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Contaminant Transport

Mechanisms and Principles

BASIC DEFINITIONS

Ground surface

unsaturated zone

ground

surface

(BGS)

Capillary fringe

Water table Water-table, phreatic,

Saturated zone or unconfined aquifer

Confining bed

Confined aquifer or

artesian aquifer

Capillary fringe may be >200 cm in fine silt

In capillary fringe water is nearly saturated, but held in tension in soil pores

MICRO VIEW OF UNSATURATED ZONE

Contaminant concentrations:

concentration in water

air

Cg, mg/L or ppmv

concentration in gas

solid

Cs, gm/kg

concentration in solids

PARTITIONING RELATIONSHIPS

Cs mg/kg solid

Solid ↔ water = Kd =

Cw mg/L water

Kd = partition coefficient

=H= 3

Cw mg/m water

H = Henry’s Law constant

HENRY’S LAW CONSTANT

H’ is dimensionless

H’ = H/RT

R = gas constant = 8.20575 x 10-5 atm m3/mol °K

T = temperature in °K

NOTE ON SOIL GAS CONCENTRATION

ppmv = parts per million by volume

Cg (ppmv) =

molecular weight g/mole

VOLUME REPRESENTATION

Gas volume, Vg

Void volume, VV

Water volume, VW

Total volume, VT

Solid volume, VS

VOLUME-RELATED PROPERTIES

Bulk density = ρb = mass of solids

total volume

Porosity = n = θ = VV/VT

Volumetric water content or

water-filled porosity = θW = VW/VT

Saturation = S = VW/VV

Gas-filled porosity = θg (or θa) = Vg/VT

θW + θg = n

CONTAMINANT CONCENTRATION

IN SOIL

CT = ρb Cs + θw CW + θg Cg

CT = ρb Cs + n CW

NOMENCLATURE FOR DARCY’S LAW

Q = KiA

K = hydraulic conductivity

i = hydraulic gradient = dh/dL

A = cross-sectional area

Velocity of ground-water movement

u = Q / n A = q / n = K i / n = average linear velocity

n A = area through which ground water flows

q = Q / A = Darcy seepage velocity = Specific discharge

For transport, n is ne, effective porosity

ADVECTIVE FLUX

material with it → Advective Flux

ground-water advection

DIFFUSIVE FLUX

motion) – proportional to concentration gradient

∂C

JD = −DO in surface water !!!

∂x

DO is molecular diffusion coefficient [L2/T]

DIFFUSIVE FLUX

∂C ∂C

JD = − τ DO n = −D*n

∂x ∂x

τ = tortuosity factor

D* = effective diffusion coefficient

TORTUOSITY

pores and around solid grains

2

⎛L ⎞

Common empirical expression: τ = ⎜⎜ ⎟⎟

⎝ Le ⎠

L = straight-line distance

Le = actual (effective) path

NOTES ON DIFFUSION

water flow – dispersion dominates diffusion

vapor transport in unsaturated zone

MECHANICAL DISPERSION

C

B

C

B

A A

MECHANICAL DISPERSION

times A, B, and C can be predicted

apparent spreading of contaminant about the

mean

MECHANICAL DISPERSION

same relationship as diffusion—i.e., that flux is

proportional to concentration gradient:

∂C

JM = −DM n

∂x

Dispersion coefficient, DM = αL u

TRADITIONAL VIEW OF

HYDRODYNAMIC DISPERSION

ACTUAL OBSERVATIONS OF PLUMES

USGS Cape Cod

Research Site

http://www.csc.noaa.gov/crs/tcm/98fall_status.html

Source: U.S. Geological Survey, Cape Cod Toxic

Accessed May 14, 2004.

Substances Hydrology Research Site,

http://ma.water.usgs.gov/CapeCodToxics/location.html.

Accessed May 14, 2004.

MONITORING WELL

ARRAY

USGS MONITORING NETWORK

OBSERVED

BROMIDE PLUME –

HORIZONTAL

VIEW

Significant longitudinal

dispersion, but limited

lateral dispersion

OBSERVED BROMIDE PLUME –

VERTICAL VIEW

LONGITUDINAL

DISPERSION VS. LENGTH SCALE

Lateral and vertical dispersivity

TRANSPORT EQUATION

Combined transport from advection, diffusion, and

dispersion (in one dimension):

∂C ∂C

J = nuC − D * n − DM n

∂x ∂x

∂C

J = nuC − D H

∂x

DH = D* + DM = τ DO + αL u

= hydrodynamic dispersion

TRANSPORT EQUATION

volume (REV) of aquifer.

REV must contain enough pores to get a

meaningful representation (statistical average

or model)

TRANSPORT EQUATION

Change in

contaminant Flux in less Sources and

mass with flux out of sinks due to

time REV reactions

∂C T (1)

= −∇•J ± S/S

∂t

∂C T ∂J

= − ± S/S (2)

∂t ∂x

TRANSPORT EQUATION

CT = total mass (dissolved mass plus mass adsorbed to

solid) per unit volume

= ρb CS + n CW = ρb CS + n C (3)

Note: W subscript dropped for convenience and for

Consistency with conventional notation

∂ (ρbCS ) ∂ (nC) ∂ ⎛ ∂C ⎞ (4)

+ =− ⎜ nuC − DHn ⎟ ± S/S

∂t ∂t ∂x ⎝ ∂x ⎠

↑ no solid phase in flux term

TRANSPORT EQUATION

CS = Kd C by definition of Kd

∂C ∂C ∂ C 2

(ρbK d + n) = −nu + nDH 2 (5)

∂t ∂x ∂x

∂C u ∂C DH ∂ C

2

=− + (6)

∂t ρ

⎛ b dK + n ρ

⎞ ∂x ⎛ b d K + n ⎞ ∂x 2

⎜ ⎟ ⎜ ⎟

⎝ n ⎠ ⎝ n ⎠

TRANSPORT EQUATION

“Retardation factor”, Rd

ρbK d + n ρbK d (7)

= 1+ = Rd

n n

Substituting Equation 7 into Equation 6:

∂C u ∂ C DH ∂ C 2

(8)

=− +

∂t R d ∂x R d ∂x 2

Effect of adsorption to solids is an apparent slowing of transport

of dissolved contaminants

Both u and DH are slowed

SOLUTION OF TRANSPORT EQUATION

boundary conditions

Gaussian cloud

- x

x-a x+a

[

[

Relative Concentration C/C0 1.0

0.8

0.6

0.4

0.2

0.0

t1 t2 t0

Spreading of a solute slug with time due to diffusion. A slug of solute was

injected into the aquifer at time t with a resulting initial concentration of C0 .

0

New York: Macmillan Publishing Company, 1992.

1-D SOLUTION OF TRANSPORT EQUATION

(for example, a spill that leaves a residual in the soil),

solution is:

Co ⎛ R d x − ut ⎞

C(x, t ) = erfc⎜ ⎟

2 ⎜ 4R D t ⎟

⎝ d H ⎠

source location x = 0

Solution is a front moving with velocity u/Rd

1.0

0.9

0.84

0.8

0.7

0.6

0.50

0.4

0.3

Mean

0.2

0.16

0.1

0.0 x

+s s

x = ut/Rd

New York: Macmillan Publishing Company, 1992.

Moving front of contaminant from constant source

10

9 C0 = 10

u=1

8 DH = 0.1

Rd = 1

Concentration, C(x,t)

7

t=1 t=3 t=5

6 ut = 1 ut = 3 ut = 5

5

0

0 1 2 3 4 5 6 7 8 9

Distance, x

Moving front of contaminant from constant source

Effect of dispersion coefficient

Effect of Rd on moving front of contaminant

Effect of retardation

10

9 C0 = 10

t=3 t=3 u=1

8 ut = 3 ut = 3 DH = 0.1

Rd = 2 Rd = 1

Concentration, C(x,t)

0

0 1 2 3 4 5 6 7 8 9

Distance, x

1-D SOLUTIONS

Continuous Input of Mass Per .

Continuous Input of Mass Per

Unit Time M Starting at Time t = 0 Unit Time M in Steady State

.

[ [ ( (

.

2

1-D C= M exp - (x-vt) C = M erfc

x-vt

C= M ( for x > 0 (

. 1/2 1/2

2np t D x 4Dxt 2nv 2 Dx t nv

M, M are instantaneous

or continuous plane

sources x=0 v x=0 v x=0 v

M

M to ∞

L2

t=0 t = t1

.

M

M 2 Mass Front at Mass

L T

input here time t input here

Adapted from: Hemond, H. F. and E. J. Fechner-Levy. Chemical Fate and Transport in the Environment.

2nd ed. San Diego: Academic Press, 2000.

2-D SOLUTIONS

Continuous . of Mass Per

Continuous Input

Unit Time M Starting at Time t = 0 Unit Time M in Steady State

. 2-D

M, M are instantaneous

or continuous line

C= M exp

4np t Dx Dy [

(x-vt)2 y2

+

4Dx t 4Dy t [ C= M

.

4np 1/2 (vr)1/2 Dy [ [ ( (

exp (x-r)v erfc r-vt

2D x 2 Dx t

C=

1/2

2np (vr)

.

M

1/2

Dy [ [

exp (x-r)v

2D x

sources

M [[

M

L t=0

y

t =

v

t1

y

v

Plume at time t

y

v

.

[ [

M x x to ∞

M x

L-T

Adapted from: Hemond, H. F. and E. J. Fechner-Levy. Chemical Fate and Transport in the Environment.

2nd ed. San Diego: Academic Press, 2000.

3-D SOLUTIONS

Transport of a Conservative Substance from Pulse and Continuous Sources

Continuous . of Mass Per

Continuous Input

Unit Time M Starting at Time t = 0 Unit Time M in Steady State

. 3-D

M, M are instantaneous

C=

8np 3/2 3/2

t

M

Dx Dy D z

C=

.

M

8np r DyD z [ [ ( (

exp (x-r)v erfc r-vt

2D x 2 Dx t

C= M

.

4np r DyD z [ [

exp (x-r)v

2D x

[ [

or continuous point (x-vt)2 y2 z2

sources exp - + +

4Dx t 4Dy t 4Dz t

M [[

M

L

v z y z y v

. v

[ [

M z y

M

T

x

to ∞

t=0 t = t1 Plume at time t

Adapted from: Hemond, H. F. and E. J. Fechner-Levy. Chemical Fate and Transport in the Environment.

2nd ed. San Diego: Academic Press, 2000.

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