute transport modeling. A generalized two-dimensional analytical solute transport model in bounded media for flux type finite multiple sources was discussed by Batu (1993). A mathematical modeling for transient solute transport resulting from the dissolution of a single component nonaqueous phase liquid (NAPL) in two-dimensional, saturated, homogeneous porous media were presented by Chrysikopoulos et al., (1994). Analytical solution for two dimensional 28 transport equations with time dependent dispersion coefficients was derived by Aral and Liao (1996). Tartakovasky (2000) presented an analytical solution for two-dimensional contaminant transport during groundwater extraction. Vogel et al., (2000) also discussed the solute transport in a two-dimensional dual-permeability system with spatially variable hydraulic properties in heterogeneous soil system. Two dimensional analytical solution, using Hankel transformation, was presented by Kumar and Kumar (2002). Chen et al., (2003) discussed a Laplace-transformed power series (LTPS) technique to solve a twodimensional ADE in cylindrical co-ordinate with non-axisymmetry solute transport in a radially convergent flow field. Some analytical solutions for two-dimensional convectiondispersion equation in cylindrical geometry with chemical decay or adsorption-like reaction inside the liquid phase were discussed by Massabo et al., (2006). Chen (2007) was presented a two-dimensional power series solution for non-axisymmetrical transport in a radially convergent tracer test with scale dependent dispersion. James and Jawitz (2007) were also discussed a two-dimensional reactive transport ADE model using a splitting technique where advective, dispersive and reactive parts of the equation were solved separately. A two-dimensional contaminant transport through saturated porous media using a mesh free method called the radial point interpolation method (RPIM) with polynomial reproduction, was derived by Kumar and Dodagourdar (2008). Zhan et al., (2009) presented an analytical solution of two-dimensional solute transport in an aquifer-aquitard system by maintaining rigorous mass conservation at the aquifer-aquitard interface with the first-type and the third type boundary conditions. An Analytical Solution for the Transient Two-Dimensional Advection–Diffusion Equation with Non-Fickian Closure in Cartesian Geometry by the Generalized Integral Transform Technique (GILTT) were derived by Buske et al., (2010). Singh et al., (2010a) were derived an analytical solution using Hankel Transform Technique (HTT) for two-dimensional solute transport in finite aquifer with time dependent source concentration. Lin et al., (2011) were presented an analytical solution of two-dimensional ADE in cylindrical geometry, finite length medium with thirdtype inlet boundary conditions has been discussed using the second kind finite HTT and the generalized integral transform technique (GITT) and explored the fact that the influence of exit boundary conditions diminishes, when Peclet number increases. Analytical solutions 29 for two-dimensional ADE in cylindrical coordinate subject to the third- type inlet boundary condition were presented by Chen et al., (2011a). Chen et al., (2011b) were also discussed the exact analytical solutions for two-dimensional ADE in cylindrical coordinates subject to finite exit boundary. Zhang (2011) was discussed a two-dimensional simulation study on longitudinal solute transport and longitudinal dispersion coefficient. Jaiswal et al., (2011) were presented analytical solutions obtained for two-dimensional ADE describing the dispersion of pulse-type point source along temporally and spatially dependent flow domain respectively, through a semi-infinite horizontal isotropic medium. Yadav et al., (2012) were derived an analytical solution for horizontal solute transport from a pulse type source along temporally and spatially dependent flow. Three-dimensional analytical models for solute transport in finite and semi-infinite porous media were discussed by Goltz and Roberts (1986), Yates (1988), Leij et al., (1991, 1993), Chrysikopoulos (1995) etc. A generalized three-dimensional analytical solute transport model for multiple rectangular first-type sources was discussed by Batu (1996). Sim and Chrysikopoulos (1998) were presented three-dimensional analytical solutions for solute transport in saturated, homogeneous porous media with semi-infinite or finite thickness. Zoppou and Knight (1999) derived an analytical solution for the two- and threedimensional ADE with spatially variable velocity and diffusion coefficients. Park and Zhan (2001) discussed analytical solutions of contaminant transport from finite one-, two-, and three-dimensional sources in a finite thickness aquifer using Green’s function method. An analytical solution of the advection-diffusion transport equation using a change-of-variable and integral transform technique were presented by P´erez Guerrero et al., (2009). 1.13 Numerical Input Data To compute the analytical solutions of the problems present in this thesis, the input data of initial groundwater velocity and dispersion coefficient are required. The input values are chosen on the basis of inputs available in the previous works. Some of the works and values of these two parameters are enlisted below in the form of table. 30 Author Seepage velocity (u ) 2 1979 35 cm /day and 8x10-4 cm/day 1981 0.005 ft/min 1981 25cm/day Dispersion (D) 2 0.1 cm /sec and 0.0001 cm2/sec 1984 1.0 m/day Dx = 7.0 m2/day, D y = 2.0 m2/day 1988 0.1 m/day Dx =5.0 m2/day, D y = 0.5 m2/day Chrysikopoulos et al. Aral and Tang 1990 0.5 m/day 0.02 m2/day 1992 0.25 m/day Dx = D y = 1.0 m2/day Sim and Chrysikopoulos Huang et al. Kumar and Kumar Jaiswal et al. 1995 4 cm/h 15 cm2/h 1996 5m/day 1998 0.01 km/day 2009 0.25 km/year 500 m2/day and 100 m2/day 0.1 km2/day 0.14 km2/year Perez Guerrero et al., Zhan et al. 2009 1 cm/hour Dx 0.18 cm / hour 2009 0.1 m/day or 1.16 106 m/s 2010 0.60 km/year and 1.60km/year 2010 100 m/year 1.16 109 m2/s 0.70 km2/year and 1.71km2/year 2011 1 m/day 2011 1 m/hour 20 m2/day DL 1, 0.1, 0.05 m 2 / hour Al-Niami and Ruston Marino van Genucheten and Alves Carnahan and Remer Latinopoulous Kumar et al. Perez Guerrero et al. Chen and Liu Chen et al. Year 0.1 ft2/min 35 cm2/day 10 m2/year DT 0.1, 0.01, 0.005 m 2 / hour The values for these input variables in the present thesis are chosen which match with above. Also in the two dimensional analysis, the lateral component values of the initial velocity and dispersion coefficient are taken one-tenth of their respective longitudinal components. 31
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