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Lecture 22 to 23

Lecture 22 to 23. Introduction to GW contamination and Solute partitioning. Sources of GW contamination. What do we mean by a contaminant Quality impacted by Natural processes Runoff from agricultural & urban watersheds Waste disposal practices Accidental spills and leaks.

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Lecture 22 to 23

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  1. Lecture 22 to 23 Introduction to GW contamination and Solute partitioning

  2. Sources of GW contamination • What do we mean by a contaminant • Quality impacted by • Natural processes • Runoff from agricultural & urban watersheds • Waste disposal practices • Accidental spills and leaks

  3. Groundwater contaminants The contaminants of concern can be : • Organic chemicals • Metals • Radionuclides • Inorganic chemicals (cl, so4m na..) Dealing with the different contaminants will depend on distribution and behavior (characteristics)

  4. Some Characteristics • Mobility • Lead and other metals are immobile (soil contaminants) • Time since release • Solubility in water • Aqueous or non-aqueous phase • LNAPL and DNAPL

  5. How humans are affected • Soil contaminants may reach through skin or breathing vapors (children) • Dissolved contaminants can reach drinking water for humans or food chain • Significant pollution of water resources

  6. Nature of Groundwater Contamination • Most of the time late discovery (hidden nature) • Clean up is difficult, requires long time, high cost (heterogeneity) • Often problem is made worse

  7. Mechanisms of mass transport • Advection: movement of contaminants with flowing water • Diffusion: movement of contaminants due to concentration gradients • Mechanical dispersion: movement of contaminants due to the complex nature of flow in porous media • Hydrodynamic dispersion combines the last two

  8. Mathematical expressions for solute mass flux

  9. Combined flux Often the two processes are combined using a combined coefficent D called the hydrodynamic dispersion coefficient If we include advection then:

  10. J in J out Δ x Mass balance equation Rate of mass accumulation in C.V. = - net rate of mass flux out + source Consider saturated porous media with dissolved conservative solute With steady 1-d flow in x-direction

  11. Mass balance equation cnt For 1-d dissolved solute transport the Advective-dispersive equation is :

  12. General form of the advection dispersion equation for solute transport in saturated porous media Homogeneous steady uniform velocity and constant dispersion coefficients The equation becomes:

  13. Multiphase contamination in porous media

  14. Solute partitioning

  15. terminology • A solute is a chemical substance dissolved in a given solution (i.e. water, air, OIL) cw, ca, co • a phase is a separate, homogeneous part of a heterogeneous system (w,a,o,soil) • A physical interface exists between each of the phases in contact, which is a dividing surface between the phases that compounds can migrate across.

  16. Study transport and fate of contaminants • deal with a multiphase system consisting of water, air, and soil and in some cases OIL • Individual chemical constituents partition themselves among the various phases according to thermodynamic equilibrium principles and mass transfer kinetic factors • models are needed to describe the mass transport processes, and solute partitioning among the various phases that are present must be quantified

  17. Continued • Most petroleum products are mixtures of many individual constituents. The physical characteristics of a mixture may be estimated from the characteristics of the individual constituents that form the mixture • A petroleum hydrocarbon consists of more than one hundred chemical constituents. These constituents may dissolve in or attach to any or all of the phases present • When considering the transport of constituent within the multiphase system how the concentrations of constituents within the various phases relate to each other

  18. Assumption • The local equilibrium assumption assumes that the problem is separable • even though a solute can exist in anyone of four phases, at any point where two of these phases touch each other, the equilibrium set up at that interface is assumed to hold independent of the presence of the other phases • the presence of NAPL does not affect the water-soil partitioning properties of a medium; the total amount of material just gets shared • If the constituent of interest is lost from one phase, then the other phases serve as a contaminant reservoir that supplies the phase that is losing mass while maintaining equilibrium partitioning

  19. Partitioning in a multiphase system

  20. Partitioning between air and water phase • Henry's law states that water-vapor partitioning is described by a linear relashon under equilibrium conditions. This relationship is ca = KH cw Where KH is the Henry's law constant KH =K’H /RT

  21. Partitioning between solid and water phase • Assuming linearsorption isotherm under equilibrium conditions. This relationship is cs = Kd cw Where Kd (volume/mass) is the distribution coefficient which depends on organic carbon in soil and the properties of the organic compound. High for hydrophobic organics

  22. Partitioning between free product and water phase • Raoult’s law states that water concentration is equal to the constituent solubility (pure) multiplied by the mole fraction of the constituent This relationship is c0 = Ko cw = KoSk Xk Where Ko is NLAPL water partitioning coefficient

  23. Partitioning between free product and water phase Where: ώ = molecular weight S = solubility C = concentration in OIL

  24. Bulk concentration for a constituent is the sum of the four phases m = mass per bulk volume for a constituent say k Bw = bulk water partitioning coefficient

  25. General hydrocarbon contamination After a leak there will be a contamination zone. This zone will in general contain four phases (air, water, soil, NAPL) The NAPL consists of many constituents (see table for gasoline) that Can dissolve or attach to the four phases Are the constituent concentrations in the various phases related? We may assume linear equilibrium

  26. P.C. Characteristics of fluid mixtures Ideal mixture

  27. Mole fraction Molecular weight of mixture Molar volume Partial molar volume Mixture density

  28. Problems

  29. Short note about half-life In this example we calculated the time required ro reduce the concentration to half and called it half life. This is used in dealing with first order reactions governed by an equation like: It can be shown to be:

  30. Compositional model Here we take care of changes in aqueous concentration due to the change in composition due to the loss of mass leached combining With the following relations

  31. Example-Compositional model Solubility TCE = 1.1 g/l, PCE = 0.15 g/l, CTC= 0.825 g/l

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